384 J. Chem. SOC. (A), 1970

Crystal and Molecular Structure of D-Histidino-L-histidinocobalt(ii) D i hyd rate

By Rosemary Candlin and Marjorie M. Harding, Department of Chemistry, University of Edinburgh, West Mains Road, Edinburgh E H 9 3JJ

The structure of D-histidino-L- histidinocobalt(l1) dihydrate, Co(C6H8N,0,),,2H,0 has been determined from three- dimensional X-ray diffraction data. The crystals are monoclinic with a = 10.04, b = 11.1 0, c = 15.31 A, p = 11 1.6". and space group P2Jc. Positional and anisotropic thermal parameters were refined by least-squares methods; the final R for 2342 observed reflections is 0.1 1. The cobalt atom is octahedrally co-ordinated to the amino-nitrogen, an imidazole nitrogen, and an oxygen atom of each histidine group, at distances between 2.06 and 2.1 6 8. One histidine group in the molecule is D and one L; the imidazole groups are cis to each other and the molecule has no symmetry. The two histidine groups differ in conformation, chiefly by a twist of 26" about the CB-C,bond, and this can be attributed to their very different hydrogen-bonded environments.

THE structure of D-histidino-L-histidinocobalt (11) di- hydrate (I), the complex prepared from m-histidine, has been determined and is described here. This is one of a

//N \-CH2-CH< NH2 ] ,2H20

'02' [Ha,// CO.0- 2

series of studies of metal-histidine complexes 1-3 from which we are building up a picture of the possible vari- ations in conformation of the histidine group in relation to its environment, and the variations in the preferred co-ordination arrangements of divalent ions. Some of the stereochemical information may also be relevant to an understanding of the interaction of metal ions with histidine residues in enzymes. Bis(histidino)cobalt has been of particular interest because it is able to take up oxygen reversibly in aqueous solution and might there- fore be a model for biological oxygen carriers4 McDonald and Phillips 5 have used n.m.r. to investigate the interaction between histidine and Co2+ ions in aqueous solution. In different conditions of pH and concentration they showed that 1 : 1 and 2 : 1 complexes exist, that the histidine may be a di- or tridentate ligand, and suggested tetrahedral and octahedral co-ordination arrangements. Further, they showed that in solution the complex ion Co(D-hist)(L-hist)2f is more stable than the ions Co(~-hist),~+ or Co(L-hist):+ [hist represents the group in square brackets in (I)]. We have prepared crystalline Co(hist), from both L- and DL-histidine and in view of the above results were not surprised to find that they have entirely different cell dimensions and structures. The structure of Co(L-hist)2,H20 has already been described; here we describe the structure we have shown to be Co(L-hist) (D-hist) ,2H20, i.e. the cobalt ion is co-ordinated to one D- and one L-histidine group. By contrast, the crystals prepared from DL-histidine and nickel ions were shown to be Ni(~-hist),,Ni(~-hist)~,2H~O although the

M. M. Harding and H. A. Long, J . Chem. SOC. ( A ) , 1968, 2554.

K. A. Fraser and M. M. Harding, J . Chem. SOC. ( A ) , 1967, 415.

R. H. Kretsinger, F. A. Cotton, and R. F. Bryan, Acta Cryst., 1963, 16, 651; M. M. Harding and S. J. Cole, Acta Cryst., 1963, 16, 643.

crystals Ni(~-hist)~,H,O are isomorphous with those of the cobalt complex.

EXPERIMENTAL

The crystals were prepared in the same way as those of bis(L-histidino)cobalt monohydrate except that DL- histidine was used.

Crystal ~ata.-Co(C,H8N,0,),,2HzoJ &f = 403, Mono- clinic, a = 10.04 f 0.04, b = 11.10 & 0.04, c = 15.31 &

D, = 1-69. F(000) = 836. Space group, P2,/c, Mo-K, radiation, A = 0.7107 A, p = 11.9 cm.?. Cell dimensions were measured from precession photographs.

Intensity Data.-Intensity data were recorded on pre- cession photographs and measured with a Joyce-Loebl recording microdensitometer, for the layers 0-5 up each of the axes [loo], [OOl], and [loll and for the layers 0-3 up

0.05 A, p = 111.6 f 0*4", U = 1586 Pi3, D, = 1.63, 2 = 4,

TABLE 1 Analysis of agreement of observed and calculated

structure factors

Range of

0-8 8-16

16-24

IF1

24-32 32-40 40-60 60-80 80-100 > 100

Number of

reflec- tions 246 785 526 327 164 214

74 36 11

R 0.46 0.18 0.107 0.089 0.067 0.073 0-082 0.105 0.09 1

Range of

sin2#/A2 0*00--0.05 0.05-0.10 0.10-0* 15 0.15-0.20 0.20-0.25 0.25-0.30 0.30-0.35 0.35-0.40

> 0.40

Number of

reflec- tions 151 259 323 323 337 350 279 189 172

R 0.106 0.089 0.085 0.090 0.124 0.123 0.147 0.158 0.190

the axes [OlO], [loll, and [ZOI]. Two crystals were used, each approximating to a cube of side 0.2 mm. For each layer several exposures were made with times in the ratio 1 : 1/3 : 1/9 - - 9 and film factors were determined experi- mentally for each set. Lorentz and polarisation corrections were applied, then scale factors for each layer were derived using all reliable reflections common to two or more layers and a least-squares procedure ; all the data were assembled on a common scale. Of the 2342 independant reflections measured 2000 constitute almost complete coverage of

D. Burk, J. 2. Hearon, L. Caroline, and A. L. Schade, J . Biol. Chem., 1946, 165, 723; D. Burk, J. 2. Hearon, H. B. Levy, and A. L. Schade, Fed. Proc., 1947, 6, 242.

C. C. McDonald and W. D. Phillips, J . Amev. Chem. Soc., 1963, 85, 3736.

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Inorg. Phys. Theor.

