the preparation and x-ray c~ystallographic ......kahli 1 gibran • the author gratefully acknm...
TRANSCRIPT
THE PREPARATION AND X-RAY C~YSTALLOGRAPHIC STUDY OF
SEVERAL ION-EXCHANGED, COMPLEXED SYNTHETIC ZEOLITES
A SENIOR HONORS THESIS SUBMITTED TO THE FACULTY
OF THE DEPARTMENT OF CHEMISTRY OF THE
UNIVERSITY OF HAWAI I IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
BACHELOR OF ARTS
WITH HONORS
MAY 1973
BY
KEVIN BENEDICT KUNZ
"
iii
If he (the teacher) is indeed vdse
he does not bid you enter the house
of his wisdom, but rather leads you
to the threshold of your own mind.
Kahli 1 Gibran
•
The author gratefully acknmoJ1edges his advisor, Dr. Karl Seff.
His supervision has made this research a unique and rev/arding
experience.
I am also indebted to Allen Amaro, Dr.Roger Cramer, Cathryn
Kovaciny, Paul Riley, and Russell Yanagida for their assis
tance, and to L.LoY.Chun and J.Niwa for the synthesis of some
of the zeal ite A used in this work.
iv
/.l.BSTr~ACT
Zeo 1 it i cion -exchange e;~pe r i fllent S 'de re Co rr i ed out us i ng J\u+3
+2 C +2 C +3 C +2 Cu+ 2 , Ag , a , r , 0 , -!-2 • +2 - +2 Fe ) hn and Zn solutions. Five
ion-exchanged samples of the synthetic zeolite A, Na12A1 125i 12048'
were exchanged stoichiometrically. They are;
CU2NaSAl125i12048
Ca2Na8A112Si12048
( 1 )
(2)
C0 4Na4A 1125 i 12048 (3)
Mn4.sNa3Al12Si12048 (4)
and ZnSNa2All25i12048 (S).
The selenium and tellurium sorption complexes of zeolite A, zeo-
1 i te (2), and zeo 1 i te (3) \-'Jere a 1 so prepared.
The crystal and molecular structure of the selenium sorption com-
plex of (2), Se8Ca2NaaAl12Sil204S·XH20, and the hydrated form of (5),
ZnSNazA112Si 1204S·29H20, were studied by X-ray diffraction techniques.
The selenium sorption complex was found to be crystallographically
disordered.
A successful structure determination was achieved for the hydrated
zinc-exchanged zeolite, and was refined to Rl and R2 error indices of
0.097 and 0.092, respectively.
The methods used for ion-exchange, zeol ite complexation, and crystal-
lographic investigation are discussed. The molecular geometries for the
hydrated zinc-exchanged zeol ite are presented.
T P.BLE OF CCH\TENTS
ABSlRll,CT .
LIST OF T I~BLES
LIST OF ILLUSTRATIONS
I. INTRODUCTION
A. r.AT I ONALE •
B. THE BIOLOGICAL ELEMENTS
C. ZEOLITES
D. OBJECTIVE OF THIS WORK
II. X-RAY CRYSTALLOGRAPHY 0
Ao APPLICATION TO THIS RESEARCH
Bo HISTORICAL DEVELOPMENT
Co THEORY.
D. EQU I Pl1ENT AND METHODS 0
II r. EXPERIHENTAL PREPARATIONS
A. ZEOLITE SYNTHESIS
B 0 ION EXCHANGE •
Co SORPTION
IV. EXPERIMENTAL CRY~TALLOGRAPHIC METHODS USED I N THE STRUCTURE DETERt'il NAT I OilS OF SesCa2NaS(A) 'XH20 and Zn5Na2(A) ·29H20 0
V. THE ATTEMPTED STRUCTURE DETERMINATION OF SeSCa2Na3(A) 'XH20
Ao STRUCTURE REFINEMENT
80 DISCUSSION
Page
iv
vi i
vii i
2
4
7
8
8
9
10
1'3
17
17
18
23
32
35
35
37
vi
A. STRUCTURE REFiNEME~T
80 DISCUSSION
VI I. SUGGESTIONS Foa FURTHER WORK.
Appendix A
,l\,ppend i x B
Appendix C
Brbliography •
55
55
56
67
68
72
79
81
vi i
LIST OF TASLES
TABLE
1. Pe<':lk pas i t ions from the Se3Ca2Nag ('0,) • XH:O Fourier maps •
2. Interpeak distances in the SegCa2Na 8(A) 'XH 20 Fourier maps 0
3.-20. Outout parameters for SeoCa2Nas(A) 'XH20 trial structure refinements
21.-32. Outout parameters for ZncNa2(A) "29H20 • 1 f") trIa structure re Inements • • • •
33" Molecular geometry in Zn5Na2(A) .29H20
34. Interatomic distances in Zn5Na2(A) "29H20
39
40
60 - 65 <
58
59
vi i i
LIST OF ILLUSTRATIONS
FIGURE Page
1. The unit cell of zeolite A • 6
2. Two and three dimensional X-ray diffraction 11
3. Atomic planes within a unit cell. 12
Lf. The ion exchange solution flovl apparatus. 21
5. The dehydration-sorption ~acuum system 25
6. Modified glass sample tubes 27
7. The single crystal vacuum system. 31
8.-12. Electron density in the large cavity of SeSCa2NaS (A) • XH20 41 - 45
13. Zinc and H20 peaks on the Zn5N~2(A) '29H20 Fourier map 57
14. XORTEP computer plotter drawing of ZnSNa2(A) "29H20. 66
The eternal mystery of nature is its comprehensiono
Albert Einstein
I • 11~TRGDUCT ION
A. Rat i ona 1 e
The rationale behind intricate and sophisticated chemical research
often eludes the layman and the scientist alike. It is of value, there-
fore, that the relevancy of this present endeavor be offered at the on-
set.
_All research, but particularly novel chemical, biochemical, and
• physiochernical research, is hampered by the inability of many methods of
experimentation to confine a problem within a closed, tightly controllable
system. It is unknown or spontaneous variables which often are responsible
for extending or perplexing any specific inquiry. In most cases, adequate,
eve nap p 1 i cab 1 e, un d e r s tan din g s vii 1 1 no t bee n t ire 1 y sat i s fa c tor y u 11 til
they account for the primary operational basis of the system to which the
scientist directs his investigations.
There is perhaps no better example of this ~han in human biology.
Early medical science could identify only blood, bone, and flesh. Later
the organs were recognized and identified. Eventually a cellul~r theory
of life was conceived. All of this knowledge was magnificently insufficent,
hO'tJever, in explaining and in coping \-oJith disease. Nor did it offer much
aid in explaining or propagating health. It was, relatively, only recently
that research restricted to l!l._y)tro, clos81y ::ontrol1able, biochemical sys-
tems was able to yield suitable explainations for disease or he<Jlth symptoms
which are, primarily, chemical in origin. The universal use of medicinel
drugs bears testimony to the re<Ji ity of a concept of life based on chem-
ical foundations. It is dist!'2ssful1y app.Jrent} n:)verthele:.~<;~ that the
extent of this ch(~rnical knov'/ledge is neither deep nor broad enough.
Unfortunately, there have been no witnesses to 1 ifcs chemical con-
struction and eV01ution, and we have thus been denied a cornplete under
standing of the mechanisms by which we function. Hence, present day re
searchers must assume the role of archaeologists in reconstructing the
molecular basis of life. 1 ,2,3
It is doubtful whether many scientists apply themselves, individually,
to the task of comprehending life. More likely, they restrict their work
to realistic, less complex, more controllable facets of nature. In such a
manner the research presented here has been confined to control l~ble sys
tems, so that a submicroscopic basis for the understanding of the macro
scopic, physiochemical parameters, properties, and interactions within
these systems may be gained.
B. The Biological Elements
It has been established that at least 24 ~f the 90 naturally occurring
chemical elements are essential to all living organisms. 4 These elements in
clude manganese, iron, cobalt) copper, zinc and the monoatomic cations of
sodium and calcium. The former five elements are all transition metals
which life requires only in trace amounts. Because of their readily var
iable oxidation states and their abil ity to form strong complexes with li
gands, these elements act as catalysts in organic and inorganic reactions.
In living organisms these trace elements often occupy allosteric sites
in enzymatic metal1oproteins. Manganese is found in Arginas~J responsible
for urea formation, and Pyruvate Carboxylase, an enzyme of pryuvate metabol
ism. Zinc is found in Carbonic Anhydrase, Carboxypeptidase and Alcohol De-
3
hydrogenase, resp3ctively responsible for r2gul~tion of body acidity,
protein digestion and alcohol metabolism. Cobalt app(:;urs in enzymes in-
valved in the biosynthesis of DNA and in amino acid netabol ism. Elasticity
of aortic walls and skin pigmentation are included in the range of functions
of the copper containing enzymes. Lastly, iron is a required component of
the well studied proteins hemoglobin, which facil itates oxygen transport,
and Succinate Dehydrogenase, a key enzyme in the aerobic oxidation of carbo-
hydrates. The existence of interactions between these trace elements and
molecular entities within living systems is thus not in doubt.
In the inorganic state, these elements appear in many minerals, exist
in continental deposits, and may be found in many forms in the oceans and on
the ocean floors.
Industrial ly, man has taken advantage of their catalytic properties to
commercially produce life supporting substances. The use of transition metal
complexes by the petroleum industry in catalytical ly producing energy rich
hydrocarbons,S attests to the significance which these elements possess in
the support of our species.
+ ++ . h + ++ -The monoatom i c cat ions Na and Ca , t oget he r \'J It K, t~g ,and C 1 ,
are also critical to a number of functions within living organisms. They
help maintain electrical neutrality of cells and fluids, playa part in
maintaining the proper liquid balance of the blood and other fluid systems,
and are critical to the proper functioning of the cell membrane in control-
ling electrochemical balances, osmotic pressure differentials, and transport
of molecules into, and out of, the cell.
Much attention and investigation has been focused on the aforementioned
elements and processes. The abil ity to create authentically modeled, yet sim-
ple, systems which may elucidate characteristics and properties of any com-
it
ponent of these processes, has been the ke.y to their successful research.
The present research is directed at a deepar understanding of several
of these essential elements. In their ionic form these elernents, exchanged
into rigid crystal1 ine, open anionic framework structures, can be expected
to display unusual coordination and to exhibit unusual chemical properties.
Further, in zeolitic framev,forks, the ions may have coordination sites which
are not occupied and not blocked, but rather entirely vacant and available
for further complexation. Substrate or ligand species may then be intro
duced into the zeolite cavities. The subsequent cryatallographic study of
the exchanged ion - sorbed species interactions may provide insight to the
role of the particular ions in biological processes. Additionally, the study
of these intrazeolitic complexes is relevant to petrochemical catalysis.
C. Zeo1 ites
The use of zeolites in this work requires that they be briefly dis
cussed.
Natuarally occurring zeolites have been known since the 18th century,
when the Swedish mineralogist Baron Cronstedt 6 , observing that these min
erals intumesce when heated, gave them their name from the Greek ~, mean
ing to boil, and lLthos, meaning stone. Since then mineralogists have
classified over 50 types of zeolites, each with its own crystal structure.
Zeolites are a class of aluminosil icates characterized by a network of
Si04 and A104 tetrahedra. The Si/Al ratio varies upward from unity depend
ing on the zeolite type. The aluminosil icate framework is anionic and
achieves neutrality through the inclusion of exchangable cations. The
arrangement of the Si04 and A104 tetrahedra gives rise to channels and
cavities within the zeolite. It is into such spaces that small molecules
can be sorbed and interact vJith tl!0~ cal:ions. It has been hypothesizc:d
that natural zeolites could have been involved in the abiotic events lead-
ing to the origin of life.?
Zeolites have only in the past few decade~ been synthesized in the lab-
oratory. This synthesis, initially achieved by DeW.Breck at tile Linde Company,S
~ • 1 d . 1 . 9 fluS stlmu ate extensive research into their use as rna ecular sieves. In
this capacity their most well knovm use is in the softening of "hard \AJater"
+ ++ +-1-by exchanging Na for various divalent cations, such as Ca and Mg I
Zeolites are utilized in industry to'purify products by the removal of trace
pollutants and to perform separations by the selective sorption of smaller
or more polar molecules. 10 A significant example of their pollutant removal
capacity is in their recovery and purification of radioactive cesium-13? from
nuclear power -sources. l1 Zeol ites are also extensively used as catalysts in
hydrocarbon rearrangements. When dehydrated, zeolites become the most effect-
ive desiccators known, and have been employed in high vacuum systems and in
12 1314 the biological dehydration and degradation of cell organelles. " Num-
erous other uses of zeolites, including those in this research, stem from
their distinctive properties of high capacity ion exchange, strong and sel-
ective sorption at low sorbate concentrations, and specific catalysis.
The structure of the first synthetic zeol ite, type A: Na12A1 12Si 12048'
was determined by Reed and Breck l 5 in 1956 and further refined by Brous
sard and Shoemaker l6 in 1960.
The structure of type ft., a unit cell of which is shown on the next page,
Ciln be described as an assemblage of sodalite 17 cages, 6.6A in diameter, each
.. f 1'+ 1+' b 'd d b .-consisting 0 2~ SI or A Ions rl ge y 3b oxygen atoms. The sodu 1 it e
units are, in type A, arranged in a primitive cubic array linked together
by .12 add j tiona I oxygen atoms. At the center of each cube of soda 1 i te un j t 5,
a large cavity, 11 .4A in diameter, is formed. In the middle of each square
... :V
, I
Ilt.K'\'D'tRTED ZEIl.. \TE ~
-------~.-
.'
large cavity
, .. \ I.'
B.
6
0(1) 0(2)
eight-window
'.
. '.
O(HYOfIATED ZEOL ITt IIR
Figure 1. The unit cell of zeolite A. A. The Gramlich and Meier conception B. Dehydrated stereoview c. Large dehydrated plotter picture
'. 'f
! ..
~; '.' I l' '.
.: ,'," :.~ .~. .~ .,', .
I. " " .~ .. ~ .' .:
: I ',.: .
c.
:"'. .'
. i ... : : \ , ... ,
,r, 1,". • . •
• I ':,' . .' ~
., ",' •• !.' • ,", ~ • -. l
. ','<:, :," ,; ., 1
, ,~;' ," '., <. ,I ••
~- . .' ' .. ~
~ 0/. ..' . • i· .
7
face a 16-mernber ring is formed consisting of 8 oxygen, 4 5i 1 icon, and
4 aluminum ions in the sequence ... Al-0-Si-0-fl-0-Si.
Prior to 1972, nearly all of the knowledge of sorption and cat~lytic
sites in zeol ites was obtained throu9h infrared spectroscopy,18,19,20 NMR
h • 21 d h • h d tee nlques, an ot er 5pectroscopiC met. 0 s. It was through these methods
that bonding involving the sorbant molecules was first discussed.
In the 19605 the crystallographic study of stoichiometrically ex-
h d . 1 fl' .. d f f . d 22 ,73 c ange sorpt Ion comp exes 0 zeo I te A \flas in I t I ate by Se an Shoernaket".
Since that time many more vvorkers have prepared var i ous 1 y i on-exchanged and
complexed zeolites. Only a few of these have been investigated crystallo-
graphically.
D. The Objective of This Work
The immediate goal of this research is to prepare variously ion-exchanged
zeolites, to experiment in complexing these with elements or small molecules,
and to examine certain of these prepared novel complexes by the methods of
X-ray crystallography.
('
\
, \
I I • X -RP.Y Cf; Y~T Pill. OGf{APHY
A. /\pplication To This Research
The ultimate objective of the research upon which this thesis is pre-
sented, is to provide a sUb-microscopic basis for the understanding of the
macroscopic physical and chemical properties of v~rious cation exchanged or
complexed zeol ites. In particular, the determination of the C2rtesian co-
ordinates of the atoms in sorbed molecules and exchanged ions within the known,
but somewhat flexible, zeal ite framework, adds not only to the present under-
standing of the forces responsible for sorption and catalytic activity, but
often lends insight into the chemistry of interaction between the exchanged
and sorbed species. It is the unambiguous determination of the atomic posi-
tions within the unit cell of the variously ion-exchanged and complexed zeo-
1 ite crystals which allows us to progress in our comprehension of these sys-
terns.
Many methods exist by which chemists are enabled to postulate structural
molecular models. In many cases the employment of such methods as nuclear mag-
netic resonance, electron spin resonance, visible, infrared, ultraviolet, or
microwave spectroscopy, is able to yield characteristic information about the
investigated molecules, but in no case do these methods yield precise atomic
positions in three-dimensional space.
Crystallography is the only technique capable of definitive molecular
structure determination. The employment of X-ray crystallography commonly
provides atomic resolutions greater than one hundredth of an angstrom, and
consequently remains unparal le1 led by any non-diffraction technique. 24
B. Historical Devclop~ent
The intrique of crystal J ine materials has held tIle attention of natur-
1 i sts for many centuries. The \-vlord crystal is derived from the Greek lsJ::i
.?J...Pllc;;s2~ \!ihich means, 1 iteral1y, frozen ice. The Greeks used this term for
the mineral quartz, which they bel ieved to be frozen water.
It is interesting that this belief was maintained until medieval times.
As the science of mineralogy developed, the ':frozen ice" hypothesis vanished
and the study of many natural crystals strengthened the evidence which postu-
lated that the external appearance of crystalline matter \A/as indicative of .in-•
ternal order and composition.
Late in the seventeenth century the French abbot Rene' Just Hauy began to
collect and investigate crystals as a hobby. Although HaGy began his scientific
career relatively late - he was thirty - he soon became the foremost authority
in the fields of crystal study and mineralogy. During the course of his invest-
igations, Ha~y once dropped, accidently, a crystal of calcite. He noted that all
of the broken pieces resembled each other, and the larger crystal, in external
shape. He continued to break the small pieces a~d found that section after
section could be removed until all of the pieces were geometrically identical
rhombohedra. Ha~yfs findings led to the concept of a crystal as a macroscopic
sample of a solid substance composed of building blocks - atoms or molecules -
\vhich are orientated to each other in an orderly, symmetrical, periodic manner
in three dimensions. Hauy is credited with over 100 crystallographic publ ica-
26 tions. His Treatise on Crystallography, a classic, was publ ishcd in 1322, the
year of his death.
27 X-rays ItJere accide'ltly discovered in 1895 by Hilhelm Conrad Roentgen, 'IJho
so named them because he was uncertain of thdir nature. These rays, which are
also called roentgen rays, have since been found to constitute a portion of the
10
r CJ d i at i OilS ,II 0 tun 1 ike vis j b 1 eli 9 h t i If Ii () l u r c ) but of a shorter \.J a vel en 9 t h ( 1 0 .. 7
tOo 10-11 ) cm •• T1I(;y are emitted from 2t():ns due to spontaneous or c.:rt ificiLllly
produced energy transitions vdthin 0toinic electro:l slwl1s. Experimentally, and
comercially, X-rays are produced by Gombarding a metall lc target with a beam of
higll velocity electrons.
28 Max von Laue of Germany, a copatriot of Roetgen, suggested in 1912 that
crystalline sol ids might be employed as diffraction gratings for X-rays, since
X-ray wavelengths are similiar to the intramolecular distances in crystals. If
such a diffraction could be experimentally obtained, then crystallography could
expand to include the quantitative study of int~·nal crstalline order and estab-
lish precise molecular geometries. Laue's hypothesis was confirmed the same year
b . d . h d . . 29 h bl b'· f . y Frle rIc an KnlpPlng, w 0 were a e to 0 taln dlf ractlon patterns photo-
graphically. The successful structure deterrninCltions of NaCl and KCl in 1913 by
W.CoBragg,3 0 the construction of the first X-ra~ spectrometer by Gragg's father,
and the applicability of Bragg's LcM, which predicts X-ray scattering) established
X-ray crystallography as a sc~ence which has since become fundamental to mole-
cular reseurch.
c. Theory
Max von Laue formulated a unique, yet compl icated, mathematical explain-
ation of X-ray diffraction by crystals. HO'd8ver, it is \tLCoBragg's treatment
of the phenomenon, ins i mp 1 e geomet ric terms, vlh j ch has proved i ndespens i b 1 e
to an understanding of the diffraction concept.
Sin c c the at 0 m S 0 r mo 1 e c u 1 e s) 0 f \'1 h i c h cry s t 2 1 s are corn p 0 sed) are c:l r ran 9 e d
in a three dir:18nsional, orderly, periodic pattern, dnd since the distances be·'
tvlcen the atomic plCJnes approximate the \'/avelei1gth~) of X-rays, cr~lstals act as
\,'" ':\
1 1
t h r e c - d i nK.~ n s ion 2J 1 9 rat i n 9 5 i nth e ira b i 1 i t Y t 0 d i f t r 2 C t X .. r Z:l y S . T h t:; fi1 ~.t1 t i .<
dimensional diffraction \!Jnich crystals produce is analo~1ouS to the diffraction
of visible light by two dimensional gratings. Indeed, the younger Dragg once
remarked that the principles of optical physics were prerequisite in the con
ception of his law. 31 Bragg's Law· treats X-rays as if they arc reflected by
the atomic planes within a crystal. In his own words:
IIWhen a beam of monochromatic X-rays strikes a crystal J
wavelets scattered by the atoms in each sheet combine to form a reflected wave. If the path difference for waves reflected by successive sheets is a whole number of wavelengths, the wave trains will combine to produce a strong reflected beam. '1 (3l)
Bragg1s Law is the geometrical equation; nA= 2d sinee ( I)
Figure 1. A. two dimensional diffraction. B. three dimensioal diffraction.
Th~ perpendicular distance between reflecting planes is dhki ' and e is
the glancing angle of the incident X-ray beam. The path difference of waves
reflected by the pl~nes is 24 sine ~. Hence, there is only one angle e ,
when A and~h\<Q.are fixed, for \tJhich the reflected Idaves VJi 11 be in phase. At
any other angle . there will be destructive interference and no reflection will
be observed. There are a large number of atoms and these atoms may be of
different types, consequently many different planes may be chosen, and for
each layer of planes a different incident angleG will be necessary to pro-
duee a reflection.
12
are
designated. These indices do not provide ~ny physical me2surement of the
pl';!n0s, but only define tncdr orion tation in space. Several visu~dizations
of such plane~ are presented in Figure 2.
:1
I, Ii I' ~ rt;;;V'
R ,.~~ ~:~
h~k. .e.~ Figure 2. Atomic planes within a unit cell.
The intensit'y,lhkQ ' of a diffracted wave and its ,phase - its time of
arrival at the detecting device relative to other diffracted waves - is de-
termined by the arrangement of the atoms vlithin the unit cell ( as opposed to
the angle of reflection being determined by the distance between atomic planes
of adjacent unit cel 15). The constructive-destructive interferences which exist
within each set of diffracted waves also effects the observed intensities.
Theoretically, the solution to any crystal structure may be achieved from
angle, intensity and phase of the reflected beam. Unfortunately, it is im-
possible to measure the phase of the diffracted radiation by any means. At
present, film and scintil lation detectors are utilized in recording the angle
and intensity information of the diffracted beam. These are "square 1 aitJ 1 I de-
tectors and hence {hke' which includes both the ampl itude and ph~se of the beam,
cannot be directly establ ished. Nevertheless, we can obtain through these
detectors a -comple~ factor, Fhkl ' which can be related to the diffraction
2 intensity; Ihkf(a:Fhk~ . Fhk~ is called the structure factor. The phase
13
of the reflection is lost when I~, II is squDred. Hence, bevond o:.W d(~terrclinati()n, o11~,J;' ,
any diffracted v/ave may be from OOto 130C
nut of phase vJith any other. In X'~ray
crystallography this uncert~inty is known as the phase problem, and is the most
formidable obsbacle in any structure determination.
In consideration of all that has been mentioned, there exist a function
which relates the obtainable data of diffraction with the electron density (~)
at any atomic positiort x, y, z within the unit cell. It is;
+~ 1 ~~"'et [
f (x,y,z)=-V ",~l,. Fhk exp(-2rri(hx+ky+iz)' ~~( ~
The yet unexplained cornpone~n ar~ V, which is the unit cell volume,
( II)
and i, vJhich is simplyf=\ . The atomic pos!tions of the crystallized molecules
under investigation may be attained thru function(1 f) by the crystallographer,
aided by the employment of the equipment and methods described in t~e remainder
of this chapter:
D. Equipment And Methods
The Bragg X-ray spectrometer, used with an ionization chamber, was tile first
device utilized to collect data on the intensity of X-ray reflections. The de~
velopment of X-ray photographic films soon replaced this method. In fact,
until the last decade, intensity data vJas collected almost entirely by fiILl
methods.
These methods were never especial Iy precise since the recorded intensities
usually had to be measured visually. Processing of the films, scal ing the data
and camera maintenance were tedious and time consuming chores. The percentage
of accuracy which was lost through the eQuipment and humQn error rarely al lowed
rel iablc determination of thermal motion or precise bond lengths. Nevertheless,
the multitude and importance of the structures which were correctly determined
by these methods remains a tribute to the crystal loYfephers working in the first
half of this century.
In the 19505 the development of auto;~latcd diffractomcters led to v:hat one
1? aut h 0 rca 1 1 e d a 'I rev 0 1 uti 0 n inc r '/ s tal log r a r h y' I • - ~. The sed iff rae tome t e r 5
mimiccd the geometry of the traditional photographic data collection systems,
but otherwise had 1 ittle in corrnon. The angles at which reflections might be
found were calculated by modular computers. Angular settings V,Jere reached by
high 1 y synchronous mot ors . I ntens it y co 11 ect i on vIas accomp 1 is hed us i ng sens i -
tive scintillation counters, similiar to Geiger counters. Data recording was
on paper tapes, punched cards, or magnetic tapes which could be directly pro-
cessed into a computer for further work in strucutre determination. The auto-•
diffractometers have decreased human error and increased experimental accuracy
and precision. Most significantly, they have contributed to the application of
crystallography in many fields which hitherto did not have the time or staff
to invest in crystallographic investigations.
A Syntex Pi four-circle, computer-controlled automated diffractometer
( hereafter referred to as the pT) wi t h graph i te-monochromat i zed Mo rad i at ion
was used for prel iminary experiments and for the col lection of diffraction
intensities for the structure determinations to be discussed shortly.
Diffractometer computer input instruction is achieved in the Pl by teletype,
paper tape, or magnetic tape. Output data utilizes these same mediums. A
pulse height analyizer and a strip chart recorder are also modular components
of the pi. The PI modular computer is a Data General Corporation NOVfi, , v"rhich
has a 4096, 16-bit word, core storage, and in a typical structure investigation
executes the necessary programs for automated crystal set up and data collection.
The first of these programs is Centerinq & Auto-lndexill9., VJhich centers up to
fifteen reflections and determines indices for these) after being suppl led \
starting input from initial Polaroid film coordinates. A !..east Squa.r.es Or-
1-••
15
i e n tSl t i 2!l...J~(l t r i x pro 9 r a in de t e r in 1 pes u nit c C! lip C1 r ti :!l'.:; t e r $ fro {;1 i n die e S d n d
2ecata and calculates angles from an ol"icn~ation matrix and indices. The
ft.utQLQjltic_D(:tJl.JoLL~.sJJ..9.rl program provides a fixed or val-iablc SC&f1 mode of
operation, records crystal X-ray exposure time, 1 ist Miller indices in any
order desired, provides a means of limiting output data recorded, and prints
out the peaks, intensities, deviations and angles of ali observed reflections.
A descriptive picture of the PT and a sample of its printed output may be
found in Appendix Ao
The methods of processing the output data from the PI rely on the acces~
sibility of high speed, high capacity digital computers. Fortunately, this
University has available an IBM360/65, which is capable of handling the volume
and complexity of the programs ~vhich are routinely used in most X-ray crystal-
lographic structure studies.
Because they have been essential to the solution ( or attempted solution)
of the structures with which this thesis is concerned, and because an explain-
ation of them concomittantly explains the method of solution, the computer
progrums employed after data collection are here briefly described. Samples
of their outputs may be found in Appendix B.
LPCOR 33 is a Fortran computer program designed to process the Pl output
tape. It selects significant reflections ( those which have an
intensity greater than three times there standard deviation) and
appl ies crystal absorption or decay correction curves to these
reflect ions if necessary. LPCOR outputs punched IBt~ cards con-
taining significant reflection indices, the reflected intensities,
and deviations.
is a simp 1 e Fort run progr<lnl ~"h i ch condenses the out put from lli_QR
by placing three reflections on each IBM card.
Fr'~LS35
16
is a Fortran program Wllich provides full-matrix least-squares rc-
finement of suitable tri~l crystal structures. It refines atomic
positional and therrnal parameters in 2.fi attcrnrt to i;iatch the cc:;l-
cu 1 ated 5 t ruct u re fCJctors \'",i t h t hose observed. FHt.;..$_ a 1 so cEil cu-
lates the error index,R,(R:::(~I£o-/.fcl)/f£o) 'vjhich is indict.1tivc
of the fit between the structure factors calculated from the trial
structure, and the observed structure factors .
. !UC-It.LJ.f..36 is a PL/l program \'ihich performs Fourier summations. This program
produces an electron density map from significant data. This map
contains peaks which may correspond to unfound atomic positions.
These positions can then be added to future trial structures.
is a Fortran program which calculates all intramolecular bonding
distances and angles from input postu1ated or known C<Jrtesian
coordinate positions within the structural model.
ORTEp38 is a Fortran program which, when suppl ied the final three-coordinate
atomic positions within a unit cell, draws on a computer plotter, two
pictures of the molecule whose structure ~s been determined. These
pictures are drawn with a 6° difference in rotationo Viewed thru ~
stereoglasses, these pictures appear as one three-dimensional mole-
c u 1 e, and allow t he ma 1 e c u 1 e t 0 be I IS e en II
A. Zeal itc Synth'2sis
The original synthetic production of zEal ites in the late 1950's was
un important brcakthrough because it made available CrJ2dtitics of zeolite
which \"ere impr.:~ctical or impossible to obtain from nature. HovJever, thsse
synthetics were either amorphous or microcrystalline, and this limited the
studies v.Jhich could be carried out on them. Precise determination of atomic
• positions by X-ray diffraction requires sing1e crystals approximately 150~m
or larger in diameter for optimum results39 . Comercial1y synthesised cry
stals range from 1 to lOrm and are thus unsuitable for this purpose40 . In
1967 a method of preparing crystals of zeolite A, with a maximum diameter of
41 ~2 lOOrrn was published By 1970 Charnell twd prepared crystals approaching
140rm in diameter, and the crystals used in this research were consequently
prepared by his method, with a modification to include a second crystall ization
using seed crystals from the first preparation. Th~se crystals are grown from
a hydrothermal gel by reacting sodium metasi licate with sodium aluminate,
using triethanolamine as a stabil izing and buffering agent. The consistency
of the crystallization yield and quality varies with temperature, reagents,
and procedure used in the preparation. An available supply of adequate zeol ite A
crystals permitted this work to proceed with the ion-exchange experiments and
sorpt ion \vork.
The sources for all chemjcals util ized may be found in Appendix All
of the analysis' were performed at Galbraith Laboratories, in Knoxvil le,Ten-
nessee.
13
B. lon-Exchange
For the following exchanges, carried out at room temperature) a ten-fold
excess of the exchang i ng ion VJ it h res pect tot he i on to be exchanged \tJas used.
Calcium
SOm). of O.lM calcium nitrate, Ca(N03)2'4H20, was placed in a flask with
0.5 grams of zeolite A. The solution was gently stirred and the zeo1ite sam-
ple was.microscopically observed, daily, for a week. The appearance of the
crystals remained unchanged during this period. On the seventh day the cry-
stals vJere filtered from solution, washed four times with distilled H20, and
allowed to dry. An analysis indicated that the sample contained 3.60% calcium ++
by weight. This corresponds to 2.01 Ca per unit cell, substantially less
than would be expected in a complete exchange.
100ml. of O.lM zinc nitrate, Zn(N03)2'XH20, was placed in a flask with
1.0 gram of zeolite A. The solution was stirred and the zeolite sample was
examined, by "microscope, daily for a week. On the third day the crystals,
which were initially very clear, had become somewhat cloudy. No further change
was noted and, on the seventh day, they were filtered from solution, washed
four times with distil led H20, and allowed to dry. An analysis indicated that ++
the sample contained 14~67% zinc by weight. This corresponds to 5.23 Zn per
unit cell, almost a total exchange. Subsequent crystallographic study43 of
these crystals confirmed this analysis.
Preliminary experiments using Linde Zeolite 1'1. pO\-Jder and Mn(C104)2'4H20 in-
19
dicated, by a fast color change( in two hours) of the white powder to clul lish
pink-brown, that an attempted Mn exchange might be feasible. Accordingly, SOml.
in two hours the crystals c:lppeared pink to the unaided eye but, \dth the excep-
tion of their slight dullness, appeared no different than untreated zeolite A
crystals under the microscope. On the second day of exchange the sample appeared
brOltln, but under the microscope they looked redish-pink. No further changes
were noted during the 6xchange period. On the seventh day ttle crystals were
filtered from solution, washed four times with distilled H20, and allowed to
dry. ft.n analysis indicated that the sample contained 10.63% Hn by vieight. This
corresponds to 4.41 Mn++ per uni t ce 11.
A second Mn exchange was performed .. It was carried out exactly as the first,
except that the crystals were not harvested for five months. There was no change
in crystal appearance after the third day. The solution was stirred daily for
the first week, and week1y for the duration of the exchange. At the end of
five months the crystals were filtered from solution, washed four times with
distilled H20, and allowed to dry. An analysis indicated 10.97% Mn by weight.
1 ++ • 1 l' f 1 ' ++ This corresponds to •. 53 Mn per unIt ce ,an Increase 0 on y 0.12 Mn after
the much longer exchange. Subsequent crystallographic study confirmed this
analysis. The structure determination of several complexes of crystals from
this batch has been comple~ed 44,45,46
Cobalt
50ml. of O.05M cobalt nitrate, Co(N03)2'XH20, was placed in a flask with
0.6 grams of zeolite A. The solution was gently stirred and zeolite samples
were observed daily by microscope, for a week. The cryst~ls appeared pink bJ
the end of a v-Jeek. They vwre al1ov;ed to e~(change for a month, at the end of
which they were filtered from solution, washed four times with distil led H20,
20
2nd all oV-Jed to dry. !t is interesting that this z801 ite s~mple) wh;ch con-
taincd larger crystals than had previously been used in cobalt cxCll~n9G47) re-
tained a pink color, as opposed to the other cobalt ze:olite com?le;.~es, \\'htch
have been brown. Crystallographic studies presently being carried out on these
++ • 1 1.[: l' 1+8 , It 9 crystals ind~cate 4~o Co per unIt ce o. zeo Ite .
50ml. of 0.5M ferous sulfate, FeS04"7H20, was placed in a flask with 0.5
grams of zeal ite A. After one day the zeolite and solution became a rust rust
color. The zeol ite appeared to be destroyed. Because no measure of success
h d . 1 b . d' Fe++ h 50 I' t d a prevIous y een attalne In exe ange ,tllS exc~ange was not pursue,
SO t hat more product i ve "'Jork cou 1 d be cont i nued"
100ml. of 0.002M gold cloride, AuC1 3"HCl '3H 20, was placed in a flask with
0.5 grams of zeol ite A. The solution was freshened every day for three days.
Although most crystals initially became pale yel1ov1, some turned purple, and
the gold soultion became purple, by the end of a week. This color, called
Purple of Cassius51 is indica~ive of finely divided gold, suggesting that other
processes were taking place besides ionic exchange. At the time of this writi~,
gold exchange is still being investigated. It has been observed that although
aggregates of the crystals appear purple, single crystals in solution are yellow-
gold.
Previous work has investigated the exchange of other ionic species into
the zeolite52 ,S3. This work has shown that some cations destroy the zeolite
framevJOrk, rnak i ng t he exchange \'Jort h 1 ess" To remedy t his, a so 1 ut jon flow
apparatus using low cation solution concentrations was employed ( see figure 4 ).
The flmv of solution passing through the zeol ite, contained in a 25ml. sintered
21
'() IIU'<=.
solu -1-'0"1
,
Figure 4. Solution flow apparatus.
•
2" 1-
filt(--:r, could be controlled by a stopcock. A frc:;h solution could be cOlltin-
ual1y in contact v;ith the zecdite S<3i:-,ple, preventing the exchanged ions from
remaining in solution ~nd hindering equil ibrium. Experimentation using pro-
gressively lower concentrations of solutions proved to be helpful in presErving
the zeol ite structure ( by vi ~ual inspect ion) .
The following exchanges were performed using this technique.
Copper
Four 1 iters of 0.001 cupric nitrate, Cu(N03)2 '3H20, v.,tere al1m·.;ed to flo""
through the filter containing 0.5 grams of zeol ite A. The zeolite was then re-
moved from the apparatus, washed four times with distilled H20, and allowed to
- dry. An analysis indicated 5.52% Cu by weight. This corresponds to approximate
ly 2 Cu++ per unit cell. This is far from the maximum possible exchange, and
work is currently in progress to achieve a more complete exchange. It is sig~
nificant, how2ver, that the zeol ite sample was in no way destroyed.
S i 1 vcr
Five liters of 0.0051'1 silver nitrate, AgN03' \-vere allowed to flovl through
the filter containing 0.5 grams of zeolite A. The zeolite ~'Jas then removed from
the apparatus, washed four times with distilled H20, and allowed to dry. The
crystals were dark, and after exposure to room temperature, atmosphere and
the distilled H20, the crystals became black. It is possible that this was
the result of some photochemical effect. No analysis was obtained, and there
is presently more work with lower concentrations of silver nitrate solution
being completed.
Chromium
Four 1 iters of 0.00511 chromic nitrate, Cr(NO )3·9H20, were al10ltJed to 3
flow through the filter containing 0.5 grams of zeolite A. The zeolite sample
was then removed from the apparatus, washed four times with distilled H2
0, and
23
allo~'jed to dry. The cryst;:;ls DpP'.3DrC;d to be: destroY;Jd. They \'n~re green-blue
in color. \!ork at lOl-"/er concentrations is being continued.
C.Sorpticn
1) el n ,..·"",J.· al I - ~:,;.\ IL.:: I I L
Elemental sorption experiments \tIere carried out using selenium and telur-
ium. These elements were chosen because they are not only of sona biological
importanee54 , but as semimetal lie elements, are known to exhibit a range of un-
usua 1 elect rica 1 propert i es. Se 1 en i uril is photovo 1 ta i c and photoconduct i ve.
It is used in photo cells, exposure meters, solar cells and rectifiers. Tel-
lurium possesses many of the same properties of selenium. These elements have
found use in many electronic and sol id state appl ications) includin0 xerography.
Previous work has been undertaken with telluriuM loaded zeol ites S5 , ,but this
study did not employ zeol ite A. The sorption of sulfur into zenl ito A and the
crystallographic study of the cOli1plex has also been completed.56 .. iccause 5e1-
enium and tellurium are also Group VI elements, it could be expected that there
zeolite A complexes might offer interesting comparisons and perhaps similiarly
unique characteristics.