TABLE 2

Observed and ( :alculated structure factors

lOFc - 1 113

- 2 2 6 - L .$ < ? t i

-121: - / J 6 -3b4

3 ,"? -??7 :? 0 4 2 9 2

- 7 4 1 -166'1

3.3 [ J

h 12 -178 - )5$

4 5 tl 5 7 7

-5f.c -1'11

1 'i li 1 i l 7

- L 1 5 6 ? -?i

1 d o 2 -70'1 - 1 5 6 2 1 1 s -195 - 3 L J

4 Y C 3 2 4

2 1 I 1 5

- 1 4 8 - . ~ l , ~ ,

2,.)3 tl 1

- 3 c z - 132

127 :t t! :i 1 4 8 1 6 1 'I 6 'i

- 1 17 -'194 - 1 e 3

: IJ? - 7 3 0 - 4 0 ' )

2 4 7 7 s

- 1 C 3 3 1 2 4

- 1 1!4 -51: 3 2 '1

- / , ( ! 1 , - 3 8 4 6Vl

- 1 4 I 1 3 5 1 3 0 - 3 2 1 1 4 150

-178 - 1 6 9

-3c> 7 0

- 3 3 3-55 ' I 0 0

- 7 c I b 3 2 2 .JO2 2 2 2

- 3 l d - 3 6 1

.35 1 - 1 7 5 - 1 1 1

-5211 - 7 7 3c10

- 1 5 4 - 2 7 2 -1.90

4 1 6 <> 2

-267

- 2 '1 R 3 7 2 21

- L G 4

- 8 - r

t o r

i e

4 -r

h k I lO[Fol

0 7 1 a4 0 6 1 5 3 6

0 7 L 1 3 3 0 7 4 4 2 1 0 7 5 3 c > u 7 6 110 o I .3z,i 0 7 b 3'3% c 7 < I r1 5 0 I 1 U 27'1 0 7 '1 1 2 3 4 u 7 12 5 4 (? '7 1 3 L U L 0 7 14 12h U 8 IJ &!H 0 ti 1 47cl G ti 2 2 4 2 0 b 3 231 0 8 4 2 5 h 0 ti > 2 4 2

0 6 3 143 0 8 ' I 2(13 0 8 13 1 3 1 0 8 1 4 I u Y 1 3 1 4 0 L I 2 ' ) I >

0 9 4 2 3 5 C 9 5 2 I 6 0 9 6 2 3 0 u 'I a L 1 0 Y ' 2 6 4 0 5 10 z 3 2 u Y 17. 75 0 Y l 3 1 0 l i 0 2 6 4 0 1 0 L 4 4 L 0 LO 2 1 6 4 0 L O 9 2 3 7 u ti: J, 12') u li: 10 1 3 3 u 11 1 1 3 1 0 1 L 2. 7 u 6 L' 1 1 3 L Z L 0 1 1 't I 3 7 u 1 1 5 2 1 7 0 1 1 6 140 0 1 1 7 212 0 1 1 8 1 4 6 0 I 1 ' I 195 0 I t 10 1 0 2 u 12 u 4 2 3 0 12 1 6 3 ti 12 2 224 0 12 3 4 3 0 1 2 4 173 Q 12 5 12b 0 1 2 6 152

0 13 3 6 1

IJ 13 5 1 4 0 0 1 4 0 115 0 1 4 3 2 2 1 1 0 - 1 6 1 1 3 1 0 - 1 4 Y:! 1 0 -12 17'5 1 0 -1u I 1 5 2 1 c -:I d 5 1 1 0 - h 1 3 ' ) 1 0 - 4 '14L 1 C -2 9 0 5 1 0 0 151 1 0 2 13') 1 0 4 2 S ' J 1 0 6 6 3 3 1 0 1u 2 6 J 1 0 12 2 2 2 1 0 I h 4'1 1 1 - 1 9 115 1 1 - 1 3 1 2 7 1 1 - 1 7 ' )7 1 1 - 1 b 156 1 1 -15 125 1 1 - 1 4 2 4 6 1 1 - 1 3 3 6 3 1 1 - 1 2 2 5 3 1 1 -11 320 1 1 -10 2 3 3 1 1 -'I 3 1 5 1 1 - I 12L 1 1 - 6 5 h 1 1 - 4 5 4 4 1 1 - 3 6U1 1 1 -2 ,717 1 L -1 . l 3 d d 1 1 G 7 9 3 1 1 1 4 3 1

1 1 .3 2 0 3 1 1 4 237 1 1 5 2 5 3

o a c, L Y U

o 13 2 1 2 6

3 1 3 4 14'1

i 1 2 3 R 9

lOFc 7 # >

-LO4 - 1 4 2 - 3 ' i G - z 0 .I

9 c, 2'4 1

-3 6[* - ' I 1, 2 9 4 2 1 L -13 - H')

90 . I t >

482 2 3 3

- 2 1 7 -29 1

2 h CJ 16'1

- 1 3 6 -I?)! -127 - >

-24 1

1 7 2 - 1'74

- 3 2 L.! - 6 4 - : 4 :1 1 L 4 'i ' I

- 1 3 3 - 2 4 4 16 1 1 1 / 1 7 0 L 1 9

-210 - 1 7 6

1 7 3 1 3 4

- 2 1 1 - L 2 8

204 9 i,

*, 2 3 7 7

-25.3 6 .>

111 2 -2s

- 1 3 5 i3 11

- 0 2 1st; 159

2 6 1.07

- L Z A 125

- 1 S U I L I S - 793

- 8 1

l t i 7 2 - 1 7.1

2 0 z 0 0

-',h7 - 2 4 5

1 7 1 h 0

2 ou -12'1 '1C6

1 3 7 1 0 1

-22CI - 3 7 'I

2 2 1 462

- 1 7 8 -3cz

6 1 74

-1122 -76U

f ig9 1 4 1 1 - 7 4 6 - 3 6 4

!> 4 5 261 176

- 2 6 3

- 2 L h

-3bh')

h I 1

1 1 1 1 1 1 1 L 1 1 L 1 1 1 1

L 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

1 1 1 1 1 1 1 1 1 1

1 1 1 1 1 1 1 1 1 1. 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

k 1 10IFo( 1 t, .3 a o 1 7 3i)Z 1 2 1RL 1 [i I B .> 1 I U 2 7 1 1 I1 119 1 I L 1 0 4 1 13 118 1 1 4 I 3 3 1 15 1 3 3 1 I I 9 5 1 1 ' 9 d 9 2 -15 114 z -13 2 3 7 2 - 1 2 lc16 L -11 3 1 1 L - 1 U 1 6 ( > 2 -9 46 t i 2 - 8 494 2 - 7 E4S 2 - 6 1 2 4 2 - 5 1 C Z h 2 - 4 528 2 - 3 775 2 -2 4MO z - 1 158

2 1 3 7 7 L 2 14: L 3 17a z 4 I 0 5 1 2 . s 2 1 8 i i , 4 4 1 2 I tlij

L ri M'I 2 3 5 9 2 2 li: 194 2 1 1 2 7 3 2 12 34<J L 14 10'1 2 1 1 , Y L 3 - 1 6 2 4 1 3 - 1 5 1 3 0 3 -14 203, 3 -13 1 1 1 3 -12 26.G 3 -I(> 1 7 / 3 - d ')2c

L c a 5 2

3 -I <!8 3 0 5 4 6 3 L 70 ' ) 3 z 8 0 2 3 3 2i33 3 4 3 2 3 3 5 314 3 6 506 3 8 &t! 3 9 1st 3 10 1 '14 3 1 1 155 3 1 3 97 3 14 3 0 1 3 15 h' , 3 1 6 113 4 - l I 83 4 - 1 4 1 1 4 4 -13 1 I . t 4 - 1 1 ti2 4 - 1 0 1211 4 -'I 2 0 ? 4 - Y 52,; 4 - ? 'tbl 4 - b 5 0 1 4 - 5 3 2 2 4 - 4 4 h 4 4 - 3 8 0 b 4 - 2 2 0 4 4 - L 116 4 c1 2 2 0 4 1 427 4 2 6 1 1 4 '3 6 L 4 4 165 4 5 3175 4 rJ 2 9 2 4 7 4 3 3 4 8 322 4 9 5 5 il 4 1 u 6 2 4 11 4 6 5 4 1 2 1 5 3 4 1.3 1 4 1 4 1 4 1 4 7 4 13 eU 5 -15 2 6 2 5 - 1 4 1 1 4

1 1 1 1 C')

-332 - 4 (1

3 9 1 4 3

- 1 2 2 - 9 !?

27 - 1 (.> 3

6 1 4 5 5 t ;

-59.3

5 16

110 i 4 3 1 9.3

- 3 5 3 - h C 4

6 0 - 1 6 2 - 3 0 2

2 6 4 4 61,

- 2 7 5 -437 9 3

i 5ii -1 3 6 -1111

145 - 16

- 3 10 -133

- Z C h

- 1 r m

1: 7 7

h k 1 1 5 - 1 3 I 5 -1U 1 s -<I I 5 -t;

1 5 -6 1 s - 5 1 5 - 3 1 3 - 2 1 5 - I 1 5 0 1 5 1 1 5 2 1 5 3 1 5 4 1 5 1 ; I S t 1 5 7 1 5 6 l S 9 1 5 1 C 1 5 11 1 5 12 1 > 1 4 1 5 I 6 1 5 17 1 6 - 1 1 1 6 -13 1 6 -8 1 0 - b 1 6 - S 1 6 -4 1 6 - 2 1 6 - L 1 h 0 1 6 1 1 6 ; 2 1 6 3 1 6 4 1 6 3 L h b l b l 1 i1 :: 1 6 1 0 1 6 1 L 1 6 12 1 b 14 1 6 1 I 1 7 - L ' I 1 7 - l > 1 7 -14 1 7 -13 1 ' I - 1 2 1 -? -I1 I 7 - k j

1 .l - 7 1 .r - b 1 7 - s L -r -4 1 7 - 3 1 7 - 2 1 7 - 1 1 7 0 1 7 L 1 7 2 1 7 3 1 7 s 1 7 6 1 7 7 1 7 0 1 7 LO I 7 11 1 7 1:i 1 7 14 1 7 15 1 7 1 7 1 8 -11 L 8 --'I

1 a -7 1 8 -6 1 8 - 4 1 il -3 1 8 -2 L b -1 1 S U 1 6 1

1 8 3

1 8 5 1 8 7 1 8 '1

1 8 11 1 6 13 1 9 -16 1 '3 - 1 5 1 9 - 1 4 1 9 - I 2 1 9 - 1 L 1 9 -1G

I 5 - r

i n -6

1 8 2

1 8 4

1 a 10

lOlFol 1OFc z 4 I> 2 I b 162 - 1 ' l J 1 iJ 7 17') 130 1 5 4 1 72. L h 3 172 1 7 U

7; -4v 153 101 4 6 2 4 4 1 3'30 - 4 c o 3 1 T -31' ) 2 7 6 2.16 237 75% 6 5 2 -744 1-32 - i4tj 5 6 6 5 6 6 7 1 8 2 3 3 2iJ5 - 1 7 1 22.2 -1'33 1 3 1 - I 1 1 2 4 4 - 7 4 6 2 5 6 216 Z ( I I 191,

93 - 9 3 R h IC5

153 - 1 5 3 1 4 3 - 1 2 4 2 4 2 - 2 7 2 3 9 8 4 3 9 47U -5 7'1 1 0 2 -96 3 7 1 36.5 3 2 3 -,!'32 2 7 7 2 5 1 115 - I 2 1 1 3 7 -11s