Selenium
The adsorption of selenium onto zeol ite A, calcium exchanged zeal ite A ( re-
ferred to as zeol ite SA ), and cu:_):..:lt exchanged zeol ite A ( referred to as that),
was performed simultaneously. Approximately 50 mg. of the particular zeal ite
sample was placed in a glass tube, 12 mm in diameter. A calculated amount of
selenium powder, cprrcsponding to 24 atoms per unit cell of zeolite, was placed
in the glass tubes. The individual tubes wc~re marked for high- tCi;1perE;turc ident-
ification. The tubes cont2inj:-,g the sa,;lples t'Jere th;·~n attuched to a vacuum sys~
tern c0uipped with a Mercury diffusion pump, and a low-teMperature gas trap. A
ur~Iion. Unfortu~~tely, the 5yste~ was not equipped with ~ McLeod guage to
neasure the vacuu:y: precisely. f\ftcr the sys<te;!lls i:::)1 vacuu::l pUfnp \\'05 Opf:t.:~~ting for
5 i x h 0 u r s, the: 1'121" cur y p U 1',1 P 'if Cl stu r n ... don. Fro m the 5 tar t, the 0 v (> n tern p c; r .3 t U r e
VJas al lowed to gradually incrense over
reached. The samples v.'ere kspt at this temperature) \<Jith not more than a 15~
variation, for another twentyfour hours. It was hoped that this procedure would
permit dehydration of the zeol ite and sorpti()n of ths selenium.
It was noted prior to the end of the final twentyfour hour period, that the
insides of tile tubes above the top of the oven, had accumulated gray and orange
deposits. These colors are characteristic of seleniu~ in the amorphous state, in-
dicating that, as expected, the selenium vaporized at the oven temperature and 501-
idified upon cool ing as it vcporized past the oven.
When the vacuum system was shut down and the oven taken off) it was observed
that the system's low temperatur~ gas trap was sl ightly glazed with shiny balck
and silvery red deposits. This indicated that more selenium, in the gasous state.
had left the sample tubas in addition to that previously noted. At this time the
possibil ity that enough selenium was lost so as not to achieve maximum sorption,
was contemplated. The samples were sealed off from the vacuum line using a natural-
gas-oxygen torch. The vacuum was not lost.
The following observations were made of the samples in the sealed off vials.
selenium-zeolite A sample;
appeared to the unaided eye, to be white in color, and under the microscope
looked to be empty zeal ite A.
selenium-zeal ite SA;
to the eye vvas dark yel1ovJ, and under the microscope the crystals looked
candy yellow. They n:aintained their crystallinity and did not in any \':2Y
seem adversely affected ~y the sorption procedure.
·,
\ K),)
Figure 5. Dehydration ~ ~orption vacuum system
Hercury
. Diffusion
Fore
Pump
2!. u
selenium- cobalt exchanged zeol ite A;
looked dark blue-black to the unaided eye. Unrler /the microscope the
crystals looked 1 ike charcoal 0ith small blue pepplcs thrown about. The
The vial contaird'lg this sample \HiS accidern:l'/ dropped, [:ind it'::. invest·'
i gat ion vIas at th is po i nt ten,li nated. FrOiO the i nrorr.lat i on recorded, it
is ,postulated that the cobalt exchanged crystals \lJore destroyed.
After these observ3tions were made the sample vials of selenium zeol ite A
and selenium ze01 lte 5fJ, "Jere placed in a rnuffle fUrnDtlCe. The ter:iperature VJ<JS
e again increased to 350Cover a twentyfour hour period. After two additional days
at this temperature, the vials were removed and the fol lowing observations were
made.
selenium - zeo1 ite A sample;
initially tan upon removal from the oven, becoming 1 ight yellow after a
few minutes upon cool fng.
selenium - zeolite SA;
initially iron red upon removal from the oven, becoming dark orange
upon cooling.
The color changes of both samples suggested that more selenium entered
the zeol ite than had under the previous conditions. The color change thus
suggested that more selenium could be sorpted.
The selenium-zeal ite A"vial contained a surplus of selenium, but little
selenium remained in the selenium-zeolite SA vial. Accordingly, the later
was broken open, and the contents plus 70 mg. nf additional selen1um were
placed in a nevJ, modified glass tube figure 6). The modification consisted
of an expansion in the upper portion of the tuLe to allow a condensation of
selenium vapor. Prior to seal off, the deposits in this are~ could be moved
back into the vial by heat treatment with the torch. This s~mple was then
27
~Q' e 0 ~~ "tM,Iq ~to", a.~C\
Figure 7. Modified sample containing tube.
+o~c.~ Vv\ € \+~ de f O"); ts loac \, \,,~+o &~W$Qlt \J\~\'
28
att2'lched to the vacuum 1 i ne ~nd the dc:hydrClt lon - sorpt ion procedure was fall ('i-.Jed
as before.
The vial was sealed off) after th2 tl,r~c day period, and it was observed that
the contents were now dark ycl1ow-or~nge.
Both the selenium-zeolite A and the selenium-zeolite SA vials were now placed
in the muffle furnance for seven days at 3508. The variac used to control oven
temperature misfunctioned during one twelve hour period t and the temperature rose
to bOOce. The samples did not appear adversely affected by this ( zeolite PI is
stable to 750C) .
After this final interval in the furnance, the f~lowing observations were
made.
selenium-zeolite A sample;
red-brown out of the furnance, changing to yel1c)',v-orangc; upon cool ing_
Some selenium remains in the vial. There is no further color change wh~n
vial is broken open.
selenium-zeol ite SA sample;
red-orange out of the oven, changing to brill i~nt orange upon cool ing.
Some selenium remains in the vial. There is no further color change when
the vial is broken open. An analysis indicated 8.84 selenium atoms per
unit cell of the zeolite. Crystallographic investigation of this sample
is discisscd in the next chapter.
Tellurium
The adsorption of tellurium onto zeol ite A, zeolite SA, and cobalt exchang8d
zeol ite A, was performed sinlultaneously. Approximately 50 mg_ of the particular
zeolite sample was place~ in individual glass tubes) 12 ~n in diameter. A cal-
culated amount of tellurium powder, corresponding to twentyfour atoms per unit
cell of zeolite, was also plBced in each tube. The tubes \!~8re marked for ident-
i fica t i (\ n 2 ~, be for" e • The y \J ere d 1 so i:10 d ; tic d for sa s. c() n 0 c. n sat i (H) ~ c! n d the n
ual1y increased to 3S0t, over a tV.J8ntyfour hour petiod. The tcr'ijJer2tU(C refl1cincd
at 350t, v:ith not mOi'C than o
a 10 vccri;lticll, for another full day_ At t h rJ t time
the samples v;ere sealed off from the vacuu\n 1 ine. The vacuum hlo.~ not lost.
The following observations were recorded.
tellurium-zeolite A sample; no change in color or eppearence
tellurium-zeol ite 5A sample; no change in color or appearence
tellurium-cobalt exchanged zeal ite A; sample appears black and destroyed
The vials were then placed in the muffle furnance, and the temperature was
gradually brought to 550°Cand left at this temperature for a week. At the end of
the \1eek the samp 1 es vJere removed, and t he v i a 1 S vJere broken open. The fa 11 oV-li ng
observation were recorded.
tellurium-zeolite A sample;
this sample contains some silvery tellurium deposits, but there is a lot of
white material which looks like melted mothballs. There are no sin~lc cry-
stals. Apparently, the zeol ite was destroyed.
tellurium-zeolite SA sample;
this sample also contains some silvery tel lurlum,some crystals are brown,
some are black. It cannot be deterMined in the zeolltic structure has
been destroyed.
tellurium-cobalt exchanged zeol itc A sample;
there exist mtJny single crystals in this sample) but they are i:lll bleck,
No analytical or crystallographic study of these samples has been initiated,
due to the 1m'l tcl1uriunl occupC1ncies anticipated; this problem prolnis(;d to be more
bot her some for the s e 5 amp 1 <3 S t han i t VJ as i nth e s i mil jar 1 y p r- e p ~3 yo e d 5 C 1 en i U ffl cry - , ' c
30
stals.
2) maiccular sorption
Zinc exchanged .~eol itc i\ \'Jas chosen for 8x?(::rir;i"ntat ion in zicr:tylene
sorption. Some work had already shovm that hyc:rocarbon-z.col ite corlplE-.xcs
could be successful 1y prepared and cryst~11ographically studiedS7 , Be-
cause this would be a gasous sorption, a single crystal of the prepared complex,
75r~ on an edge, was selected and placed carefully in a small ,100rm, glass
capillary. The capillary vIas then scaled onto a vacuum systclIl equipped Il!ith a
zeal ite buffer system to insure that the acetylene vapor exposed to the cry-
stal would be entirely dry. Tile system was also equipped with a McLeod guage,
S0 that the vacuum could be measure~ accurately. In order to dehydrate the
crystal, an oven was fitted over the capillary and the tenpcrQture ele~ated to
-6 pressure of approximately 1xl0 torr for fourtycight hours. The cr'l-
stal \oJas then exposed to 650 torr of 99.60;.) pure acetylene for t'/Jentyfour hours.
Amarols work \vith unexchanged zeolite p" indicated that this would be sifficicnt
to introduce about six molecules of acetylene into each u~it eel! of the crystal.
Afte·r reaching equilibriuM the crystal in the capillary Vias carefully sealed
off the vacuum system. A diagraM of the vacuum system set up is presented in
figure 7.
It is knovJn that zinc exchanged zeal ites are very hydrophi 1 ic. Thi s \Vas
firmly establ ished for zeal ite p; after this author CQ:npleted the crystal iographic
study of the zinc co~plex presented here. Although no acetylene entered the
zeolite, this vJork did permit recognition of the hydrophilic nt3ture of the com-
plex, and further was able to yield a val id structure determination of the hy- .
drated zinc-zeolite complex.
l \
I , B I I /- OV'CM
31
Fig..ul·e 7. Single crystal Vacuum system.
Hercury
Diffusion
Fore
'Pump
,""
The i on -exchange and corno 1 exat i un 0 f $;!rCa '; r·lu<-J /"'\) • X!-hO, refer red to in t '...1 •. : (,) \ L..
the furture as (I), and Zn5Na2(A) "29H20, referred to in the future.as (I I) ~
has been d3scribed in chapter VI.
A single crystal of (:), 75r on an edge, was placed on a glass needle. This
and the capillary containing the single crystal of (I I) were each mounted on a
Stoe goniometer head of a type de.signed to make adjustments in the x, y~ and
z directions. For each data set, a Syntex four-circle computer-control led dif-
fractometer vJith graphite-monochromatized t10 Ko.,. radiation \'Jas used thr~u9hout
for prel iminary experimepts and for the collection of diffraction intensities.
The data sets were collected at approximately the same temperature .(200 C) and
humidity. The temperature range during anyone data collection never varied
more than 0.5°.
Both structures have been refined in the same spcce group Pm3m rather than
.Eru3£, because of the suspected absence of long range order in the silicon and
aluminum positions. Due to the possible excess of silicon to aluminum, as in-
dicated by elemental analysis, an occasional silicon-oxygen-sil icon bond is
probably present in some unit cells \."hich strictly prohibits refinement in .E!J.3£.
A check r:R
of Graml ich and Neierts')" most intense lib" reflect ions ( vJhich could be.
present in the f.ill3.£ sp()ce group) \'Jere found to be absent in materials from the
same 5g 60 61 crystal1izations-' , as those used in this work. Gramlich and
have shown that, even wh~n appropriate, framework deviations are small. re w&
fore, in structure refinement, no distinction Vias nJ·E:de bet~'Jeen silicon
lu~inum atoms; they Were refined at one equipoint and were considered as one
33
t yp~~ or <::tom.
t'"lo rec'I' r- rC)C:1 'I 1.,,::; '-L t. 'I' CP.. po' 1 '" T C \.!:"::. rr> n ,.;>.:;; nE' c!, ~ hr- \Ie (. .. h;;; r. e \("" 1 • 'n ,-.. .. : -, nO l'(e>_ _ ~- ~ _ _ 4 I~ .. ~ ,-... '-' ,,_/, .. 1 •. 1. _ ..... fi ... ·d. L .,~ . .!:- .. <.;1 ' .. ;~ '.11 I ", Ij_~
cause previous data sets have indicated very few reflections of s~gnific~nt
intensity in this range. For each dDta S'2.!t the 9-2.0 scan techni cue VJD:?, em--- j
l It t' t- f O. r; <>/. ( • ')0' p oyea a a cons ~mc 5can ra .. e 0 - -" 1'(11 nute ! n-!~) . The scan range was
varied betvJeen 2.00
at 29 =:; 30 to 2.5 0 at La :::: 70°. A time equal to half the
scan time was spent counting background at each end of the scan range.
Standard deviations on the nct counts sampled at each point in recipro-
cal space were assigned according to the formula:
where CT is the total integrated count obtained in time t c , 81 and 52 are the
To account for instrument inst~bility, a value of 0.02 was assigned to the em-
perical parameter Q. The rntensity and standard deviation for each reflection
was corrected for Lorentz and polarization effects. A reflection was determined
to be significant, and therefore included in least-squares structure refinements,
if j·ts intensity .:!xceeded three times its standard deviation.
Each structure was refined by a combination of full-matrix least-squares
methods and three-dimensional electron density Fourfer maps using phases detcr-
mined in the previous least-squares refinement.
The two error functions used as criteria for suitable least-squares rc-
finement are Rl == (~ lEo -(Fell )/£fo and the generalized "'Jeighted index,
~ 2 2 1/2 R2 :::: (c..~(Fo -\FcP IfwFo ) In general, a lov/er set of error funct ions
indicates the possibil ity of suitable refinem2nt of the atomic positions in ques-
tion. However, other factors are considered - the equipoint in question must also
refine to physically reasonable position21 and thermal parametcl-s. Because 3
thermal parameter is sensitive to' the occupancy of the equipoint, the occupancy
cc:n be largely determined by requiring that the correspcmciing therm,31 piJrametcr
be reasonable.
where F and F.. have the prev i ous 1 Y de! fined va i ues, i12 i s the nt.Jmbc r of OD5-2 r--0 -c .--
vations, and 2. is the t-)tal rrJinber of individually v2:ying p,3rameters. The
goodness-oF-fit indicates the s,lit2bility of the v,'e1ghting scherne; its ideal
value nt the conclusion of structure determination is 1.0.
Possible atomic positions are obtained from peaks on Fourier electron
density maps in which the contributions of the framework and of some ~ations
have been subtracted out, and Fourier elect~on density maps in which all atoms
in the structure are ciisplayed. For such small data sets as are commonly ob-
tained for these zeal ite structures ( less than 250 observations), occasional
erroneous peaks can be expected. Because the atoms we wish to locate usually
have only moderate scattering factors, generally have higher thermal purarneters,
suffer from the effects of disorder, and have small occupancy para~eters, their
peaks on tIle Fourier maps are not expected to be large. Therefore, it is crucial
that acceptable refinement, when and if it occurs, successfully describe previous
ly unlocated atoms. Such refinement has proved succcssfuP:3. p,ll peaks above
the 3.2:: 1 eve 1 vJere tested in 1 east -squares.
The form factor tables needed for Si++, AL+1 . 5, 0- 1 , Zn+~ Se, Ca++, and
+ 61 Na were taken directly from the Intcrnatior;31 Tables for X~Ray Crystallography
or interpolated where necessary. The charges assigned to the ions were generally
taken to be half of their formal charges, to account for partial covalent bond-
. TI Z ++ f f 62 - L f ~ f 1 d· • Ing. 1e norm actor was correctCG ror tile e-tccts 0 anorna cus IsperSlon.
OF THE STt<.U eTI!f\ c: OF Sc~~; ea ~),! CLI,). XL 2 0
Th~ output of the LPCOR co~puter program indicated that of 376 reflections,
99 were significant.
Initial full-natrix least-squares rcfincm3nt f,;:;c;~r{ upon the refined frDme-
work positions of the sulfur co~plex of 56 'zeo 1 i te F. c.onverged, in six cycles, to
an Rl index of 0.211 and a~ R2 index of 0.175. A sodium ion ~~~ition at .15, .15,
.15, was al1m'ied to refine anistropical1y in these reflneii:ents. ( The tables at
tLe end of this section give the! coorclinates of all models discussed.)
An initial Fourier electron density map based upon the refined positions
produced 10 peaks in tho intensity rangs
deviation of the electron density was
to
- °3 e fA .
()~
e - / A..J: the est i rila ted s t C'm dar d
The st rongcst peaks found fror:l
the map, at .22, .22, .22, and .23, .5, .5, \\'cre included VJith the previousiy re-
fined positions in four cycles of refinement as four sodium and four selellium
atoms respectively. Although these new positions refined relatively well, the
anisotropic sodium thermal parameter refined to physically unreal lstic values,
and Rl rose to 0.25, and R2 rose to 0.23.
The anisotropic sodium position was removed. A calcium position at 0.0,
.34,.34, and a second selenium position at .25, .25, .5, were added. After
four cycles these positions converged to an Rl of 0.198 and an R2 of 0.18. The
isotropic thermal parameters for calcium and 5e(2) rose, frrnn 3.0 to 30.4 and
34.2 respectively. Sc(2),( here on called 5e(1) ) V/DS allo'vwd to refine off the
three-fold axis for four cycles, but its ther~al parameter went do~n only 51 ight-
1y (26.4) and Rl and R2 both increased, to 0.21 and 0.19 respectively.
Four rrlJre cycles of least-squAres \'/f:;rc run, \id th onl y the fr(.li"t:::V:();-,I~ ,
,:'.1(10
the stable caiCrUiil and selenium positI:.'ns, prior to executing a second Fourier
seleniurn position ( occupancy of four) at .32; .32, .32, but its thermal pafB-
meter diverged upwards. Hence a second Fourier three-dimensional electron den-
sity map was produced based on only the framework and the stable calcium and
se1eniuID positions. The map contained 14 peaks in the intensity range from
to e-Ift?; the estimated standard deviation of the electron density vIas
_ o?
e IA~. The peaks from this and the initial map are 1 isted in Table 1.
Analysis of this m~p guided the input of four selenium atoms at .34, .34, • . . 34, and four sodium ions at .24, .5, .5. Four cycles of least-squares conv~rged
to an Rl of O~24 and an R2 of 0.21. Thermal paranIDters remained stable except
for that of 0(2), which rose fro~ 3.3 to 14.25, and the added selenium, which
rose to 41.+.0. In an attempt to remedy this high thermal parc1nleter, 5e(2) VIas
taken off the three-fold axis for further refinement. This, howeverm caused only
a sl ight decrease in the 5e(2) thermal parameter, and incre~5ed the Se(l) thermal
para~eter to 25.2. Rl and R2 were now at 0.199 and 0.184 respectively.
5e(2} vJBS then placed back on the three-fold axis, in a slightly different
position, but agin did not refine well.
At this point the calcium position was allowed to refine anisotropically.
The thermal parameters for both selenium positions rose to about 30.0, and Rl
and R2 decreased sl ightly to 0.19 and 0.16 respectively. After one more cycle
of refinement, however! the selenium thermal parameters rose to about 40.0. Rl
and R2 rose significantly.
T\"/o more positLJi',S found from the second Fourier map VJere assigned as
H20 positions) although they had initially thought to have been background
noise. After four cycles) their thermal parameters became negative. They'l'Jere
:.j 7
2nd R2:::: 0.142. Th2se ere the"'! lo~:/est indices t:1c:hievcd in this study.