7 3 72 1 3 3 - 1 3 6 1 3 0 -119 4 0 1 4 1 3 b 3 b b 1 2 l l r ! - 1 C 7 757. - 5 l A 4 2 4 400 1 3 0 - L 2 9 7 0 2 - 1 7 6

1 4 6 - I !>+ 2 2 4 - 2 5 4

t3 t; ti 2 114 -15.; IIC 1 2 1 1 2 3 - 1 5 9 Z S U 256 112 1 5 4 Z ' J . 3 - 2 7 : 3 2 0 -315 4 9 1 -1,

695 ? I 3 495 -!;Gal 2 3 7 - 2 4 0 5 3 0 47 : 221 -166 394 - 3 4 7 233 -247

' 112 8 3 185 1 6 2 92 - 7 0

1 7 9 i 6 5 120 1 4 0 102 - 1 1 4 113 - 1 6 3 2 8 5 362 2 0 3 37s 07 - 7 0

17> - 2 0 7 1 4 0 1 3 6 315 - 3 4 2

3 3 2 2q6 911 10 90 -L)l.

328 -313 25'3 - 2 6 1 13'1 5 4 2 6 3 210 3 3 7 -29') 31-7 .1c3 1 1 3 110 2 5 4 - 2 4 0 1 4 3 139

6 3 -9 ' ) 56 -74

1 6 2 191 1 4 6 -164 245 ,711 1 1 3 154

it7 - 8 7

h k 1 1 9 - I ,

1 Y -7 1 '3 -> 1 c) -11

1 '3 -2 1 4 -1 1 Y 1 .

1 Y l 1 9 2 1 Y .1 1 Y 4 1 0 5

I V Y 1 Y 12 1 9 13 1 Y 1 4 1 1ti - L l 1 1 0 - < I 'I l u - 3 1 10 - 7 1 lti -'I

1 lU -+ 1 Ill -3 1 10 - 2 1 10 -1 1 li: (,

1 1 0 L 1 10 2 1 1 C 4 1 1 0 5 1 1 0 6 1 10 7 L 10 i; .L 10 '1 1 1 0 l U 1 10 1 1 1 1G li 1 IL; L'* 1 11 -1.5 1 1 1 - 1 1 1 1 1 - < 1 1 1 - '> 1 I 1 - 3 1 11 - ? 1 1 1 -1 1 11 c 1 1 1 L 1 ,11 2 1 11 3 1 1 L 0 1 1 1 7 1 11 1 3 1 12 -12 I 12 -1c 1 12 -0, 1 12 - I , 1 L Z - 5 1 12 -4 1 12 - 2 1 1 2 -1 1 1 2 1 1 1.2 3 1 1 2 4 1 1 L 6

1 I 2 '1 1 12 l U 1 1 3 - 6 1 13 -5 1 13 - Z 1 13 - 3 1 13 -2 1 13 -1 1 1 3 I 1 13 2 1 13 4 1 1 4 - 1 2 0 - 2 , : 2 0 - 1 6 2 0 - 1 4 2 c -12 2 C - 1 U .2 0 - 3 2 0 - 0 2 0 - 4 z 0 -1 2 c L l 2 0 2 2 2 4 2 0 6 2 C d 2 0 1 0 2 L: 1 4 2 c' lf , 2 0 13 2 1 - 1 I 2 1 -15 2 1 - 1 1 2 1 - 1 3 2 1 - - . I

2 1 - J

1 4 t.

1 12 r

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J. Chem. SOC. (A), 1970

h k I 10[Fol lOFc 2 1 - I 810 171 2 1 -6 7 2 3 6 1 3 2 1 -!J 307 - 3 2 0 2 1 -4 4 5 0 4 9 4 2 1 - 3 326 - 2 3 6 2 I -2 195 - 7 4 2 2 I - 1 4 5 2 - 4 4 1 2 1 C, 5 U U -,t17 2 1 1 2 1 49 2 1 2 4 4 0 - 4 4 8 2 1 3 321 - C V ) 1 2 1 4 162 - 1 ' 3 1 2 1 I, 9'1 -46 2 1 6 1 1 0 - 1 3 6 2 1 1 6 6 1 Z r ) 5 2 1 d 2 8 6 -261 2 I ci 4 2 d -376

"2 1 1O 162 1 5 3 2 1 I 1 4 3 0 4 0 5 2 1 12 4 2 1 Y 2 1 13 208 - 2 2 1 2 1 14 1 1 3 1 6 2 L 1 1 % 4 6 4 3 2 2 -15 162 -L5L 2 L -14 1 4 1 -127 2 2 - 1 3 4 1 6 4 h 8 L L -1.2 2Y7 262 2 2 - 1 1 3 1 1 - 3 4 3 2 L -10 4 5 3 - 3 1 4

L L - 9 3 0 5 2 9 4 2 L - 1 1 6 Y -160 2 2 -6 7 4 3 C?6 L 2 -4 321 - 2 2 3 L 2 - 3 802 -879 2 2 -2 2 2 0 - 3 5 5 2 L - 1 5 4 2 -',90 2 2 0 137 1 4 6 L L 1 V U 5 1 0 1 4

2 2 3 >25 -460 2 2 4 3 3 1 - 3 5 4 2 2 5 5 1 % 5 7 4 2 L b '31 00 2 L 7 116 -112 2 2 ti 2 9 4 - 2 4 2 2 L ' I 1 3 1 135 2 2 10 65 104 2 2 1 5 3 0 3 - 2 6 1 2 2 14 1 4 1 - 1 4 0 L 2 15 1 5 4 18 2 2 11 1 6 3 -163 1 3 - 1 6 1 4 3 - 1 1 1 2 3 - 1 5 Y8 -15 L 3 - 1 2 9 4 - 7 3 2 3 -11 98 -110 2 3 -10 215 - 7 4 8 2 3 - < I 361 -36') L 3 - Y 8 2 5 tl2.2 2 3 -1 1 9 4 2 1 1 2 3 -6 h 1 7 - 1 r l 2 3 - S 14U 152 2 3 - 4 4 0 1 4?U 2 3 -i 2 3 8 -211; 2 3 - 2 H 5 2 - 1 1 7 6 L 3 - 1 4 0 9 362 2 3 0 597 b 3 6 2 3 1 4 6 0 415 2 3 2 143 128 2 3 3 316 3 5 1 2 3 4 331 - i M 1 2 3 5 2 1 4 -171 2 3 b bb3 I 7 1 2 3 7 215 - 2 1 1 2 3 H 3 U l - 3 3 4 2 3 4 265 - 2 3 1 2 3 IC .32 47( 2 3 12 3 5 7 - 4 5 b 2 4 - 1 3 166 If id 2 4 - I 1 219 - L 5 0 2 4 - h > b l l 115 1 4 - 5 137 - 1 2 2 1 4 - 3 1 5 1 ~ 1 1 % 2 4 -2 d Y 3 - I 1 2 7 4 - 1 2 7 0 -21') 2 4 u 284 - 1 Y ) c L 4 1 b l 3 142 2 4 L 6d5 -011 2 4 3 9 7 4 - A 6 1 2 4 4 3 5 1 3 2 1 2 4 'I I 3 7 1 2 4 6 7 2 -1lh L 4 I l h l - 1 8 3

2 4 I O 164 1 4 3 2 5 -d 2 5 1 253 2 5 - 1 4 0 9 - + 6 L 2 3 - b 133 -?1b L 5 - 2 8 4 1 <J5tl L 5 - 3 682 - 1 I 3

2 5 - 1 7 2 - 4 3

2 2 - Y 381 31'9

2 L 2 r 5 t 154

2 4 a 7'37

2 5 -2 i i u - i c a

h k 2 5 2 4 2 5 2 5 2 5 2 5 2 5 2 5 2 s 2 5 2 3 2 6 2 6 2 6 2 6 2 6 L O 2 6 2 6 2 6 2 fl

2 6 2 6 2 1 2 7 2 7

2 1 2 1 2 7 2 7 2 7 2 7 2 1 2 7 2 7

2 1 2. 7 2 7 2 1 2 7 2 8 2 8 2 8 2 6 2 8 2 8 2 8 2 8 2 8 2 8 % 8 2 8 2 0 2 8 1 8 2 8 2 8 2 8 2 v 2 9' 2 9 2 Y 2 9 2 9 2 9 2 9 2 Y 2 Y 2 9 2 2 9 2 9 2 9 L Y 2 10 2 lU 2 LC 2 10 2 10 2 10 2 1L' 2 10 2 10 2 10' 2 1c 2 10 2 10 2 10 2 10 2 1 1 2 11 2 11 2 1 1 2 1 1 2 1 1 2 11 2 11 2 12 L 12 2 12

z r

2. 'r

1 0 1 2 4 5

I 3 9

11 13

- 12 - H -6

- 4 -1 -1

c 2 4

9 - 12 -9

b

-

0

- M -5 - 4 - 3 -2 - 1 0 1 L 3 4 L,

I d 1

10 - 1 1 -10 -7 - 7

0

-6 - 5 - 3 -2 - 1 L 1 2 3 4 5 7 >

15 -10

- 8 - I - 6 - S - 4 -2 -1

0 2 4 5 t!J

<I 10 12

- I -6 - 5 - 4 - 3 -2 - 1

0 1 2 J 4 5 b d

- 7 -5 - 3

0 1 L 4

- 5 -2 1

>

lOlFo} lOFc 5 2 2 - ' I09 375 -344 128 1 3 3 1 4 h 1 4 9 > 1 1 '>35 4 0 3 15Y 2 3 R -',(I7 2 6 5 - 2 3 3 4 0 6 3 1 0 2 4 1 - L O O 1 1 8 I O U 314 -301 2 0 4 - I ? *

3 3 1 3 5 0 512 'ICU 7 1 0 - 6 3 2 I d 3 - r r 3 5 6 - 3 3 1 4YL *a33 620 -002 1 0 0 -155 1 7 1 - 1 0 5 2 Y 2 J22 261 -292 2 4 0 ) 4 L 1 2 1 - 1 4 6 4 6 3 - r 3 0 660 571 1 7 1 1 2 1 YY - e 9 94 tro

207 - 1 7 1 84 -hit 9 3 Y'I

7 8 1 2 5 7 1 8 0 - 2 0 0 3 2 9 - 3 c 3 162 1 L l 312 2 3 1 1 2 1 - 1 3 2 340 4 L 9 166 1 6 1 256 - 2 9 0 1 5 2 -162 110 11'1 1 1 2 e 7 2 6 1 -2'11 150 - 1 5 4 45 ' ) 4 5 Y

J4 5 5 6 2 1 -5t4'4 27'3 - 2 4 3 5 9 1 5 7 0 2 8 5 3 G 6 165 - 1 1 2 305 3 0 4 1 7 0 - 2 1 9 I 7 1 -138 111 2 3 5 259 -317 113 14'1 2 U I 7 2 8 l a b - 2 1 3 128 - 1 4 )

86 I 6 255 - 2 h b 114 -100

3 1 ~ 3 4 r

r v r 144

sot, 3 r 1

Y I 8 4 I l l 1 3 25'3 -? t ,? 2 4 2 239 2 I ' ) -222 2 3 2 195 168 185 1 2 4 -12 1 S d Z C H 1 2 1 -165 1 4 1 -115 2 7 6 2 7 0 1 0 4 - 1 C l 333 -33R 110 - 1 5 4 3 1 7 263