Q 11 o',ved to ref in,,: ar; i sot rep i ca 11 y. FOlT eye 1 es c-f ref i ni~i:~ent produced no chC:3nge
in either error index.
v () rio U sot hE:: r po sit i em s f (.\ U n d fro rn the sec 0 n d F 0 U r1 i e. r- rn c3 p f ail e d} VJ hen
included in least-squares refinCM8nts, to lower R1 or R". L
Other trial structures were postulnted and refinement attampted, but a9~in
no success vms ach!eved in lOitJering the error indices.
All i~terpeak distances were calculated, in the hope that enl ightening
bond lengths might be observed. These distances are recorded in Table 2.
B. Discussion
Most of the nadels used in the atter~pted solution of this structute as-
summed that there might be a Seg ring in the large cavity of the Zeolite. This
r.::: 7
was not unreasonably expected since Seff~' found two S8 rings in his ~ulfur com-
plcx. Selenium has a greater atomic radius than sulfur, and thus tVJO Se8 rings
could not possibly fit into the large ce~tral cavity. Analysis had also in-
d i cated approx i 1I\:;)te 1 y e i 9ht 5e 1 en i lim atoms per un it ce 11 •
The location and the stability of the t'dO H20 positions indicated that the
zeolite w<)s not hydrophobic, as \;25 Scff's complex. The occupancL.::~; \.)f the
selenium positions correspond well to a total of eight atoms, yet no arra~ge-
ment of the tv/o posrtions v-iould ~;ignificantly 1m'Jer the error indices or the
selenium thermal paran-:'3ters. The cDlciul"1 and sodium positions \-J8fC found and
rcr,lained stable throughout subsequent refincrn~nt.
{'IS became obvious in the structure refinement section, all attenlpts at 10-
eating stable selenium positions \"Jhich vwu1d yieid 10\" error indices or therclt.i
parameters successively failed. For this reason, after over 80 cyclss of least-
credence to the bel icf. Figun:'$ c~ thru 12 illustrate the electron density
in the center of the zea1 itels large CDvity. It is bel ieved that selenium ar:d
water positions varied in alternating unit eel15, giving rise to the disorder.
39
Table 1 • Peak positions fro':! the $;; i en i um COinp 1 ex Fourier maps
Peak Coord i nEitcs X y l
S i I~ 1 0.0 O. 1 [;OC 0·3700
0(1 ) 0.0 0.2250 0.5000
0(2) 0.0 0.2900 0.2900
0(3) 0.1000 0.1000 0·3200
Na 0.2200 O.~200 0.2200
Se (1) 0.2500 0.2500 0.5000
Org 0.0 0.0 0.0
x( 1} 0.0 0.2600 0.2600
x (2) 0.0 0.4000 0.2600
X(3) 0.0 0.5000 o .lfOOO
x(4) 0.0300 0.5000 0.0300
x (5) 0.1000 0.3000 0·3000
x(6) 0.1300 0.1000 0.1000
X(7) 0.1600 o .Lloao 0·5000
X(8) 0.2500 0.5000 0·5000
X(9) 0.3000 0.1300 0·3000
x (10) 0.3300 0.3300 0·3300
x ( 11 ) 0.3300 o. 1300 0·3300
X (12) 0.4000 0.5000 o. 1600
X (13) 0.4000 0.5000 0.0
x (14) 0.5000 0.4000 o. 1700
X (15) 0.5000 0.2300 0.5000
x (16) 0.5000 0.5000 005000
~ ALL D STANCES ARE IN A
. ~ • r- r~· • • ~ • ~ • ~ • \. ~ . •• . .. I <:t -::-. N' ~ '. j ::::;. ~ ~ N ~ ~ 'G "3' ~ ~. ~ 'C" '2" ~ ""S ~ ~ Q
I . V ~ ....;, u, ~ .so' -.. ...... ___ '-- ~ -... --- ......, ~ ~ -......> - '-J 0 ~ -
~L0; .. _9J_ .. 91_.9~ ~:. Vl 0, ~_~ Xi ,x, ><~ ><~~ XJ x. ~~_.s:: .. x .. _~. ~.~ <-S,1l L!~'~l- .:1 ,Ik : ' ; •• 2'7:...' ! i,uG-: "Os'; 3"3 : z' 1" 2,O{ ;J·n _,: _. ~ ! l.}~ ; z,ol7: ! 3 .I~ . I , j • I ! . I j j r ",!,." ; :O(1}~.itl_~~I. __ .~;2'fI-i:2.qS; ..... "''' __ ''''jl .. -- I!Z.~1!.'.30 ~12.'/?:1.·(IZ.Z.fq;. u+- : 'fi~.~.~~ ____ ~~,{fZ~--~.~Oit,J1{ 1. --- • I ! I I I . I : I! ! i :: .!
O(2).II~b;2.,j.,~: 12.~:2.tfs" ' O,s61,'tcJ!2.CfO I ·/·'2.*-:3,Z)': 1/,,,0, :1,14 !1..C(() .- -- .. ; : . : .. ; ! t- i ; ~ : : . ~: --,--.... ~ . ~... I
',0(.3) ; II~ :2/6-::2.(£ •.. ,. i2~~~ j .. _ .... _L. __ ... , '; 1,'I'Z; 205' I 11216"1, Z.% 2/33_, _..-__ ___ l- ..... !t,Yf.i_ ._. . 1- .. ... ' , I' I ,: i :'. i I . 1 : I I ' . .N~J~'~9~_ ... __ .j1,q5;2.<l1 131'H~; .. _ iZI']f1 12.(/t:~ .~,3Jl ; .. _!!77:_~J'3;t,ltJ~ ...... - .... , 1 .. .
'.SeOL_j3.CJ8I!. , ... jb! 3'~">"i~_.~ 1- Lo ! M i J~!'Il~<Qb:~'~2. UOlz. '3: 3~~;1 __ ,.2,08 '. 310 7!.,
~ I I 1 I I I Iii I I I I I I '..oyq ~ ___ ~. ______ 1 _ :. ! .1 ... - . .". 1 2'>~1 I .' .-_l --, t .... - L_-_.~ ... -_L ... _-~ J, i I I i I I I !;: I I . ' I I i I ~:X(I) ;1,,"" :2,Q7
10oSZ, Z.'I~ Z,7fj .. l 1 13,'IC. 2.10 __ : _J_P'~,L __ ;t,OO .1 3,<10:_ .. . } ... i --_ ..
,"){{Z):3,O/ ~ 'IJ01J1'fO,.:Z,S-1 '3130jl ___ .t/,7/1' /1.Q4 "3'(l«, ~,?~~gl--.- l't'01! _ !t/.ro ____ iZ,qf >.qbl I ._ i : ; 1 I ,I I . I' I
t_X(3) ),u ;Z.I~ !2,'1' i .\ i i 3.~~ 12 ,/1 I" 73 ~t[{~!!~~t3,d_ y.7b 2."'1,.13' z.oh,01; I . 'I ,I I I ' I I I I' I
~X(Ij);2.'I".1''fS-l .. ~_i~~~i_ . ..! " .. _ 1 13/09
1 .1 I ? ! 1----1.--.1--- . -.Xls) ,2 ,09
i2.8'1 ! / :2'1,Z.W, r·02! 3.12L i /,~6 i '.~6 iz .~? M~ 3.z 1~V.3 L 1·;}7 : Z.Yb! ·~i : 2,r; I,qq, fol'h
; ! ' i I ! I ! ! I 1 ' I . i I I I 1 :X l~) j 3dJi
13,Zi'i t, 72 :z,.5.)1 i 2,35";Z,8'61 ; 3.4J oaJ.. r IM"'i ! i· Ii. ·X(7lJ!._._~. ~~~"i---II __ ...,,- .ll~ ·'t\._ 1·2,~i I t'('1 Z.iJ ! /1(,5'"~i~il~_' 1b~-.3~O .. !~~.j .... -... _.1.'.'% ~ '.,7tf .', It'lq. I , I . I I I ! I iV, , . ,
~X{~)I ! ! _ )3/0£';" I 112 •30 J.-- i ti~ . .,q{:~~.l«?+Q_?,Jo.: . . __ :.lS":3;ob.
X. ,I I I I I I I,.,. I I " '
._ 11):~133~}.ob !"loO~2.Lff ,I,77:1.,c('2.1 .. 1,7'1-11.0713,/1, ;,l/ 3.U2..!1~~ ___ i~·~~j ~~zl7b i3 ,,1.Z,7%j ; ._ .. 'I I 1 I I I I I I iii ; r. ' ! 3.10 .
:X(lu)l.. __ .. J ----1.--. 2,~}_;:2 . .'~6.: __ .. - __ ",._ .. " 1,f{, ~?~~~7}-'!Q.t_~i~L--.JI~-'!J-3,(2"- -- ._,.,!!~r:~~_._. __ ,I Ii! I ,1'7-"1 .. ' I I . I " -X(Jl)~.2,-~t~.?/12.."7"112.Y'l2.W2'73Ii ___ ,00 IjL.oo,'Z.7b 13 .. ~_bl@):9~S'l.:~'C/~1'~."Y"~Z'?!_ 2,1(.,;2 • .30,1 I .... I I I I I T i : Iii I ' I I
~x.(L?)t--r~1Q'+'-'f-,-' ____ ~~N.L .. , .!'2,YJ\2."" Z'U lQ_l'!tt[il.'2b.:).,o~j __ I .. ". . .. ;','11(1 , . . I I, I I ~(~~~'13'i?~'f ~2.qo __ .. _.... ''''1'.-- '3
8012 ,'11-11,13 1. • .,'1 -+-.I.~ .. ~.,~~39 ... 3."~~_. _ .. ~. _. Ilq/" 12,7d l, ...... ,.r.07
[ ..... _-
f~{N): __)2!99 L_ T ______ . J'Wr _! 2 .q" 12.0.. 2.1'1 1/.7fj 1 •• 7 l.7!; - t.3O /,7f I _~ --I Id3 1_
Table 2~ Interpeak distances in the selenium compiex Fourier map
r-
o
f-~' !
j. ;"'4-i
- --=4 -.;t.--;-r-"--l-r-Z-- -2--C--~ !
-=4-- - ---~l--~Z'-,;;'l--r\-·--r'- -'2--"- f-C---~
n
, 1--~"
\ '')
!
.... ; I i -I j
-' i I
; ...
\ ... ,
J I ~
i I
I I
"
I .!.\
I ~; ~
! !
... ! -: ! I I
I ..... 1
'1 I I
, ... , i
:)1 ... ;
, v
~
.!ol .1 ,
:I ~.
,I 1 ,. ",I "': , I ,! ,I ,I N' 1', ...
.t N:
,; N; ,: ....
, . ....
i .i ~:
" .v
.,:
1 t· "i
I!.:
; ,
1 ..
.: 'j
" 1I -1
1 '--j if: I I -c: I I,
r 'f'!
II I ,.,. i'
!.". "
-r ft ,- k ....
j '.
~ .. ,.. I I r'" -I , i..o !
c:.
Ie I !.o.
-j' , ! ....
j' ,
: .... '.
I I '-
~ I
17 .c I' ! I
i~ I
.... .,. I", , __ ~ __ , ___ .1
iI
'N L " "
l I !'" >c;. :. ! !N k ic II i , ! I I
.:L __ r: __ ~
Figure g.
I ...
~ !
jc
-c.
;c ! i iN ~
l i ~ I r
I
_i· I ~ I
I I
e). __ Z_l
.< l t ---.--.-, ~ _____ t ____ u ___ ._l __ ~~ __ ~
! 1
"
j ! -,
~i I i .1 ... j.'
,) i
...
.. '
, i I
;>
I ... ' ,
t ____ ~, _ ' ' ,2 __ --' ___ ' L
_ L-y __ l __ ~. __ J::
.,- (-
'.1 t _ Z __ Z __ L __ J __ ~_, __ ~:_ ~":- z-
I .cO, ,J ,- -,-,,--_._*1. I I ~iJ __ " 1-
Electr6n density in the zeolite cavity.
!
l ~ i 1 j l
I
-5 -4 -2 --1 -- "'-J
-5 '-5
~- -()---l--r- -1---
~ ? r-2---'!
1 -r-!.-:--{-
:) ---,,-----C --1 ~/\'--l---
Z'-- Z- -1 - • 2 -- T - --1
l- et ~ ~ l.. -,_. ---,
'" '" N
C. C' ~ ~ L.
:' ... :-
c '" '" I i - c ~ -, ! ! - ~ ~ - ~
" I " :1
.. ... :... N
I , j' '. I I
t .. ... ;... , I
,.. on '" II I il 'I
i ". .. ' '.., ~ !... I .1 I ;1 ! I ! '\ '" ~ N - 'C' i ·1 I ;1 I
I I ¥- .... ii ~ - c. II
, II .1 I
I J i
! '~
I I j' !
I I -I
L-
_. n
1-----1 --Z-~
,-~
I I I 'c
~ ....
C'
i I r I
rl
~
N
.1_. ___ L _ . .1 ... (
~ .:>
~
I ....
! 'i .J
-'"
I I -. N
.; ! I .: I!
N
I I I #- ... #-
I, I I ,,It J', #-,
I I
'" \It
I I I .,It ~ #-
I I ~ ,!. N -I ,!. I ,!. .- ...
, :> ...
tv' ,
.,
._~ ___ , __ _ .i
I
__ 1_. __ ' __ l ___ 1 ___ C,
__ t-__ .J=- __ 1-_1~
--,- -'. £:-.-- z- -l~'i
! .11- -~-. _ ~---I
, s-_ _s-...;
1- __ 2- .,- s-
oJ _ 1- _i- _ 1-".- __ li- . ~-:: ___ ~-
F i gu re 9. Elect ron dens (t yin the zeo 1 it e cav it y.
'-,
-1)--"":;-...... _- ":i -" -,
::::~:~.~_:: __ ::~:~_::~."-. .--.,. --.~' -.: go .~, !'.l)~) • :.;\ 1 ~, ...
I
oi '.2333
"I.3!ob1 -.-- -
(.4 "r (
~,.~l3'3 - -----,-- - 2
~.4!>'>; .,
0) " -.. U" ,..-, ....
c-1
r i I
e !...
'..,
'" I I
";' .,.
N 1', ~. C
" " , !
N r. I
"<4-, ., ,
oD , # ·or ,
i'
.c ~ ., ;1
-~-'- ---1-
~- -~ --,,-
.:. "c.
o 0 1 j I I " f' i ! " .
~
!
i~ I
l I
fO\ Ie " " I I ", :'" ... :, I' I'
I fO\ .... .., t , I
:,..
I
"if
I -2 - -- -2---'C" --- 'I)
-2 --r'--o-J -Y---]--~J
I . ' -'--l---~I
-' ~
". j c c PI
.N r I
i
1-1
I .. , L..
-=-
i ... I --1
Q
I
i 0'
i ;\1
I .' ,...; i 1
:----1-"' "--"-~ ~; ~ !":" ~~"" ~ N .... .... ...
\J C"I '" V IJ 0'" -II- ',I U -.I WI .,.
:1 :, I .1 4-1 . I
.1 " I 0'1 #. 0-
" .1 I
';'1 #j .. , II I
WIll. N' .. ! I
aI I!"':'
Ni ] .;r. ~
. WI
. I .1 .., i I
~ ~ oJ ~..l ,j I I j I I, '>1 ..... , ... : 4
'_~ I
I ... d ~ ~ ~ ~
~l_J_j_.L© .J 1 __ ,,_ . ,, ____ "' ___ 1 __ ' __ Z __ lj
1 1 ,1.1 __ 1_1
1 1 .J ,Z _______ _ :
"="-.._-----..- t
E L -' 1_1 ~,
I.; tJ I-
t. E- z- z-
X:" Z~~ 1
Figure 10. Electron density in the zeal ite ,cavity.
I 1 i t
I t !
'.
c.
c
.. I
" I
c
4-'I
V\ II
:.ro , ".. ,I
I , v-II I
~- .. • I I ,,:) .... N 4-
~ • .' ,.". ... 'Jt
I I I ,! , t! .... N ...
' .... .... , ! I
! I :
'N ... e- N :1
I '.,. !' t ,
i ;
L I f' !
.1.. _ .•. L ._." •.. _ I
Figure It. Electron density in the zeolite cavity.
• ... I, ~ .
I' N
" -
I ''/<
I
'" , ~
• N
I -
I I'
" I'.
• '" , ~
I -I ... ,
, .
t-- -i -'\
i--''-4-I
-I !
t I 1-
I . J -.--
r i~ I I~
l' 10# 'I
------·-'--"-t--!'>--::i - -·I'-·--1.--r--O--~
; . ---=4 ~-:-~1)--:r-r---2-- -2--1-~
1
-~ - -~3--;2----1--6-·-r-· --2--' f--l---~
i _N
. I ,.. I L l
e
!c .... I i ' !... 1 .. , I' . jl I I .. II I
!.. I ! ;- ;N
,
;e i
1
\
'''. ,
.... I
I
J I i
I' i~ :~ N i ,'N :.t. ___ t.
i , I i .• '1
II ; 1
jc I
i ~ I
~~--. _ -' : 'f
'N .... '0# I,.. ..... i ~oJ_ CJ_. __ ' __ . '_' __ • ____ J __ L __ ,~ I
1
! .!o\ v I
:t
I .!oi
i ,! ., Nt
It N:
\-
II I-
~l ~-
I 't " "", ~:
I I I
II .: I'i ~-
~. I, Nt
I
" "'i
.!.:
I-po
, ,:
'i !
,....
.,
j
_'-_"' __ l __ C __ J~
z-
c.- . __ ".-__ '7-
Figure 12. Electron densit\l· t'-I In ne zeal ite cavity.
Table 3. Initial refinem~nt of the framework and one sodium position.
S\..i,"" ~l)US = 5 5 5 S ., t 1 Jr' S L j'I . / i) t L F / .=. __ ._.. 1.1 7. J <) j 1 8 '-. R. = U Q 2 i t O)~ 7. . N U .~ C r: H E F L ~ I N L '> S 0 = 99
r~E lE~(R~LIl[C ~E[G~T~O R l~[EX {R2} = Oo1748S -.-' - '-.
~Ok~ALIlEC SLM LF S~G~ktS CF kESICLALS = L2503S2~
1\ (: (l S C t~ L E . F fj eTC K F L R Fee s .. = .3., 9 1 It S S ~ . T HIS I S (U lOS C .L\ L t F ACT Uk.) r L~ F. S G / .< G + DEL TAG ) .)
"')TCK .1
2 J I.t t:. J
l\ E \., X l\ E /I Y i\ E h L' N t..: '{J Ell L R e i".~ c Vol tJ 2 2 i'J t ~~ '0 3 3 .c" is 2 3.j.l_._ .... __ l ~.15 2. j j 1. ___ .. C 0 1 5 L. 3,3.1. __ .. _____ ._._ C .. " C () 5.3.4 (5 .. __ .. _ 0., I.) 853 43 ....... Q.'3 06:5,3 L~ 8 C')C C?C C 9 C ...... . ColCdlCS
G " J d ·:t 5 S 1 C?~2(;EOt
l.;) 2dd(;21.
C"lCulCS
00374600 Go5CCOao C~2EE621
OoJJ~010
l.,4S7J O~43~485 SIAL 1~S552 O~i23jJ5 0(1) ~o2538 J?214940 0(2). L~E264 OQ~4628d O(3}
:j : ~\ J 1. 2 ,) 1 717, '3 l) ."
i\ [ ~'1 i':· L J 0., L 717JO
Table 4. Refinement with a selenium po~ition and another sodium position, both from the initial Fourier map . . . "~. ~----,. ~--- -- - ._- - .. --. -.•... - ~--.-. -- .... - .---.-~--.-.- --~. - ....... - ._-- .. - . - .. - .- - . ~ .. -' .
SU'~ rrjUS::: C~33<;3g:'3, SU(·~ /rJ~:L F/.:: LS5~,,55;:1 i·~ -:=' i)25'~:"~, ilO o OF 1~~~f:L" Ii\ LOS9 == 99,
TH:: !;E~~F? t,L! Z(: U . ~.·/~: I .~~.r..-:: . .D_ . .3.J i'r~f:.x __ J f\2 r . -:._ .. _D.f) 2~ 5 29
~\!;j;-:~11~Lll:i_1 Sd\1 !.JF S(~iJ~~~CS elF :~~:S 1'::UALS ::: 2!)1<)~)~)q~·
1<~,·. S(/.lE F'!\CT~)R- r-eF: Ffl:3S =·;:~~,/12·i7')() ----·YH·[S IS (OL~) scA·L-(··r-··!ic·~fr.F--j··Tli":r=.5 G/ts' J- DELTf\ Gl3
!~ T (1 ;·1
1 ..., '-
.) -
4-5 (,
7
:\~ :: it! x - i: 0 ~ 2 :3 ,3 L:- 1
r r • 0 ~
r~c (: 0 1 f; :- t' c; C '''':o.2?( )C (' 0 2 ~ 5(;'..: 2
~ \~ Y _I." 2 3;·Yt 1
'; 0 8 ~) : C) It
'~<l _3~\)C
" ~ 2.(3C; ~~ 56 r 0 l ;~. 5 <; 9 ('j
. _ . ':'." 2 2 1 I: ~} .:J !~ 0 i5 (I.";) (; ~.-,
J\I[:H Z __ - ': ~ 3 ? j ~3~· 1.
\~. (J '3 7315 S
NE ~'J i1T 1 . i};:' B rn: w P, 22 -1. ? ':u: !. (Y t' 1_ <) It:? J fF, 6
1 ~ ;~)~) "\ ::. 0 5 i'~~: ;:~.') i; ': 0 :5 ,';(:::':'\: ("~ .. _. __ .... _ ... ?-? 23.2 3. ___ ._._~\.o_~_5t." ,"i;'! ('
"? :2 .~~ s ;=) 5 6 (03?--3655
It.., Q 1'131 2 0 5:):" ~
(. 0 2 '"):: ." -:.. \~ ,,0 5:.'\(\ (; :";0
I'Jt:: ~.J B'3 3 :"'1{1-2lP,.~6
S1 .l~ L Q ( 1 ) 0(2) D ( 3 )
r.l f \.~ 812 '. 0"
r,; c: '.: "1, 1 "J, ------.~ -- ... ~~. --'- _ .. __ :.: ._".- -: ~----
0 1.'
r-' 2 Z r ('" (\ 4 ,~.t '. ". (. .) S 3 ~ 3 '3 ,\1 {\. " . .1 \, ~,_. _ ~_,_,.,_~ ___ . __ __ 0:* ... _._. ~ __ ._~ ____ .. _ . __ ". _' .~~. _~. ~ .. "..~ ... ____ . ___ ~_ .• _.~._~ ___ . ~ .~. __ . ____ .~ __ .. __ . ___ ... _ ' ___ '~.'_ .. _. __
~l ., 5 (,'; ':~:. ~) 19 0 351l'
(, <) ,'i 33 333 SE 1
c~-·~
Table 5. Refiriement with the anisotropic sodium deleted, and a calcium and selenium position added.
---.--- .-. _._.- ~ ~ _. .. - - - - -_ .. _." .. - -- - ~
'SLK FOuS = 590535CO, SL~ IOEl F/ ::: 1170Qt15, R ::::O.lS822, NUo (f REFl~ IN l,So = 99·
T 1- r: (E N t: R i~ L· I ZED h E I C: t- T F. 0 j~ INC t X (R 2):::: 0 ') 1 7 9 4 4
(\ C 1 ~ r J ;\ L I lEe S L. f<l C f S (~ l; J) RES C F RES leu A L S ::: 1. l+ 8 ~ <; ~ s .,
.. -r ~ E \.~ S C ;l L E F ACT (J R r- () R F (J t: S = 4 0 1 SO It l~ ~ T HIS I S (0 CDS C!\ L EFt. C T I.) H ) . T rr~ c S G I (G -{- 0 [ C{J\ G) Q
ATe j\i j\ ch X l\ E ~I Y i\ [~'J L j\j E Vi Ell OR 1J N E ~" b 2 2 r~E'v\ 833 1 C,)C C .) t r ~ L ~
:) -J t:,).... 1 ... o ~.3 4 5 5l~ 5 30.,4C20 0,,\)03333 CA 2 C.C Cl)1843CS C., 3 7 f , 115 lo~CJ5 C" 5G 0 CO:) SIAL ::3 Gee O')2~38:3 0')5COOOO J<')S7CJ4 U()L5t;OOu o ( 1) ---._---- _ .. - -"--'--'---"- ----- .. ---.-. -i l CloC 0.,20.3391 002<;3891 5o!iCC3 Oo25CCOO U(2) ~ C"lC27<)0 ColC279C 0.,329177 Jo(J54 'Jv5JC~:;OO O(3) 6 C'J (~2S/150 C., (:;.: C) I~ :; C Go L ~ <j It 5 0 0 0 ?595 ~ 0:)J(33333 1\1 A 7 C~LCS213 C'o)~COOCC OoSCOOOO 3'~c) 1680 U';) 08.33J3 SE 1 a C')258S67 C.,25dS67 0.,500000 6() 2 165 O~O83333 S2 2 -;. .
...... J
Table 6. Refinement with Se(l) off of the three-fold axis . .. . - .--- ._- .... _--, - - .. -. __ ... - --- - - -. - . - . - - - .. - - - .. --.. -. - -. . - - - _ .. -.-- ---~- .. --
SLt-l foes = 6169~~38, SLM /DEL~ F/ = 12810716, R =0020776, NO~ OF REFLo l~ LoSo = 99
T h t: (E N i: R I~ L I l. E: D hEr G H T E lJ R I 1\ C E X {R 2 ).::: 0 0 1 9 2 <j C --... --- - ~ . ..---.----.-.--- ...... ---~.--.- .... --.- .•.. - "----.~ .-.
1\ LJ I< lJ ,\ L I lEe . S l lv1 C F S C LJ;j RES C F R t SIC U A l S :::: 1 d 7 0 8 4 1 Q
NEw SCALE FACTCR ~O~ F~8~ = 4 0 365250 {filS IS (Ol.D SCAl.E fACTOR) T I tvfES·· G/{G ··+--·DEt~T/\--G·T~-·
/\ rei' i\t~ X . j\[lti Y 1\ E ~~ l N E~~ tll ORe HEh 822 NEh 833 -.-. - . -'-'~ .. ~ ... - ...... ~
1 c?( C • .335i355 0 0 335855 j7.,~859 I),) \) J 3333 NA 2 (oC 00 1 iJ J (r 92 0')373790 13C853 CI)50,)()CO SIAL j C..,C 0., 2 2/1 L 7 C O»5COOCO 3.,1717 O.,25C0J0 o ( 1 ) t. C,( C " 3GOGJ l f C ~ ~O::1 0 3!t 611 :3 It 76 C ~ 2 S I] Q()O U{L) 5 C . ., lCj~20 C.,lC322C 0.) 3 31~ 6 61 L.,'i543 0·.)SOCGGO u (.3) f:. C,,22~733 C.,222-1?3 C,~.:2Z733 I~., 125'-) O~08j333 CA 7 C"Li7150 C , Ii :; 3 3 L.1. O.,~COOOQ LO,,'1Cj3 i)a083.3J3 ~E 1 e (.,256223 0.,256283 Ol)5COOOll Ii" ... 31 Cd 0,033333 SE 2
T()ble 7. Refinement of only the fra'mework and the stable calcium and selenium positions.
S U ~~ F 0 ;J S = 6 2 J 8 It 3 2 8 , S l,; M / 0 ELF / -:: 1 3 <) 5 , 2. t 5 7 R = 0 <I 2 L 3 66 , N LJ ;) U F H E p' L ~ 11\ L.) 54) ::: () <)
T r E ( E i') E f< /)' L I LEO h E [G r TEO R INC E X (R 2 ) =:: 0 ') 2. 0 0 G 4
i\ l~ F :. ;) L I LEe S l) r·~ Cr' s (~U ,6 i{ ESC F f~ t SID U A L S = Z 0 b ~ 5 4 1 ;--.
~": ~: "1 S C ;-1 L E f- /\ C r L11~ F UHF II [3 S ::: It ,) (t 0 6 8 't J) T I-if S [S ( 0 LOS C l\ L E f .~ C T U f~} r [f'1 E S G / {G + 0 [ L T.4 G) <) ,
{I reM I\E~ x f\ E \'t Y 1 0.,0 C ;) -1 d J 5 (38 2 c . .') C 0, 2'2.-7 ~29 J c., c o .) 2 \j {t .l 3 5 it C~lC{1515 o i) 1 r) It 5 '7 5
" . c:; C,222{;2S Co 22262S --'
6 C:l~tCC62 00260062
NE'tJ L O.?J72.102 O.)5COOCO O,,29~135 0 0 328(376 Ov22262<1 O.,SCOOOO
N C '{J E 11 0 f~ B 10(<;133 3., (239 [to 1 /,J2 2 -0 S <) ()5 5 o C6'j/t
ll~;'3(J7
N E ~~ e 2. 2 Oo5COOOO J1)2500()O Oo25C()OO O<l5GUQOO 0,,0<33333 0.) Ob 3333
;~ E y. 033 SIAL U ( 1 ) U{Z) U ( :3)
C;\ SE 2
Table G. Refiner.1cnt shov·Jing the high thermal par()meter of an additional selenium posit ion.
SL.;t-, f08 S ::: 64380133, SL~ fOEL FI ::: 1 J 6 6.~ 1 1 2 , R.::: ;) ~ 2.1 2 3. 9 1 NiJ :l 0 t: i~ E r- L, I N L., S" =
1 1- E l E:\ E !< J\ L I ZED ~ £: I G h TED R 1 N LEX {1< 2 )=:: 0 0 1 9 7 3 C
i\ L }~ jJ ;\ L I lEe S U f·1 C f S c,;. L t RES C f RES IOU J\ L S = L 1 J :' <; S 5 <J
, . ~. ,
<,--'I :; C j\ L t~ F;\ eTC R Fe f< F U e s .::: /1 \) 53 f t 1 7 ? T l-ll SIS (LJ L D SC j\ Lt F he T () f\ ) r 1:'1 E S G f (G + DEL rAG) "
J.\ Te tJ. ~, t '.\ X l\Eh Y N E\'/ l N C ~'J ell ();~ u h El;~ f)L 2 I'l F. h l3 j 3 1. <;.,C C,)122972 Co3722.dJ I) S D I.t 9 0) ~ 0 () 0 ( 1) S r J\l I.. G"O G? 2 ~ 5 (; 2 S 0 . ., 50()()CO :) .. (dlB
. - . '-~'.. - •. - --_.
O,,2500JO U ( 1 ) 3 CoG c~ 2().:.)( .. :3L o 0 .(~ CJ 3 t, J 2 J r) ~ 2 (t.J 0,,25CJCOO o (2) 't C~1047[;2 C>9 1 Cit 7 t 2 C" 3 2()~~/t6 C~., 79<j2 0., 5;J0080 U Lj) ~~ (."I.L7361 G1)21736~ C,211J(;3 Lr :) t 2 tj7 v'JOF33JjJ CA ~
b (.,/.~(jSj C :) ~ :; t; J 53 C?5COOGO 8.;) 7956 0'30833J3 SE 2 "{ C ;) .~ i.. S 2. 'j 7 \) ,) J 292 S 7 o ,) 3 ;:. <) /.. Y 7 6 a r) I. tJ 1/1' 000('.IJ333 Sf:: 3
99
\ .. '.l
:
Table.9. High thermal parameter of added selenium does not decrease.
S LJ I"" F LJ 8 S .. _:=: .. __ .? 6 OJ G ;)_ -( 3 G , S L 1\1 / 0 ELF / = 1 :} 2. 1 ,) 9 7 8 , R::: 0 ~ L 1 It tt 5 , N tJ) C F REf- L I) I i\ L '> So:: '0 9
T 1- t G c i\ r: f-~;\ L I l E C,'i E 1 G~" TEO 1< INC EX (I·~ 2):: 0,) 1 CJ 99 ;2
. ~ --_. -- •.. _- ...
~CR~~LIl~C SUM Cf S~LA~ES CF RtSICUALS = 23300(So
NE~ SCALE FACTOR FOR FOBS::: 4 0 594210 THIS IS {OLD SC,f)..LE FJ\CTOR) Tli~tS G/{G + DELTA G)~ - .~- ~. - -- - ~-.- .- •.• -~. - --". _. - - • -. ~- <-- _._- _. -'-' - ... - .• ---
ATCM ~[h X ~Eh y NE~ l· ~EW Ell OR B NE~ 6ll __ ._ .... _1 _. _____ O~C ......... __ .... _____ 0".132811 .0.,372231. ______ ._.0\3 <;333 ... _. O,5l)COCO
2 GGO O~225329 Uo~COJGO 3~C669 O,250000 .3 CoO OqLg~499 00293499 303437 00250000 4 C, 1 C It 7 U 4 . _ C <) 1 C it 'I [3 Lt . G 0 3 2 d 6 L 2 ;2 :> (: 7 <J 2 . 0 ~ 5 0 ~~ G C 0 5 Go 21t266 CQ 2i6266 0 0 216206 4.3584 0~Oe3333
6 Ca2S5373 C~255373 Oo5000CO 80 ISll O~0UJ333
. __ . _____ . _.7 G <) :3.~ L G It J . ____ . __ G" .::! 32.6 It,} _______ p" .3 8 5 <3 J (~ .. _ .. ___ ... ~6 ':) ,97:> 0 'J U J 3 3 33
Tab1e 10. Refinement after second Fourier map, new positions are atoms 7 and 8.
N E \'1 U 33 SIAL
0- _.. • ___________ ~_._
o ( 1 ) 0(2) O(3) CA SE 2 SE 3
S U [·1 f LJ b S = (J84~,,27-1, SLI~ JOEL f/·= 1631~6f3, R =OD23850, NO? CF REfL? IN loSo =
. . ~"" .-
T 1- t G [ ~i l: l~ J\ L I ll: 0 )'\ E I G i-; T E () H 1 NeE X {g 2) = 0" Z 1 :.) 1 3 •
:'\ 0 i~ r· !J. l I lEe S U H OF S ~ U A R. ESC F H E SIC U A L S = L d 1 I) 9 11.. ~ _._., - --~
~E~ SCALE F~CTOR feR foes:: 4 Q 812440 THIS 1S (OLD SCALE FACTUR) Tli~tS GJ(G .. DELTA G)o . .
..
,"11 eN i\ E \'\ X i\ E \\ '{ i\ E~ l NE ~ .• Ell Of{ B N E ~~ 822 NEh 833
1 CoC C,ln~72(; C.,37 tt149 00c(:52 J"SCCCOO SIAL
2 ('-' C .. , - --, .. - ,--Cc231i58 OoSCOOOO 1,,/509 O?25CCOO o ( 1 )
3 (,G 0-> 22d5'1C G.)2Ec5 /.6 14.>253 l t 0<)2:50000 0(2)
It (.,cseS82 CoCSbS8.2 0,,322631- 2.oc5S4 G 0.50 0000 o ( 3)
c- C~~1'i1.t6 C.,L.l'l71.f:. Q,!)Llt716 L.J /I!l 9 I.t O~O83333 CA :J
6 C,?:2tlSC9 C~26iSCS u'J 5CO~Jca (j~~l)ll O~OU3JJJ SE 1
7 C"ji1 t130 C~34113C 0., 3 /11 t 30 10·) CCGO 0,,083333 SE 2
(3 C') L {j C t 7 a C)SGCCCC OoSGOUCO l:)~COGO l)~O83333 NA
99
r--\))
""--,'- ... , ...... ~ ... "-, .. "' ..... "-, ..... ~-' ........ ' .- .. ~ ... -,-., .. - .. --~---.... - ........ -.-...... ~ - .. -~,-~.- .. ~-.
Table 11. Se(2) thermal parameter increasing.
S tJ :'-1 j= J B S :: 6295,711, SUM IO~L FI ::: 1 2 [3 6 ? 0 6 1 , f~ = 0 0 2 0 t} 2 8 , 1\10 " (J f R ~ r l 0 I N L" S ~ --
THe G E i'H: PJ\ L I lED I:; E I G H T E [) R I N [) E X (R 2)::: 0 0 1 9 0 0 5
I\l G R. i -1 {\ L I L t u S U t>1 0 F S (l U f-\ RES 0 F R r: S I [) U t\ L S ::: J g.;) " 8 (:; 9 ~
01 E ,<f s: t .. L t F A C r 0 R FeR 1- 0 n S ::: lh 3 8 It 2 1 \1 T HIS I S (O LOS CAL E F 6, C TOP) T I r·1 E S G I (G .j- 0 E L TAG ) 0
i\ rU,"l 1 2 3 L~
5 o
7 8
. _ .. Nc'~ X
O~J
0,> \) ---..... - -- -_ ...
(jo 0 (j;a 103556 ()., 2. 2 2. <) It 9
Oo201F3B9 00 33.f) 7BO 0') 2 j 0 {~"11
NEW Y 0.) 1 [3 3963 0.,227930 -- .. .
N E'i~ l 003-'31.02 O~5COOOO . - -.~. -- . - - .
Oo29~477 00294477 C3103556 00330483 00222949 0~222949
0326188G O~500000
00336780 00336780 00500000 00500000
f<E ~~ B i '1' '0 R,"h" '--' N-!~'W' 'B'22------'· '--"-"i\TE-~r'B3j---1~~064 O~500000 SIAL 3 " '200 2 0 ~ 2 50 000 0 ( 3. ) 7 ,,-3 i3 (~ 66;) 2 's' 0 0 0 O-------~--O· ( 2 ) .-.'.--------.
2 0 9956 O~500000 O(3) 5 0 3089 00083333 CA
15,»291 0 0 083333 4400553 On083333
7" 1767 GoOg3]33
Sf 1 Sf 2 NA -_ .. ,. -- --. . -~,------ .. -"-"~ .... ... ---_. __ ... -
Table 12. Refinement with S8(2) off of the three-fold axis ..
S0r'1 FOGS ::: 6110~sdG, SUM ID~L FI :: 12180665, R =0019942, r\O" OF Rf:FL" fN L.~So) = -- .•...
THE G r:~ E R i\ LIn: 0 \'iE I GH T F. f) R r N 0 EX (R :2) :: 0018355
,\1 U R. 1',1,':.l I lED _ S U) ~ ,. 0 F._._ S Q, ~J ARE S .0 .F R t S IOU A L .S, -= 1 ~ 6_ <).8 ? 5 •
j\J E ~J seA L t F t. C TOR F 0 ;~ r= (J US:: It ? 2 3 7 6 5 0 THIS IS (OLD SC:~LE F;\CTOR)' Tlr<1(:S G/(G +- DELTA G}q
.\ TUi·l N ~'I1 X :\J Flri Y 1 O~0 0., J (j It 1+ 9 It
2 . 0 ~ J. _______ , ____ . _ 00 22 r.] 69 3 0" l) ()-)2)30~3
It 0., 10 I" 051 C~ 1 0 !tt) rs 1 5 Ol)2270~5 O?2~70?'5 6 O~c..66152 00)266152 7 VI) ~ 'J 3331 0., I-t002 71 8 U <I 2.3 8 t+ 1+ 6 '. o~ 'JOGOOO
~\J E'rJ l 0·)373322
.0., l30()OOO"
00 2 l) 3 02 J o " '3 -3 1 2 2 t+
0,,227025. . 0 0 500000 O,~3J()161
NEW Bl1 O~ R 1~2092
305932 707387 2~9436
5~9lR4
25.2038 37~78j3
-_ .. ~-.--.- ... ~.-- ---_. - ..