' 1 2 3 111, 1 2 7 - 1 3 1 137 - 1 1 4 1 5 , ) 2 7 2 . LI'j - 1 b 4 3 2 9 3 7 3 3 3 1 - 3 8 7 1 2 1 130

1 2 6 1 1 4 123 1 4 3 '113 I 1 5

90 52 117 R')

90 6 5

'3.i - i C a

9.3 -nt3

TABLE 2

h k l 2 I2 2 2 12 3 7 13 - 4 2 13 -2 2 14 - 2 2 14 I 3 0 -2u 3 L - l J 3 ( I - I 6 3 0 - 1 4 3 u - 1 2 3 0 -d 3 L - 6 5 0 - 4 3 0 - 2 3 0 0 3 0 2 3 0 4 3 O b J 0 d 3 L I2 3 0 14 3 0 16 3 O 1 t I 3 1 - I 4 3 1 - 1 3

3 1 - 1 5 3 1 - 1 4 3 1 - 1 3 3 1 - 1 2 3 1 -11 3 1 -lL 3 1 - Y 3 1 -d J 1 -6 3 1 - 4 3 1 - 3 3 1 - 2 3 1 -1 3 1 0 3 1 1 5 1 L 3 1 3 3 1 4 3 1 5 3 1 b

3 1 8 3 1 9 3 1 10 3 1 11 3 1 12 3 1 13 3 1 15 3 1 I6 3 1 17 3 2 - 1 1 3 L -1b 3 L -12 3 2 - 1 4 3 2 - 1 3 3 2 - 1 2 3 2 - I 1 3 2 -16 3 2 -9 3 L -Y 3 2 - I 3 2 -4 3 2 - 5 3 1 - 4 3 L - 3 3 2 - 2 3 2 - 1 3 2 0 3 2 1 3 2 2 3 2 3 3 2 4 3 2 s 3 2 h 3 2 1 3 L d 3 2 9 3 2 IG 3 2 I 1 3 2 12 3 2 15 3 L 14 3 2 i5 3 J -16 3 3 -1s 3 3 - 1 4 3 3 - I 3 3 3 - 1 2 3 3 -11 3 3 - 1 G 3 3 - I 3 3 - 1 3 3 -6 3 3 - 5 3 3 - 4

3 1 - 1 1

3 1 1

(Con1

1OlFol 172 L O O 1 Y L 1 9 1 6 9

224 128 L 4 0 1 0 4 1 2 1 1 0 4 95

8 5 0 5 7

735

L 3 d Z Y 1 IrbU 3 1 1 46[1 LYO

96 4 1 9 2 64 3 5 A 2

3 3 0 3 0 3 5 Y U 345 35rl 35 1 4 5 6 1 3 7 54Y (13 1 830 1 5 4 4 2 1 5 3 '3 6d3 6 4 2 6 2 3 3 6 4

20Y

8 0 1 1 7

4 3 1 5 6

I15

1 5 1 7 6

58 l d 6 5

119 3 0

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3 72 5 2 6 130 4 1 8

36 4 0 5 167 7 0 8 4 0 3

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3 3 - 3 3 3 -2 3 3 - 1 3 3 u 3 3 1 3 3 2 3 3 5 3 3 4 3 3 5 3 3 6 3 3 8 3 3 '3 3 3 10 5 3 11 3 4 - 1 1 3 4 - 1 0 3 4 -Y 3 4 -6 3 4 - I J 4 - 6 3 4 - 5 3 4 -4 3 4 - 3 3 4 - 2 3 4 - 1 3 4 0 3 4 1 3 4 2 3 4 1 3 4 4

3 4 J 3 4 ' I 3 4 1J 3 4 1 1 3 4 12 3 4 13

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3 5 - b 3 5 - 4 3 5 - 2 3 2 - 1 3 5 1 3 5 2 3 5 3 3 5 4 3 5 5 3 5 0 3 5 1 3 5 8 3 5 9 3 5 11 3 5 12 3 6 - 1 1 3 6 - 8

3 6 -6 3 6 - 5 J 6 -4 3 6 - 3 3 6 -2 3 6 - 1 3 6 0 3 6 1 3 6 2 3 6 4 3 6 4 3 6 1 3 6 6 3 7 - 1 5 3 7 -13 3 7 -12 3 7 - I 1 3 7 - 1 G 3 7 -7 3 7 -0 3 7 -> 3 7 - 4 3 1 - 3 3 7 -2 3 7 -1 3 1 c 3 1 1 3 7 1 3 7 3 3 7 4 3 1 5 3 7 6

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4 a i - 4 1 7

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8 3 - 8 0

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108 - 1 1 11') - 1 4 1 12% 118 82 lt(

196 135 2 6 2 - 3 1 3 185 1 3 Y 1 4 6 1 5 5 372 - 4 8 6 217 2 5 6 1 1 4 '19 4 6 1 - 3 8 6 89 5 7 8 0 -?d

2 9 h 2 4 7 5 4 5 52'1 3 0 1 2Yb 59') -032 131 1 4 3 4 5 2 4 3 6 3 3 0 - 3 4 6 3 2 1 -29Y

' 1 6 1 0 4 2 1 4 24 ' ) 2 7 5 - 2 6 s

7 1 - 1 6 2 142 -101 2 4 2 7 h l 16t i 1')R 3 8 6 - 3 6 9 2 0 1 -11'7 504 >oo

4 9 a - 4 6 9

h k 1 lOlFol lOFc 3 8 -2 7 0 2 1 8 7 3 ti -1 2 5 6 - 7 3 U 3 0 0 86 - 4 4

3 8 J C o d -272 3 a L 195 -195

3 a 5 1 2 3 1 2 1 3 8 0 6 3 - 5 7 3 6 7 156 180 3 M 8 3 0 9 167 3 8 9 1 1 1 -115 3 9 - 1 2 24Y 3 4 ~