N E ~ i B 2 2 . ~~ f.: ~J B 3 3 O~5COOOO
O"2S0000 O~~~JOJO
0 0 500000 O~Oq3333
O~08J333
o~oa3333
SIl\L iJ L 1 J ________ , ___ . __ ,_ Ll ( 2 ) {l ( 3 )
CI\ _. _. __ .------ .. _ .. _-, .. _-SE J.
O~ 5COOOO __________ , __ (to 108 /_. ___ O~_003~.3} SE 2'Nt\ -- .. -. -- ----------
C- t"" , 'J
so
\Jl o
Table 13. 5e(2) back on the three-fold axis.
SUFi fJdS .:: 6137 0 605, SUM IDEL F/ = 1 2 32. , t.;. 26 ., R::: o? 2 0 a 8 0 , !\! 0 0 f) F R (:: f L I) I N L ., S.) :;: () C)
rl-iE 'G~~Nt:i\.,\CITf:'r:5'-\~~'I Ct,j-rf.D R I~:'DEx' (l~'2) .:: 0') 187.62
~ORMALllED SUM OF SQUARES OF RESIDUALS = 166,624 0
,\JLI~ SC/\L~ f;\CTCJR fOR FD~~S ::: !!,?~1612o T HIS {S «(1 LOS C /J L E F ACT 0 P) T I ~Jl E S G I (G + 0 r: l TAG) .,
;\ T ON - i i'~ f: i'l X 1 -·01) 0 II
- . ~! E \.,' ,. y'- -----. - - jH: ~J' -Z·- --.--.- .... , N f: W' . !3 1 C' () R '. 'B ------N E I/J [) 2 Z'- -,-- --.- N E ~i ' B 33 "'-- ,. -... ,_.. .
:O~ l8{t292 1'.: ':00 373111.'':~ ,.10 lB~,O"f 0" 500000 SII-\L
2 00) 0 I" C ~ ~ 2 f.i 0 .8 0 ! .' 0 <) ::: COO 0 0 II 3 ~ 5 J 4 5 11 0." 2 5 0 0 () 0 0 ( 1 ) . - 3.--'' (- 0.) 0 17\ . " 0,; ;~(j 366 2 ~") !. 0" 2 9 3 66'z"C\ --.-'--~ ~'':'l", 07 9:f:'~ --"--O-:;'z'SO ocfo---------- (J ( iY''''-'-- ---.
it- 0 0 103?09-; , 0 ~ 1. G 3 9 a <)' ; '0 \') 3 30 7 8!t '. ;_. (") 2 Q 9), 1 0 .":" 0 9 5 0 0 0 0 0 0 { 3 } S' 0 ) 2 (: 6 '26 1. ':,'; b 0.) 2. t; 7 6 1 1 ,,/.. 7 7 Oo216989?-(
e _:,0 <>.2 j 1 0') ?3S>~
O? 22 626 1 ',';: ~·O '.) 2 ? 6 2 6 1 ,: (1 ~ I, 5.) 89 g It - :0:, 0 ~ 0 B 3 333 CA' ,.::'>~\'--O')26-r611~;~'/ - Ot)5000'OO'/l(( -5.':21~81ll-'730 '0\)083333 Sv:-l-------° tI 3 7 ') 11 8 ~: 'I,.. \: 0" 3 7 5 11 8 -g. f ~). '3 2 ::. l~ G <J 2 " -t 0 $ 0 g"3 33 3 S E 2 o Q 5000. (] ,0 :J;/~ ___ 0, 5 0000 o __ } ~~. __ <~: It ~ It 1. It 6 /O;(S O!> 0 n 3 3_ '3 3.,~_,. ____ Nt\._, ... ___ _
.., /, ,J I
Table 14. Refinement with the calcium ion anisotropic.
S l. ;'1 F \.~ L ~ ;: 6J~J~4~1, SL~ /UEL F/ ::: it:.. 1. !i , J t .:'t 7 k::: r, <, if; 1 29 , ;~'J.),~ 1: i~ L: F L ~ I f\ L ") S " :::: 9 (;1 ------~.-- --.- ._-
r I-!:: C c ~ C f~ ~ L I l E L ~ l: I G h 1 E [) H I ;\j C (~ X (i~ L j::: Q;) 1. (:, "-t it I
h U I' ," /. L 1 LtC :) t.-I~' ·u f 'S·l-.-. GAr'. E. S'CF"- k I: ~ i"L U:~ CS'--=l 't2t-~ 'j sr;-----'----
i'~ .: ~i :) -:, ;\ L t 1- /1, C r ~ j .e< F C t1 f:..; uS::: "t 0 il- 7 7 '-t .:3 0 T H f ~ 1 S ((J L tJ S C ,\ L E t= II C r .. ) k} f [ ;1 t: S G / (G tOt. L T tl G) '0 ~---- ----------
1\ L ~, X ~ L: ~'.. L 1': ~: Ii c 11 G R G i ~ :: v. lJ !. ~ f~ I: ';--j t312 I~ 1 c.. IV
l
2-C .) L (.: :; :: L .J
(.; C C , (~ ,..' n
l\tf\ Y C')c:~55~~ \) > U) j~: 77 U)22t::;3f.
C.)C~iL06 8)C~1~06 . ~--:)~ 1.) .:;-" ,\Yi S-J \j (j 'OJ
,\j [~, d 3 3
J~C2.1~')6 C; ., /1 /r :5 7 () 3
3 /1
('
'. ) .. () ., t. S ,) 1 .; t
--ST,~C-- ---- -, L J tel I J .) 2 j C J d 0 u ( 1 )
.) 2. ~) \ ~ /. '):.) d ( L )
v,
J l; l. C :; (; 1 '1 ( , t. "; -: 1 :; I r. 0 27 L 3 (, :;
\.. ) i. C t; <; 1 S c ., (_ i .; 1 : I
C.) c ~ ':; 5.: j () ;'j 7j~3[~ C,:;CCJGJ o {l ~.; -.; 130 G -: 3"~ "..:-2 .l H
o .) (: () 'j 2. (:)~r.:jJ - .. - tJ'J !j J C (] 0 ]"------.:1 (j ) '---.------,- ... ,- ... ,-- .. ----, -----.---- ----.
(;
"I c (=L'~ll~~U
C " 3 -J ': J ':: ~ C,:;CCCGlJ
Ol~C~J~J
Co3~GjS~
CJjG~CGJ
/... '3' J C ,; >J l I.. -j " Z; 1 ~ J
jo lB:)')
'-~\J')C.~dj.)jj ~E 1
,~\ ',), \) v j .J j ,) S E 1-t) )0 .3:; :L3 .3 NA
·~ .. ~! ......... _ .. ~ .......... '......-Jl ........ o .. _ ... -""'~ ... ·~."'" ...... , ... _' ..... ' •• .-_ ............. * .... ~. ~ __ •••••• _."_
Table 15. Both selenium positions with increasing thermal parameters.
S U~l f'J B S - =.. . .. 9 5 310 .133 . .1 _.S lJl:-LJ DE L F I _ = ..... 13 Oa.)B5 •..... R =.0., "0030, NfJ.oOFRr:F,L • IN L 0. So .. "' .. _. 9_<)
T H [ G E'-4 ERA lIZ E 0 h' E I GH TED R I NO c: X (R 2) = 0 _, 1 7 1. 09 .. - -. - ~ .. -..... _.,..- - - - - - -.. - --- .• _-- .----_ ·_·_v· ____ ~ __ . ___ .~___ _ . __ ••... _
~U~MALIZED SUM OF SQUARES OF RESIDUALS -- -.-_ .. __ .. _-
= 165.,59{ro
N E ;;.. S C i\L E 1",\ C JOR F: (JR. ED B S.= I+? 59Q 0 '5. o. __ J 1-1 L S .. IS (0 LJ)~ Ct. L FFAc:I Q R IT HIES.GLeG + D F. LTA. G) .' .. _
i\ T 0 H N E t~ X N E VJ Y i'-! E ~~ l (\j E H P. 1 I 0 R B NEW f3 2 2 N E ~'J 8 3 3 NE\-/ B 12 1 -- O~ 222<)18 _______ . __ 0" 222918 ________ .0.,222_9.1 8 O~0239~j_O ___ .OQ 02399_0 _Qo023~90
2 O~0 O~184076 O~373672 1Q2611 C,500000 SIAL _. ________ O_~.Q 5?PJO. __ _
3 0 0 0 O~225561 OQ500000 2~7874 OQ250000 0(1) --- - __ 4_ ----.---- 0" 0 0;) 2 9 0 5 8 5 0,,290 I) 135 __________ . ___ 6 n 11 :3 Lj- ____ ~ ____ ~O_C' 250000 Q{ ?-.>. _________ _
5 O~106578 O~l06578 O~332453 2~0813 O~500000 O(3) 6 00268944 O~268944 O~500000 3703419 O~166666 SE 1
._-- .7 0025821.1 ____ . ____ 0,3 n0451 ______ 0" 3 80Ll"51~ . ________ -''-7.1 <) 0761 0" 166 666 ...:~ ___ . __ sr~ 2_. _____ . ___ _ 8 00241643 03500000 00500000 209573 OaDS3333 NA
Table 16. Refinement vlith 8 H20 included. -.. . _. - ,--- ,._._-_ ... __ . --_ ..• -.. -.-.------- - --- - - ---.-.- .. -----.--------
SLM FeES = 6J45of32, SLM fCEl FI = 11171) C ~ S t ---if-~6~-1"--Y6 G -4-;-·----NO ;----ci= --n·EF- C-;--·"! r\ -i~- ~-s -;--.~---. -----9 9
... _. r ~J_~. iN ERA L I lEe hE JC.h J_~u ____ E ___ L~cJ:_~_J_H ?) __ = ___ Q.~J_2.Q_~_=_ ________________ . _____ . ______ :_._. __________ ._. __ ~ __________________ . ___ _
~CR~ALIlEC SCM GF S~LftRES CF RESICUALS = 121~lf5o
N~~ SCALE FACTCR FeR F02S = 4~52492o T HIS I S -- ·~(clD --sf I-\ij~-- F ~A(fo-R-f---fiME·----··-----------· .-.-.. --- ---.- ----- .------+ DELTA G)o
pTe M f\E~ ). f\Eh y 1\ E \, Z N E \'1 E 11 ORB ' N E \~ f3 2 2 N E 'n 13 3 .3 NEh Bl2 - - - ._._. __ ... _-_.- _.- ---.------- - - - -- .. -.-----. - - .. - -_. __ .--_ .. _ .... - _ .. -." .. _- . --1 CoL1S2~1 Co219241 C.,Z192'-tl C g ClgS41 00019541 00019541 o <.l 0 l~ 1 doD 2 C~C Co1<33.2.2.6 C0374321 lo~C34 00500000 SIAL -.l eye ~¢L?'5127 C {) 5C C 0 CQ_ ..J _.3.,C563 ._~ .. O<)L5CCiJO_ O(t) 4 (.')C C~2(;251E C,~2S2518 6?(217 Oo25COOO 0(2) ~ (~ lCE122 (;)lC~122 Co3J52t5 ... jo4591 O~500COO U(3) 6 (",2/L.73 /-{ C)~7?.1j'-1 Co5CUCCO 38,., 1103 0",083333 SE 1 7 C,,~tj~ES (,j(;lSLt.c Coj81542 llo~4J4 OoOB3333 SE 2 8 C .. 2~~le(; Co5COC(O Co 5(~JOr.O s c '~ ( f :3 1 (; 8 C,C"i21S8 C)U7~lS8
10 C~(Sl-L12 C , . .j ~ (; It C C I) ~ 326 It 00
2~~502 a~083333 NA /:'~c;, ~~-G~ ___ OouH3333 ___ . H2Cl __________ ._ .... \. ~- 6 <) (2 <3 L/J Q ? ') (3:3 333 H 2 C2
V, .- .. -:'~
Table 17. The H"O positions refining well. - -____ ------------- ---------------------.t..--- ----------- --------------_.---.----.-.. -.. ---"--.------.-------. ----. - ---.--- .... ".'--"-- ---
50'1 FJBS = 6303Q<:8+,sur~ IDEL F/ = l03t3.,9()6, r. =O~16t.J-Rl, r\;o, OF R f r- Lot ~l L", <; ,,--' ;------- 99
T Ii E G c ;'J t: R ;.\ L I lED l~ E I G H TED R I "J 0 E X {r< 2) = Oo141d3 _. __ • ___ • ___ •• __ .w ___ ._ ••• __ .w _ • ___________ ._. ____ • _ •• ______ • ___ ~ __ • ____ ... __ ._ .. - --.- .. -.. _._.-.
>~CHd,11_\Llli:D sUr!; OF S()lJ~\Rr:s OF ReSIDUALS = 106,,030')
.- ". __ •.. _----- - - --........ _ .. --- --- - _. - -.---.. --- . -.. - -----. --- --.----------.------ .. --- ._--- ------.---.. - ... -....... - .--------.-.. _-.---_ .. - - .. -.--~---.-------~-
j'JE:',.: SCALe Ft\CTO:~ FOR FOBS = 4., ( .. 50 68 ~ T H r SIS (Cl L D S C /\1 E F ACT () R) TIM f S G I (G t- 0 E l T~, G) 0
f~ r;J i'1
1 c.. 3 4 5 6 7 d ~
N t:1,I X 00222319 0" 0
N t:\'\' Y - -- - -- ---. -
O.,222n19 0·) }_8 38 j 2
j\J E W l N E 'I; rn 1 (l R B i'l E H B 2 2 -.---_. -- --- - - ---- ---- .- ••••• _--_._- - > ,. -- -. _... - - -. - - -. - ._._---- - .-- -- - --. -~-
O?222819 0,016460 0,016460 0" 3 7.3 ~; 92..- 1 " 337'2 G" '5 CO 0 0 0
0,) 0 (;.) 0
_. ____________ 0 <) 2? 5 !;- 60 C, 2 () u() 30
O~500000 3,6026 Oa250000 . . - . ------------. -- ..
O,;?C)t)030 5)>3')0 /1- Oo~(jOOOO
0) 1 J. }. :3 '-1- 3 0" 2767.-32
i)" 3 3 3 5 0 7 3.} !~ S 3 0 0., 5 O;J 0 () 0 0,5CC000 36J?6 h A 0,083333
- __ .~_. _w •• _
()... ~) r3 ') 7 :3 a (),' 3 d 5 ;( 3 0 ? 8 () t:. 7 7 9 0" 0 (5 '3 3 3 3 0, 5 0 Ch) () 0 0 0 :; 00 0 G a 2., l? 7. 7 0 ~ 0 U'3 3 '3 3 00096157 O~086751 O~2740 000P3333
;'!FI.'i B33 O? I) 16 td:O
SIAL fl ( 1 ) O{2) o ( "3 ) SE 1 SE 2 r,; A
\j:: H [\ J ? 0., r;3 2 ft! S
\)1
10
o 1 11 J. 5,"!" 3 Uc,I.."/h'232 o ) 2 D 7 'J 5:5 u:) 2 It- ~ 27(3 () t) 0 13 6 -{ 57 Oe.lu~921
•• __ w_ ••• _._ ••• _ _ _. __ __.~_______ __ •
o <} .) 1 <j 0 5 a J" 3 1 9 0 5 8 2 ,) >~ 3 5 1. 0 l> a :3 3 3 3 3 H201 H20?
-- --- -- ------ --- t_~)
Table 18. Refinement with bot;, selenium positions anisotropic does not significantly alter R1 or R2 · _ ... -.---- - .. - . . - . -" - .- - -
s U j'·1 F J !3 S = 6 30 8 <) 9 8 It- , S U 1'-1 lOr: L F I _ :: ------i-0-3-1- ~()-00 ~---- R--=- 0~i-() 3 56-~--- ---~~()-~--0 r=- ---p- [~'f: t~-~ -i ~J---l_-~-S-~'--'~ ---- 99
T liE __ G t"J E i{_ALll. ED ~i EJ GH TEO._ P,_._I!'.J f)fX __ { 8..2) __ = __ o_01 'JQJ -------- ---.-.. -------- - -- -... ----.
i'iOR:y\AL IlED sur'1 DF S\)UAP,ES OF RES IGut,LS = l03~ r?.21)
~EW SCALE FACTOR FeR FOGS
ATUM 1 2
_3_ (~
:5 6 1 8 ')
10
_N~:',i_X_____ Nf\-l Y o .., 2 2 {t 7 f3 9 0., 2 2 t+ 7 B 9 o () 2 1 (~ 16 1 O? 2 7 !t 1 6 1
_0" 2 72 3aO ______ 0., 392102 040 O~lr3202
0.) J O~O
0., 110285 0, ,~(~ -, S~) 1 0" ,J(J j ZIt (
00123063
0., 227328 o " ? <) 3 ') 7 9 r. " J. J. C 8 B 5 (}.,:500:)00
. \)., () ()'i. 2 It 2 C,3?7C)?.3
____________ - _.w ____ ~. ___ .~ ___ ._. _._ . - ~_. ____ - •. _ . __ • ____ . - - __ " ___ .• _____ - --,. ---.- --- . -.-. -- _.w. ~ -.
= !t ~ It- 2 2 1 8 0 T HIS i S (0 L n S C (\ L E F fj. C T 0 ~ 1 ' T I ~ 1: S G I (G t D ~ L T tI, G).,
___ N E hi l_________~J E vI. B1I __ Q~ __ B _____ . ___ ~I[ IJ _8 22 __________ . _____ }\: t~J·J ..f33 3 _______________ ._ NEW E J. 2 () ~ 22.' .. 739 0 ~ () 10 q <~ 1 0., C 19 92 1. . 0" G 1992 1 C" {: (t () 3 r.<~
O~0534S9' OoO~04~2 Oo13~663 01)0 O.,5CUOOO 0.,392102 0(> 3 7!~ 165 O .. 'SGCOOO 0,,293379 r):l332932 0) :; 000,) 0
00 D 7 LI-_7 63____ _ _ 0., 08 n (,5_ 5 ____________ o? 0 It .0 1+ 16 ________ _ - a ? 0 B f) fJ) (~
1?3472 C~5COOOO SIAL 3,,6~-)69
7?030~ 30 :;C)')3
1,,3009 _0" O<':;}_2 I t2 ______ . ____ o.~ 58 /t8 o 0 :) 2 I 9 2 3 !t ~ ;-? 1 :3 1
O . .,2~)OOOO Oel) o?? 50000 ____ . __ OJ 2 ) ________________ .. __ C) ~ :.> 0 J 0 a 0 (l ( 3 )
O"OG33J3 C~OR3333
0, J B'3 13 "3
I\J,\ H20J. H202
__ •• _____ v_~ ____ ~ __ - .--- - -~.-- ._-
Table 19. Still no anisotropic selenium refinement. • • -_ .. ->- •• _-- •• ~- -- . - -- ... _ ... --~
SUM FJBS = 6267.867, SUM /O~L F/ = l035 0 80l, R =0016526, "lOt) OF REr':L,) IN l,So = 99
THe . G E\ L: RJ\L I Z E f) 'yJJ. I G~~J~f)_f~. J.~l9 E~< ___ Le.?}_=:_Qo_l~~~J5-~._ ... -____________ . __ .. __ .. _________ . __ . ____ ._. _______ ... ____ . __ . ______ . ______ ... _____ _
·~LJR',t!.I,LILEO su;·, OF SQUJ\RF:S OF RESIDU.ALS = 1()tt,/tl.~31)
-- .. -. -- ----- .. _- ... ----.-.--.. ---- .. ----- .------"---~Eh SCAL~ FACTOR FOR FOGS = 4~L95Bao THIS IS (OLD C'~LE FACfOP.) TI~~f::S G/{G r D~~LT .. ~ G}o
;\ r GM NE',-l X --1 VI) 219':t-52 2 0<> 25 it- 287 3 Oe264328 .:.. o 'J (j
S 0.)0 6 00 f)
. -- .-
7 a c 1. U 8 6() 0 :-, 3 () ') ,~ j 080 8
'-) ()"v<)082l
N E_W ... '! ____________ .J'1F: ~~ Z ___ .. _______ N~_ t .. I _____ ~Lt_Q 3 __ j2 ______ ~l~.!4 __ B_~l_._ . ____ ._._11f_~L __ !1 ?}_ O~219452 00219452 O~020160 O~020160 O~020160 O?~54281 00500000 -OQ077981 0 0 1356)0 Ol).~ 9 2403 0 I) 3924-0) .. __________ . __ -0" 0 2 5 ().i_~ ___ . _____ o0 C!.l-6]9 5 O~183093 Oo37~095 -)_03133 C~500000 O~226753 0 0 500000 3o~825 O~~50000
0" 33n/~90 0" 0(-1-68 a 7
srAl o ( J. )
O,29~549 O~292549 508951 Oo~5aOOO 0(2) 0.., 1 () 86 60-'-------- 0 (> 3 ~ 3 3 -(6'-- ------------3 ~ 1. 1 <5 i-l- -- 6~5 OO-(jo 0-' -------0(3 ) ----- -- ----.-- --------- .. O~500000 00500000 200621 O~aG3333 f\l<~ 0,) 0 (j 0 B 2 7 O.~ 0 C; 0 82 " 0 ., LI_l~ -r 6 0., 0 ~ 3 3 '3 3 H20
NE ~~ 812 O{'OCJl?·g O~ 0
-0.,318897
00 -32 Cj 78:3------0·" '329 7 a 3--~' -'''-- 6,,- J () bi----------C) q 0 f3 '3 3 -:3 3-------I~i-2 02 - --------.-.. --10 0.157703
\-'-.
Table 20. Refinement with a planar Seo ring as the soecics within the large cavity I,J I .. I·
sur~ FOGS = 66320]R8, SUM /D~L F/ = 1126 0 463, q =O~?OOOO, NO o OF ~EFLQ IN LoS~ = 9(;
. r H [ G::'\j E ~{t .. L IlL:;) \~ E I Gl { TEO F I ~l 0 E X (P. 2) = 0 <, 1. 7 572
---- --- -'------N:J l:z-,·f.\LTl Eti---S-lJi";-'- () F- -S () U ,\ f< -:::-s-rsr- -f~ '~SI IiU:d.:-S----;--· [8 (T~-r-3'rl)
N c > IS:: ~\T-c--F t\ (1 0 R---F ri? F tn3s----;---t~ -Q E7(Y9-Q-~----'--nrr S -'''1 -s--TD C IY---$t-~f[--t:----F'~L\C f'CHCf -, r;v1 E-$---G ITC--- -~·--DE C T -A --G l~--
~\ T U i~ 1 2 3 't-~
o
1 ()
9
N E \1 X I\; r: IJ Y -- -.---•. - - -
GoO O~lB3652
000 0~~2q734
0')0 J .) 1 J 'j a a 1 J .) c. 1 .-~ !. It S ~) '> .~ 'j ') () ;: ')
dol J.. oj 'J 36 0,,0 i) ~ 5 ~)i}:; 00
l~ " ? :H) 637 o " t J <:~ -:1 d 1 () .) ~ i (,- 1. /~ 6 () 'J -'~ :? ::. 6 ~j
0.) }, l G? f)
0.:.0 (I ,) ~ I) S 1+ :; -:
f\J r: ~'I Z Bll OR R 8 2 2_ [J l~ 0 C C i'-\ E 'It} B 33 -.- .-------.• --.--~--- --------
O,312515 0" ':00000 ()_~?~3r:6~7
-- --0" J ' ... (~6. 1 -3 o ) 2 1 ,1~ i I .. !)
'J ) '5 i)OJ()O 0" 1 1 U -j 36 1) .. 0 () ) ~ fJ () I~ 00
o 0 9798 (:'J 6536 "{ 0 4 r: 1... It-
'S" '30l18 ;)'J 1 S '5 0
;~ ~ ~ /7 ~~ ~ J" Z 1/~-2
16, 6 5~j IIr
It (~ ~ ~ 7/t 6 -- _.-------.- - --.~.. . .--.
-.. -- -0-.;:5 ) 0 0 00 s r !\ L
G~?)OOOO ()(l-)
Oo2':)CCi)') (1(Z)
0.,500000 [1(3) 0.) j () 6 6 00 i'J A o ') 0 :3 .3 3 :3 -3 S;:: 1 0.) 1 ') 6 (d:; .) H :2 o:i -_. .. -. -0,,0:::03'30 C!\J. o " 0 :~ 3 3 3 3 S E 2
--~.-'---~-.-~
A. Str',l...::tur8 Refinemsnt
-l ~ f t~ LPC"D t pr,ngrd-~," 'Ind;ca~e-d that o.f o,~O~ rp-i ne out pu ... 0 - . 11e ... h\ CCfl'pU e r J I: ,I.. . -' ~ ,,\. '- -
flections, 179 were significant.
isotropic zinc positions found in Amaro's43 partially dehydrated zinc ex-
changed zeol ite A, converged in four cycles to an Rl of 0.24 and an R2 of
0.20. /;n addil:ionDl four cycles of refinerr:ent lovJered the error Indices
Rl and R2 to 0.21 and 0.13 respective1y.
Because its anisotropic thermal p&rameters wore bccomin~ unre81 istic,
the zinc position at .16, .16, .16, was deleted. The single zinc position
rema in i ng, and the frar:-'8h'ork, ref i ncd tCJ an R 1 of 0.21 and an R2 of o. 18.
At this point a three-dimen~ional electron density Fourier map ~as pro-
Ouced. r~ large peak at the origin \'!CJS assinged as a zinc pc)siti()!'~ and in-
dee d, ~,! hen t his \'J as inc 1 u de din 1 e a s t - s qua res t" e Fin em 8 nt, R 1 d r () p p ,~~ rl t 0
0.14 and R2 to 0.13. In subseauent trial structures two other positions
in the sodal ite cavity were refined. These positions, which were first
thought to be acetylene carbon positions, were assign2d occllpancics of
4, and considered to be H2
0 molecule.s.
Because it V-I,)S sLlspected that there might be no acetylene at all in
the zeal ite, it \"ras decided to assume that the structure vias completely
hydrated. Accordingly, all of tf18 peak postions not yst refined from the
Fourier map Vvere inc.luded in least'~squares refincme.;-lt .:::JS H"O positions. L
Table 31 prc::sents tile refined poslions of these P~';D~~S) and i:lith this
h y d r' ate d t r i 3 1 :; t rue t u r G, R 1 and R 2 bot ;'1 cJ e c: l' cas c c: t:) O. 1 0 . /'. s e v 2 nth
and produced finDl error indices of 0.097 and 0.032 for iZj cud R2 5 rc-
spectively.
B. Discussion.
Crystal logr0ph!c analysis has indicated that no acetylene entered
the z(:ollte. !nstecld, the zinc exch;:~nged crystul tfT,ained completely
hydrated. In 1 ight of the dchydr2t ion procc(~ure er:ipiol'cd, it is ob\/loUS
th~t this complex is very hydrophil ie. Four H'lO lTlolccules arc tetra= L
hedraaly bound to th'2 sodalite zinc, and t\:cntyfive additional
cuies are found in the remainder of the unit eel i. f\ port ion of the
Fourier map generated in this structu~c determination is reproduc~d in
Figure 13. It clearly indicates the z!nc position at the origin ( in
the center of the sodalite unit) a~d the w~ter molecules associated with
it. Final molecular geometries and distances are given in Table 33 and
Table 34, respectivc-:.ly. Tables 21 t!1ru 32 Tollo';1 the course of the
structure solution. A XORTEP cornputer plot ter dr(Jv.:i ng ~ shmvi n9 the
frame\"Jork, zinc, and 'dater positions is presented in Figure 14.
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o o ::l :J (,!)
\)', ........ ,.,j
Table 33. Holecular (' "",,-,;Y":>; r \' "I'/i f'j(:1 Z i lie <:xehanccc.i Z e.o 1 it c u \.....- _"'11',,-,"... I . '- I ... ' J
Selected intGratonic angles
?,(om A P,tO(;i B (\tom C J\ngl e in deg ree~. Deviation
0(1 ) S i p.l 0(2) 111.19 .69
0(1 ) SiAl 0(3) 111. 51 .70
0(2) S i J'd 0(3) 106.71 .35
0(3) SiAl (; (?) . \ .} 108.92 1. 17
SiAl o ( l) S i!-\ 1 157.81 .63
S j (-\ 1 0(2) S iP,l 1 Slf.)6 1.18
SiAl 0(3) S iP.l 139. Lf7 1. 19
0(3) H201 0(3) 36.24 2.15'
o (-:s) \~ Zn (1 ) 0(3) 1 1 L~ • LtS 1.22
0(3) H203 0(3) 63.42 2.02
0(3 ) 11202 0(3) 78.83 1 ,J42
H201 Zn (1) H203 171.87 .39
H206 H205 H2O? 96.31 2. 15
0(2) H206 H205 97.54 .48
0(1) H204 0(2) L~5.01 1 .09
0(1 ) H204 H203 102.55 3.36
0(1) H207 H205 104.58 2.48
0(3) Zn (1 ) H203 103.38 2.3'-f
H204 H203 H207 89.40 2.76
H204 H202 H207 75.L12 3.21
Table 34. Selected Interatomic Distances, in Angstroms.
Atom p, JUom B Distance Deviation
0(1) SiAl 1.635 .005
0(2) S i /\ 1 1 .Of5 .005
0(3) S i A 1 1.676 .006
H2O, 0(3) 2.763 .01,l9
H201 Zn (1 ) 2.Ll37 .069
H201 Zn (2) 3.060 .013
H2P2 0(3) 2.974 .062
H202 H20 l t 3.062 .066
H203 0(3) 3.592 .100
H203 Zn ( 1) 2.316 .125
H203 H20L• 2.679 .066
H204 0(.3) 3·300 .090
H204 0(2) 3·792 .066
H205 H207' 2·393 .116
H206 0(2) 3.542 .019
H207 O( 1) 3.303 .127
H207 H202 2.712 .052
Table 21. Initial refinement with only framework and two zinc locatio~s included
SUH FUGS :;:: 9591.324, SUM /OEL F/ :;:: 22544190, R =0.23502, NO~ OF REFL~ IN L.~4 = 179
THE GL:N2Kt\LIlED if'JEIGHTEO R INDEX (RZ) = O .. 19721t
NuRJ\/\LI lED SUr1 OF SQUARES OF RES IDUJ\LS :;:: 1.':.3,,060.
NE~ SCALE FACTOR FOR FOBS:;:: 3054284. T HIS I S {O lOS CAL E F ACT 0 R) T I r'i E S G / (G + 0 f L T J\ G)"')
1-\ TUI\1 Nc~~ X j\1 E\~ y Nf:H Z e 1.1. OR 8 822 OR OCC ;-,1 E ~·I [~3 :3 ri E ~1 81. ~ 1 ()~214213 o ,,21 I t 213 (],. 2 1 1,e213 (1 <> OU 1 792 ;) .,()(l1792 f) <) I):~.ll 792 ~~. ~ ~ j ,"., 1 () (j 2 o , : .. j t) 5 /'f l O,,}. 50 5 It 7 0 .. ).565'-:- 7 o ,~ 02;2 t;- 3 5 0.) 0 22l} 35 0,.. 02? It' 3 5 OQO?53? j 0 ... 0 0.179661 0.3 6 75/~ 8 0-29!.93 0 .. 500000 S r;\ L 4 c: .. u 0.,2:.;2?69 IJ ~ 5nco~)O 3')1-395 /]" 2 5C',')f)O O{l} 5 u.o 0.,300116 0 .. JOOli6 o " H o~) 1. 0.,250000 O(2) 6 00).1.53d3 O.~l153B3 0,.322197 2., 6~J03 0 .. 500000 0(3)
Table 22. Four more cycles with the just refinad positions.
SU;'1 FeeS == 1(;.J38 .. 273, S Ui"1 Ir) F L F'I ~ 2167,,830, 1"\ .:::: J .. 2 1 5 96 , f .. jl) GO (1 F ? E FL" I i'J LoSo :::: 17r;J •
j! i;: G ~': ~ I ;,: ~ /" LIZ F. D \,1 i"-: I G Ii T F. D I~ n') c r: x {F 2 ) __ = 0 • 1 7,9 It 3
j'; C i: ~; [., L I L~: D S U i'-1 (J t-= S (~ U f.. P. E S (J F R F SId U t\ L S :::-; 1 2 9 .. 6 8 /+ 11
;\i:-: I:: :; C 0. l F F.' eTC ~ F (I r~ F iJ ~1 S ::: J .. 6 f) L 60 0 T f I I SIS (O L D S C \ L E F 1\ C T D P) T I I"~ :: S G I {G -1- D t: L T .t'~ G} • .. --_. - -- - -, _. .. .,
J\TCn I! ::1'1 X !'.iF'd Y f\l f \~ L 511 DR B B22 () ;), (Ie c \:~ \-1 d33 ~l [:~'I f) I ? o • ~~ ]1. (, S 6 007. 1 /rt- 5 6 o .. 2 1/~S ~) f) 00003178 O.CC:J178 O~OOJ172 011 OU j.;'~ %q
') J • 1 (:' 7 6 'J () () • 1 (:. 7 () 0 () a • 1 () '7 f) J f~ 0.007010 o .. 00 -(01 V O .. C()7010 --0 ~ 0;) lU03 ~ , -
~ 0.0 0 .. J ~~ CPH~ 7 O .. 3S7Z':J2 O.8l5? 0.500000 S 1;\ L l- 0.0 o '" 206/ .. 8 (t o .. ::-,(;O~) 00 2,,5706.- O.25JOCO D(1) 5 0.0 O .. 3(~Cll() O.3C()710, 0.,9369 0 .. 250000 [1 ( 2 )" 6 O.1127S3 C.ll27S3 0 .. 32'1,006 2., 6 ~-;p 7 U .. ;),) 0 0 (] 0 ,)(J)
Table 23. Refinement with only cne zinc locati9~
SUM FOGS = 10722.238, SUM JOEL FI = 2:t:?7,,818 1 R =0 .. 22923 1 NO .. OF REFL., IN l",S4:-: 17()
TH[ GENr:RJ~LtZr:D t·JfIGHTED r< INDEX {RZ)::-; 0,.19363
i'PJRj·i,\lfZED sur·, OF SQUARES OF RESIDU;\lS== 172!»306"
1'1 E\'1 S C ;\ L E r- /~ C TOR FOR FOG S ~ 3 '. 9 :3 1 1 3 .. THIS I S (OLD SCALE F;.\CTOR) TINES, G/{G +, .DELTA G) <l
ATOj·1 NFH X NEH Y f\! FH Z Bil OR f3 822 OR oce Nf H G33 i',!~\-l B 12
1 0 .. 213727 O~213727 0,,213727 O~OO5729 O~C05729, . 0,,005729 o ... 0 0 Ii' 5 {r 9 .
2 0 ... 0 0.,100177 0,,, 3 66;]/;.0 0.,6156 0->500000 S I/\l · 3 o,~ a Oo?022F37 0-0 :500000 2 <t 36 1+ 7 0,,250000 o ( 1 ) l'r 0 .. 0 0.,. 300.31 () 0.,300316 0,:) [) 59 /1- 0,,250000 o ( 2)
5 0,,112380 0 ... 112380 O~323129 2., It- 529 0:»500000 O{3) C'...,
Table 24. Four more cycles to refine this position.
s U ~·1 r: D i1 S :.:, S ;·1/3 7. 11 6 q '5 , S U :·1 I D ~ L f J -:: 7.. :J 7 7 G or; 7 7 R -:-: () • 2 1 0 1 7 f NO. 0 F P. E F L... r N l., S ...:-: 1 7 <)
r Ii F G t~ N r: F ; \ L r l ': 0 ~'j F. I G H TeO R I N D F X {R 2) :: . 0 9 1 -, 9 3 0
1'·dJC::<,\LIzro sun fJF S()U/~Pf':S OF Ff~SI[)Ui\LS -:-: 125...,508.
,.~ F ~,; S C J\ l r.: r: ~\ C T n F r- Ll FZ F 0 ~3 S :: 3,~ 6 26 1 7 0 T II I SIS (n L D S C \ l ~ F J\ C r CI R) T I tV,: S G I {G {- f) E L T J\ G)'J
~.Tr:f1 N r? ~., X N f ~'J Y Nf\-i Z B 11 OR 13 B22 UR nee NF:W B33 i\l r: 1.-1 B 1 2 1 0.213737 0 ... 213737 0 .. 213737 O~OO3573 'J~OOJ573 0,.003573 o cO OOJ/.-9<1 1 O,~ 0 0 .. 1 eo ') e /,. 0,,36(,950 003733 t),., '500000 S I !\ L 3 0 .. 0 O.20]f)iJ3 O~500000 ~ " 'r'<~ 7 OJ.)Z50000 o ( 1 ) {~ 0 .. 0 O,,300n31 Oo300;i31 1 , 0 f)5 8 0,250000 D{Z) 5 0 ... 1-12629 0 .. llZf: ~29 O~3230Ha Zo9083 0,.500000 0(31
T""l ?.... R.c· '!. ( aD e ,-:J •. 8. Inement It/lt 1 a zinc at the origin found in the Fourier map).
SUH FOBS.= l0455~547, SUN IDEL F/": ,. 1508.700,' R :0.,lL}430, NO., OF REFL. IN l .. S. = 1.79
THE Gt\l ERAL I lED ~1c I GHTED R INOE X (R2) := [) .13241
NORMALIlED SUM OF SQUARES OF RFSIOUALS = 76.617.
NE~ SCALE FACTOR FOR FOBS = 3.83644. THIS IS (OLD SCALE FACTOR) TIMES G/{G + DELTA G)~
- AfOM-- ,-- NEH X'-'" --------NEVl Y-----
1 J~2i313~ 09213133 Z - O.v 0 .. 18 277 3 0.0--- -- 0.20 652 L~
5 6
O~O
o .. i i ~ It- 45 0.0
0.301884 O~112445 OQO
f\l E W l ---- - ------ --, B 11 0 R . B -- . S 2 2 0 ROC C --- -- ,-.. N E 1,-1 B 3 3
0.213133 0 ... 003261 o~on3261 O.()D3261 0", 3 6 6 7.27 0 .. 8 J.O 4 -0 '" 5 0 0 0 0 a S I A L o • 5 00000 2 .. 2 12 3- .- . -0 0 25 00 00' 0 ( I ) -O~301884 1.8891 O~25Q000 0(2) O~323701 3.2326 O~500000 0(3) 0.,0 -, 3,,5218 0<3020833 IN{2
-- NEW 812 o~n04~J4
Table 26. An additional four H20 molecules have been included in the sodal ite unit, on the three-fold axis.