3 3 9 Y -10 - 8 284 1 1 1 - 3 7 1 'I3 3 Y -1 1 4 5 -12Y 3 9 -4 I I M - 1 7 1 3 9 - 2 165 111 3 v - 1 9 3 - 7 3 3 9 0 305 - 2 e l 3 9 2 4 0 5 3 h 0 3 Y 3 2 4 0 L I J 3 9 4 3 4 0 -345 3 9 3 254 2 3 3 3 9 0 3 9 3 3 7 3 3 9 1 92 - 1 2 1 3 Y d 1 3 7 -111 3 10 - 8 2 1 6 761

3 10 -6 8 8 - 1 1 4 3 1c - 5 1 3 4 - 2 5 7 3 10 - 3 2 6 5 2 4 1 3 10 -2 131 -14'4 3 10 - 1 14'4 - 1 3 9 4 1 0 L' I17 1 2 1 3 LO L 118 - 8 5 3 10 5 15q - 1 P 6

3 t o - r 270 1411

3 1 1 - r 131 -113 3 1 1 - 3 2 0 ~ 1 1 1 4

3 3 1 1 I 1 - 1 3 3 2 3 100 - 1 0 s - 3 0 9 3 11 5 2 2 9 2 3 3 3 1 2 - U 1 5 4 1 5 6 3 12 -6 155 - 2 4 8 3 12 -2 l Y 0 -17Y 3 1 2 u 21Y 2 4 9 3 1 3 - 3 154 I 3 3 3 13 -1 1 3 5 - 1 2 2 3 13 3 117 -110 3 14 - 3 2 2 0 - I 8 8 4 0 -10 2 8 2 -2h2 4 0 - 1 4 4 1 8 3 1 0 4 0 - 1 2 4 5 2 - 4 4 5 4 O -Ill b l l 6 3 3 4 0 - 8 3 5 Y -352 4 0 -6 35'1 3 2 8 4 0 -4 1 6 3 -1h0 4 u -2 7 9 -11 4 0 0 1 4 4 I51 4 0 2 6 5 3 - ? 9 1 4 0 4 11'30 I 2 7 1 4 0 6 618 - 6 E B 4 0 8 191 18'3 4 0 10 2 9 2 -266 4 1 -70 120 1 2 4 4 1 - 1 3 2 0 1 1 0 4 4 1 -16 112 1 2 3 4 1 - 1 4 1 4 2 -132 4 1 - 1 3 4 0 -15 4 1 -12 327 - 2 6 3 4 1 - 1 1 129 7 8 4 1 - V 1 3 7 1 3 1 4 I - 8 100 - 8 5 4 1 - 1 650 -h60 4 L -6 4 9 1 48s 4 1 - 5 7 3 h 7 t 8 4 1 - 4 4 4 % - 4 2 1 4 1 -3 382 - 4 2 3 4 1 - 2 4 1 9 3 ' )C 4 1 -1 6 2 1 6 P )

4 1 1 661 - / 5 6

4 & 3 139 -168 4 1 4 359 - i 4 / 4 1 5 2 3 2 205 4 1 6 O4 - 7 h 4 1 7 6'. 1 1 1 4 1 u 122 11'. 4 1 i t l i b L 4 1 l b o -143 4 1 12 9s P 7 4 1 I 17U 1t .4 4 1 1 4 JY - 3 3 4 1 1 2 121 - 1 3 H

4 i 0 1 8 8 It20

4 .I 2 1 2 8 L Z ' D

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Inorg. Phys. Theor. 387

h k l

4 2 - I 4 2 - 6 4 2 - 5 4 2 - 4 4 2 - 3 4 2 -2 4 2 - 1 4 2 0 4 2 1 4 2 2 4 2 3 4 2 4 4 2 5 4 2 6 4 2 7 4 2 8 4 2 9 4 2 L O 4 2 11 4 2 12 4 3 -10 4 3 - 1 0 4 3 -16 4 3 -15 4 3 -14 4 3 -12 4 3 - 1 1 4 3 - 1 0 4 3 - 9 4 3 -6 4 3 - I 4 3 - 6 4 3 -5 4 3 -4 4 3 - 1 4 3 -2 4 3 - 1 4 3 0 4 3 1 4 3 4 4 3 5 4 3 6 4 3 1

4 3 Y 4 3 I 0 4 3 11 4 3 12 4 3 14 4 4 - 1 7 4 4 - 1 6 4 4 - 1 5 4 4 - 1 4 4 4 - 1 3 4 4 - 1 1 4 4 -9 4 4 - H 4 4 - 1 4 4 - 6 4 4 - 5 4 4 -4 4 4 - 3 4 4 -2 4 4 - 1 4 4 0 4 4 1 4 4 2 4 4 3 4 4 4 4 4 5

4 3 8

4 4 1 4 4 8 4 4 't 4 4 10 4 4 1 1 4 4 1 3 4 5 -19 4 5 -17 4 5 - I t . 4 5 -15 4 5 -14 4 5 - 1 3 4 2 - 1 1 4 5 - Y 4 5 - 8 4 5 - I 4 2 - h