_ SJI1 FJ8S = 1(';386 .. 180, SUr1 10Ft FI = 1354.372, R =1.13~40, NO. OF R~FL. IN L.S. = 170 -- -- - -- -~ -_ ... ~- -
THE G E \l E }< A L I lED ~I E I GH T I: 0 R I i'l 0 EX (R 2) :: 0 ~ 12 380
-." -,. . -- ~ ---.- - .-.- - ._-._"-- - - - ---._-_ .. _---_._---- - -- -- ._.-_-------\lJ~~~_IlED SUM OF SQUARES OF RfSIDUALS = 66.089.
~E~ S:ALE FACTOR FOR FOBS = 3.3!11~~ THIS IS {OLD SCtLE 'F-ACTORr'-'rIMES--G/{G +--Oc.=L"Ti\- G}-~
t;. TO'1 \j Ell X NEH Y NEH l [311 OR B 822 O~ DeC Nt~1 B33 !',U=;'l ~ 1 ~ J. ).213J.24 0.21.3)24 0.213124 0.00332S 0 .. 0033?6 0 .. 003326 O. OOl~ os! 2 0.0 o .18 ~_ 386 0.366631 . 0.83fl3 0.500000 S I tll 3 ).) r.?'~~J698 .) " 5 r ') ~) {) (l 2 .. 35 / ... 9 /) .. 250'")00 (l ( ~) 4 O~Q 0.30}. 73 ~ 0.301732 1.8632 0.250000 o (;?) ~. ~._ 0'"- ••
5 J .. J.1Jt J 97 o co J ~Jr 1 S7 0.323563 3 .3 l !-71 0.500000 () ( 3 ) 6 J.O _ r..~) 0.0 3 .. l}-595 0.020833 IN(?. 7 o .. 0 <31 5 /tl o ~O rn 5 1tl O,~08154t 5 1> 9501 0.083333 H2nl . -. _. --. ~.~--. -. ..
\ ,--..
c\ . ~~.~ .
Table 27. Refinement with the sodalite waters taken off of the three-fold axis,
SUM FOBS = 10414.047, SUM IDEL F/ :: 13l )-6.603, R==0<9!.2931, NO. OF RCl-l. IN l",S.:: 179
T H t G E \ll: R A LIZ ED \.; E I GH TED R I N D E X (R 2 ) :: a • 12 3 "3 8
"ljK>1/\L-r lEO SUM OF SQlJARES---OF--RES IDUJ.\L S---:-- 65 ~ c)93.
r'~Ei" SCALE F.~C{OR- fOR-FOGS :: 3~Bi.919;--- THi"S-IS(OLO SC"\LE FACTO~) TrH~S G/(G-+ DELTA G).
{,TO:'" t\ E ~~ X NEH Y NEW l B1J. OR B B22 OR Gce NfH B33 N [~.; (3 'i. 2 -; O .. 2)'3l.00 O.2:i3JOO a ~ .2 .l 3 1. 0 0 o ~ 0 () 13 It'r O .. OO33 /t t t 0 .. 003 3"tt/t -- 0,. OO(~:: SL. J.
2 0'$0 o .. 1811~C 5 0.366616 ,:.8356 fl.o 5 1):.;r.\ nn SIAL :, o.v O.20J3B5 0.500000 2 .31 79 0.250000 0(1) It 0.0 0.301570 00301:;70 J " "161 7 0.250000 O(2)
- - ~ ..... -.- - -- ._.- - - - ~- --
5 ~) .. 1 1 '-tA· 5 1 C' • ). ].It- II- 5 7. f) '" 3 ? J 8 7 It 3 .. 3123 r . 5 (L) 'j (. r 0(3) 6 0 .. 0 0.0 0,020833 IN(2 Cf'
0 .. 0 3 .. 5264 \..0
7 o .. 0 :>'1' 209 o .0 'i5 6 76 -- _.- --" - ----'-" .--- ---- .
0.095676 a It 932 0 0 .. 083333 H201
Table 23. Refinement with the sodalite waters back on the three-fold, and four additional waters at .31) .31 .. 31.
~UM FJBS = 5168.180, SUM ID~L F/ = 625 .. 221, R =0.12098, NO. OF REFL. IN L.S.:: J7Q
THe Gt~ ti~AL-I L,::D wE I Gl-fTED-R-- INOE-X-(~~ 2)"' -= -'-0-.11625- ----' •
I'~ 0 K :·L\ L I lEO SUi·' 0 F S () lJ ,l'. RES 0 F RES IOU A L S = J. 4 • L1' 28 •
i'J t: .~ SeA L E F A e TOP, FOR Foe s :: 1. 8 9 6 79 • THIS IS (OLD SCAL2 FACTOR) YIM~S G/(G + D~LTA G).
1\ TU,'1 NEw X NEW Y N Ei~ l B 11 OR B 1322 OR fJce NE~'; B 3 3 i\! E ~~ S!. ~ 1 0 .. 213301 0 .. 213381 0.213381 U .. 00338"5 J ",:J n 33 85 r:' • (' iJ 3 3 8 5 r .it '13 ~16:3
--. --- - .. - .- - ~ _.. ---
2 :l.1) O.J81563 0.366759 0 .. U3 l r5 0.500000 S LA L j 0.0 o • 2. 0 ~. Lr 2 6 0.500000 2.t.~735 0.250000 0(1) It 0 .. 0 I:~ • 3 (; J. 3 3 2 0 .. 3 .,~ 1:3 E3 2 1 .. 97 /t-3 n .. 2 5~1:1 C~ J 0(2)
- - - .. ---,"--~.-.
5 J.ll:)823 o .. ". 1. 3 U 2 3 0,.325250 3 ~ 8!.?. 7 O. :-:00000 O(3} 6 U .. O 0.0 O~O 3 • 3782 0.020033 IN(Z 7 .; .(;331 75 (:.l)H3175 ;J • !j B 3 J, 7 5 6 .. 69!t3 C\.C~33333 H201
- -
8 0.3064136 O.306~a6 o. 3 06!~86 4.290J. 0.083333 H202
Tab 1 e 29. The firs t H20 pos i t i on was at first erron i ous 1 y ca 1 Led __ a .carbon---. ...... __ ._. ____ .. __ .
su~ FJBS = 10311.785, SUM JDEL FI = 1267~169, R =0.12289, NO. OF REFl. IN l~So = 179
THe GeNERAL I ZED WEIGHTED R INDEX' (P2) = o " 11593 - .-. -'. -.. - .. -.-..... -..... -. - ... -. ---.--. -.-.. ."-...... - .--._. - ..... -....... '" ...... -.... - .
NOR"\i!\lllED su;~ OF SQUARES OF RESIDUALS:: 57.12!t ..
NE~ SCALE FACTOR FOR FOBS = 3478348 • THIS IS (OLD SCALE FACTOR) TIMES GJ(G + DELTA G}~ . _- - --,_. -".,- .. _... --- -- ' ... - ---. -- _._._-- - ------ ._---- .
A T 0:'1 N E~~ X NEH Y NEW l B 11 OR B B22 OR OCC i'lEH 833 rlr:H 812 1 J 0 ~ 13 4 07 0 .. 2 j, 3 L:·07 0" 213 /r07 0 .. 003363 0.:.003363 04003363 0.003583
..
2 0",0 0.,,181383 00366799 008509 0.,500000 S I t\ L 3 J<tO ,0 .. 2J 1 7/+5 O.500DCO 2;)5318 o .,2 5 ( .. ;J (. f) 0(1 )
. It' Q ... O 0 .. 30:'003 0" 30J. 003 1 "aO'39 0 .. 250000 0(2) 5 0.,112810 0 .. 112810 o~ 3250/1'3 3 a 9592 0.500000 0(3) ~~ 6 0,0 000 0 .. 0 3.~ i r373 0,,020833 IN(2 7 0 .. 083253 0 .. 083253 0~08J253 7 .. O!j91 0 .. 083333 H20l e 0.312617 0,312617 0.312617 1 ~ O~)(:-O 0.,083333 C(l)
."- ,."-_ ••. --. -p- p •••
Table 30. And another carbon was mistakenly assigned a H20 position.
su~, FJuS = 3.0329.895, 'SU,\1/DEL'F/'; ·-126J.ol)33-~ R =C.12208,- NO~' OF' REFL ... 'IN L'oS~ = 179
THE GENERALIZED WEIGHTED R INDEX (R21 = O~lJ. 700
~O~MALIlEO SUM OF SQUARES OF RESIDUALS = 58.393.
NEw SCALE FACTOR FOR. FOBS = 3.78920~ THIS IS (OLD SCALE FACTOR) TIMES G/(G + DELTA GJa {\ TOH N E~~ X NEW y"'" NEH l Bl1 OR B'" 822 OR' oce' NEIl' 833 ---'--- "Nc~'1 812 1 ).213398 0.213398 0.213398 0.;(:<"'3323 0,,003323 0 .. 003323 o .003 5l~8 2 0<:>0 0.181350 00366818 0.8 /1'56 0 .. 500000 SIAL 3 0.0 o Q 203. 759 0.500000 2 .. 555? 0.2500G':1 0(1)
It- 0.0 0 .. 301057 0.301057 ). • -r 7? 3 0.250000 0(2) 5 0.112662 0 .. J.12662 0 .. 32 /+561 3 ~9787 0.500000 O(3) 6 0.0 0.,0 0.0' 3 .. /~ 851 n q::~ 2 (, 833 IN(2 -. "-'- --. --.
7 0 .. 083143 o .. 0(331[t3 0.,0831Lr3 "7 (t29 l 1-0 0 .. 083333 H2O]. 8 0 .. 31.1.<)02 0 .. .311.'702 O .. 31}.902 o .8 7 /t4 0;)083333 C ( 1 ) <) 0 ... 260655 ,} ., 3 () (~ 6 5 5 0.36(:655 15 .. 3 /-+61 00C83333 C(2)
Table 31 .• Reflection 2-10-15 has been deleted. All peaks are added as waters, S U ~·1 F 0 () S -:: .. 11 R. 1 ~~ • 0 66 , S U H /0 E L' F / = 1 2 ::, 1 • 0 56 t . K -:: 0 • 1 0 4 19, .
"HE G'r~:~R;\L I ZFD \.Jr: IGHTCD R 1rJDfX {P.2) ":: 0.10164
NQQ~AlIZ~J SU~ ~~ SQU~PES OF RfSIDU~LS = 31.424.
N r- i·J SeA L f: r 6 C Tn P. r (j R F 0 a s = 3 .. If 03 t., i) • T If r SIS ( () L D S C /\ L:: FA C T 0 ~) T I t"i:= S G / (G + 0 E l TAG). GIS N r) T C (.j:" :'1;') ;:: D
,T{if·i
1 2 3 14-
5 6 7 p .
g
0 t 2
N r- ~~ x f-.lfhl y - - --r'
-.~-~--------- ~.- -~
" "-\ --=-. --= . -- - -- - -------~---~
HYDRRTtOZN~.ONR2-ZtOLITE R
_ _ ~~ c.r2':J!ns c'f the hydrated zinc zeo1 ite Fic.ure 14. Computer .nlc;t7p.~ I
The Successful prepar2tinn of the sto!chiui,,:::tric, Jiva1ent:1y ex-
changed zsc.l ite 11, in thi S vJork \.Ji 11 a11m"} future ~'JOrk to proceed in
introducing substrate 0;4 1 igand species into th;: exchanged zeal ite, for
the purpose of mimicing the geometry or action of these ionic ond
zeolite could be pdftiBl 1y dehydrnted ond then CO2 could be introduced
into it. Crystallogrc-:phic study of this complex l1!ay then elucidate
the mechanism of catalysis of Carbonic Anhydrase, which, containing zinc
at its active site, promotes and regulates the equil ibrium;
CO iJ 0 - __ '.;lI!o t' "0 . 2 -!-1 2", - rl i.. 3 .
in u sirniliar- manner, the other exchanged zeolites eouid nInde, upGn
introduction of specific specles~ f:~any of the other enzY~ilatic metal1o-
proteins, providing they catalize reactions involving molecules which arc
small enough to fit into the ze,Jl ite cavities. The use of the ;;:eol itr-; CQin-
plexes in this v:iJY, could then quickly ctnd inexp;:,:nsively produce biologi-
ca) models of enzyiile systems which presently ~ire studied crystal1ographi-
cally at the cost of much time and nnncy in entire three-dimensional
protein structures. Often, these completed protein structures are still
unable to allow postulation of the specific action in cataiysis, thus any
results at all from a zeal ite complex nodel system would serve to progress
the understanding of this catalysis.
The results of the sorption work in this research also Gncourage
further v,Jork with these model sySt~~;'15. !l,lthou'Jh not yet ent irely satis~
f2ctory, our sorption methods can now be anal izcd and improved.
68
/.iJ'FEND I X .11.
1) The PI Diffractometer·
r,) f) <, rfr-·,..j-""'li~;,t·Or C;'I'l·'.PU i-L .- t. ~.- ..... \.J'I.·~'#_'-' l ... '"
/ ~ ..... =:!J compute" ~ ~
/ magnet~C
tape input
moun te.d cr:.y5 tal
0perator control console
~
phi boX
1) The pI Diffractometer
-,-t ~ :1
\' ; '~ . I
f~ i; fi ~ J
H , , .,.'.: I'
~ j I' ~ ~ i .t
',~ ,
~ .-;
I! .1. ~ ' , ;-'1 i 1 t~ )
'. l', z..l ~ ,. 1 '
~' ~
i } I ! , !
; , I ; " j
r I , i ~. f ; J
1 \
\<
1 '1 If ;> ~ " .. !
'1 1
i , j
70 ~,- ... -- -'
... ..!- ••
6676666676666666 -~~~~
412 828 331 42 19 55" 80 3(2 2 3 18 '64.77 32.33 352 .. (;0' 348.13 2.44
6666666666666666 331 672 326 7 18 550 ! 6 363 2 3 19 6S~ 69 34.35 352&24 3470 60 2.47
6666656666666656-355 696 " 365 -12 \ ' 18 551133 364 2 4 4 20.17 10.08 031.73 19.25 2. 12,
8887787888777777 '-
1024 2044 912 54 31 55047 . I -365 (3 " 6 20.16 10g08 356~9 6 3374083 ' 2. 12
766SS9ABCDDCA98B 1027 22907 1545 10166 79 55~ 6~
'/
-355 (1 5 , 5, 23e8l 11.91 319<144 3.92 2$ 15 ' 77B899ACDDCA9688
857 17379 ' 1175 " 7923 70 55" 75 367 2 4 5 22.51 rl
1'1.29 '335&21 13.81 2. 14, i', , ,
7777777861777777 860 1843 757 113 29 55.90 363 2 4 6 25~22 12tt 61 3371167 ·9. "l2 2. 1 6 "
7771777777777777 \ • \ ~!.
781 1473 ',740 "24 27 56~04 I,
369 2 4 7 26.05 14-03 ' 339,,97 5085 '2. 17 7'/77S3f39A9987777
760 3214 763 8L~5 '34 560 19 370 2 4 8. 31.02 15951 341 CI 67 2.94 2019
7777777886877777 674 1826 683 ,23,~ 28 56033 371 2 4 ' , 9 ' 34010 17.05 343006 .53 2.21
,/,7777777877777777 ' -
7,,~3 1482 591 71 26 56Q1/j8 372 2 4 10 37~28 180 64 34L~<> 22 353it 51 '. 2.23
7777767767766767 '\
570 lOS7 .504 ' -8 23 56063 373 2 4 i 1 40.54 20.27', 345,,21 356(180 2.25
," 7667666676667666 456 953- 472 15 21 56;) 78' 374 2 4 12 43088 21~94 346.06 ,355034 2.23
2) Diffractometer output sample. 1st ro\',; the reflection peak
2nd rov!; sequence number, h, k ,Q,2. e. J W , ~ , X, scan range, scan rate
3rd rm'i; left background, scan count, right background, intensity, standard deviation, exposure hours
A negative sign in front of the sequence number desfgnates a check refiection.
.50
,.50
050 .
I'
:" • S0 j
e S0
.50
.50
• S0
.50
'.$ S0
~'SO
.50
.50
"
I
,
71
•
f.;PPEND I X B
1) a sample of the LPCOR output
2) a sample of the P P.Cr~EH output
3) a sample of the F!'~LS output
4) a sample of the V,GEO/", output
Sarnples of Oi\~r:P and SFC-I\LFF Fourier
map outputs have already been presented.
.iJ
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0 0 1 10 64 4 • 513 • 17.1156 0.9'~99 1.uOOO 33. f3.~ 7.58 750.0 70.3 6. b j 3.35 356.96 B7. a3 0.50 2.040 0.5 5ll0. 10636.
6666666666666A66A6A66666~b66666676667777777777777777776666666666666666A~6h666666A6666666666A66~6
0 0 2 750. H '). '3.5244 C.Y99':l 1.0000 9.313 4.5;; 2528.0 70.6 10.04 5.02 3'56.16 3 j7. HJ 0.6 0 2.061 0.5 40'J~. 12/.88.
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10459.5 79.6 20.16 10.u') 356. 0 f) 317.'j 3 1.12 2.123 a.5 1059. 2~113.
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0 0 6 10467. Ln. 2..72~·3 C.9<i13 1. GOG 0 61.97 2.33 311.5 30.FI 2j.57 11.7tl 3:)D.'iA nLt33 1.26 2.144 0.5 841. 2211.
34443J434343334434444443~43334334~45445~55~55S~55~~~5544544444444443433433j3432333344343343244j3
0 0 7 312. J? 2..2 0 77 C. Ci QQ2 1.0000 11.65 1.5'.:) 74(\.0 33.5 26.99 13.50 35b. rJ 6 33T.el3 1.<'0 2.166 0.5 746. 2 Q (H.
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1). lPCO~ computer program output.
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-, • 3 "" ,-''-.7 ~" .',."1" ')., e-
~ • ~ {!.* .~ r; '" ~)" ~ 1\ /. /~ ;: C'
'. " ' 1 ,... I .. ,~ ~ ~') •. ~dll.'~ .;
;:. 71)<'.(..
~. 2 J '} 7'; ~
;-' }.. :-),~
"': " .
'.,J C)
7S
{WPEND I X C
I, '
Chcmic2is Utilized
1" acet'/lcne .,
2., ca 1 c i um nit r2lte .,
30 chromic nitrate .,
40 cobalt nitrate
50 cupric nitrate
6. gold cluride 0 o
7. ferrous sulfate 0
80 manganese p~rchlorste •
90 se 1 en i um " . 109 silver nitrate
110 sodium aluminate
12 .. sod i um n'¥..;tas i 1 i cate
1 3 • tell uri urd
140 triethanolamine
15. zeo 1 it e A o
160 zinc nitrate
crystals, Mal1inckrodt Chs~ical Works
reagent crystc:.ls, hathe.son, Coleman & De 11 Matheson, Coleman & Bell
J.ToBaker Chemical Company
reagent grade, Merck Comp~ny
JoToOaker Chemical Compony
The G.Frederick Smith Chemical Company
reagent crystals, HBtheson, Coleman & DO 11 Research Organic/Inorganic Chemical
Research Organic/Inorganic Che"lll i c21
99.5% pure powder, Matheson, Coleman & Be 11
Matheson, Coleman & Bell
powder, Linde Company
Corp_
Corp_
crysta 1 S, i"~d 11 i nckl·odt Chcmi ca 1 Horks
81
8l E::L! OGH;-'\PHY
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370 JQSoHood, HGEO!1 Computer Program, Mellon Institute, Pittsburg (1964)
380 C.K.Johnson, CRTEP, Report ORNL-3794, Oak Ridge National Laboratory, Oak Ridge Tenn .. (1965)0
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33
l~ t • 373 (1967) 0
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47 P eR· 1 d K S ff J C' <: C' I" 12 07, (1 cf/?) 0 o ci.." I e'l an ,o~e·, __ nem. ::!"s!£o ...12£r.!2. ~mm., v ~ ....
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