4 5 - 4 4 5 -3 4 5 - 2 4 5 -1 4 5 0 4 5 1 4 5 ) 4 5 3 4 5 4 4 5 0

4 5 6 4 5 69 4 5 10 4 5 11

4 5 -'J

47 r 120 3 1 1 2 6 7 462 163 722 473 5 7 3 203 402 421 44 1

36 4 74 172 216 108 105 110 63

152 220 110 132 152 2 4 0 163 4 1 1 101 2 14 9 34 290 783

5 5 652 44 1 495 171 4 6 4

6 1 8 8 4 1

407 TZR 246

6 5 201

Y O 1 5 1 171 142 77 100 443 590

65 4 12 235 24 Y 27) 265 6 5 1 163 455 310 79 97

101 2 54 165 20 1 Z l b 175 125 1 2 4 145 1 2 4

163 13-J 2 1 2

8 6 392

7 1 6 3 0 1 1 2

9 2 473 50 1 4 d 1 d'33 14 1 55') 579 1 3 3 l 8 V 1 '1 z 104 1'1 1 14u 22u

8 6

lOFc

4Pl - 8 3 - 5 4 0

-2 14 - 393

7 5 b % b

-424 - 3 6 b -262

4 1 Y 4 3 6

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4 6 3 164

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-119 P Y

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25R 147

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6 2 79 39

4 06 - 1 1 1 -228 -70 190

-103 -176

32 144

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4 C Y - 6 0 5

7 b 4 32 212

- 2 4 6 2 30 2 0 5

1 5 1 -4R9 -342 LO0 103

-102 -286 148

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-127 1 3 6 119

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2 2 7 - 0 8

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1 5 3

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2 0 7

i r 4

h k l 4 5 1 3 4 6 - 1 6 4 6 - 1 4 4 6 -13 4 6 -12 4 6 -10 4 6 - 8 4 6 -6 4 6 - 5 4 6 - 4 4 6 -2 4 6 -1 4 b L 4 6 1 4 h 2 4 6 3 4 6 4 4 6 6 4 6 3 4 6 l U 4 7 - 1 4 4 7 - i 4 7 -7 4 7 - h 4 7 - -z 4 7 -4 4 7 -3 4 7 -2 4 7 - 1 4 7 0 4 7 1 4 7 2 4 7 3 4 7 5

4 7 l J 4 a - 1 3 4 8 - 1 1 4 b -'1 4 8 -6 4 8 -7

4 8 - 5 4 8 -4 4 M - 3 4 8 - 2 4 M - 1 4 8 0 4 8 1 4 8 2 4 8 3 4 8 4 4 0 5 4 8 6 4 8 1 4 8 8 4 9 -7 4 Y -6 4 9 - 4 4 9 -2 4 9 0 4 Y l 4 9 2 4 9 6 4 10 -11 4 10 -10 4 10 -9 4 1c - H 4 10 -4 4 10 -2 4 10 1 4 1u 2 4 10 J 4 10 4 4 10 5 4 1 1 -9 4 11 -7 4 11 -6 4 1 1 - 5 4 11 -4 4 11 - 3 4 1 1 -2 4 1 1 - 1 4 11 0 4 11 1 4 12 -14 4 12 -12 4 12 -11 4 12 -10 4 12 - 4 4 12 -8 4 12 -& 4 12 - 1 4 12 1 4 12 2 4 12 4 4 12 z 4 12 L 4 13 -4 4 13 -2 4 14 -4 4 14 -1

4 1 1

4 8 -6

lO[Fol lOFc 152 -17% 174 160 143 - 1 l h

I7 3 2 340 7 9 8 704 - 6 7 5 412 4 6 3 537 -<I22 245 - / 4 6 416 $77 262 1 3 V 233 197 ?4? -147 13'4 164 2 6 R 783

2 4 1 7 1 - 2 3 9 255 247 33Y -330 221 213 1 2 0 1 3 1 2 3 Y - 2 2 7 1 9 3 I 0 4 317 - 3 S Y 305 - 3 2 6 432 457 4 0 6 35U 262 -269 4 1 1 - 3 q 3 327 276 126 1 2 1 292 - 3 2 2 120 -141 186 ?24 128 L O 4 64 -101 33v 5 c 3 2 6 4 -22Y 22') 2 0 2

412 - 4 2 1 144 - 1 5 5 341 3 1 4 37 2 5 87 - 5 1

355 365 lY4 -2Ch 307 -32.2 141 146 124 - 1 1 8 232 - 2 2 4

t a o 198

140 5 9 460 4 6 4 113 133 2 6 1 - 2 1 2 115 -105 L O Y 149 391 -407 396 397

2.28 2 7 2 'IY - 35 Y 3 - 1 q

l d 4 8 4 192 - 1 4 8 169 159 lI2 184 U l -72

143 -141 9 3 '11

1 4 7 1 8 6 214 -770 2 1 7 - 3 4 4 3 5 3 392

121 1 4 6 728 -228 139 -171 9 1 105 141 I 3 5 131 - 1 3 5 147 - 1 7 5 3 1 1 3(!6 119 1 4 H 332 - 3 2 Q 116 98 l l h -144

85 6 3 1 4 9 1 2 1 1 2 4 - 4 1

8 ( > - V % 1 4 1 d7 00 -15 d 3 - 1 U 6

1 5 9 -254 252 2 2 9

8 6 -47 141 -163

5 1 - h 4 1 4 3 1 3 4 37 -3

234 :c7

2 7 9 -263

a4 tl4

TABLE 2 (Continued) h k I lOlFo[ lOFc 5 0 - 2 0 128 1 6 4 5 I, -1" 119 -116 5 0 - I t , 1 5 1 1 3 6 5 0 - 1 4 130 - 1 6 1 5 0 - 1 2 ? b h 2YI) 5 0 -10 273 734 5 0 - 8 374 -176 5 0 - 6 362 352

5 u -2 359 342 5 c (r b l l - h j C

2 0 4 24ft - 2 l H 5 C 0 6 1 9 3 2 U H 31'1 3 1 1 5 0 1U 2 4 1 - 2 4 0 + 0 12 7 6 7 1 5 0 14 122 -133 5 (r 16 193 114 5 1 - 1 ) 47 - e 8

5 1 - I ? 115 - 1 b l 5 1 - 1 b l l l c -7c 5 1 - 1 5 2 4 3 2 3 6 5 1 -14 262 -2hV 5 1 -13 58 -L,h t, 1 - 1 2 148 126 5 1 - 1 1 169 138 Z 1 -10 41U - 7 H O 5 1 - 9 454 -440 2 1 -8 307 . ' R l 5 1 - 7 h 7 1 7 C l z 1 -6 1 4 3 - 1 1 0 2 1 -2 2 7 3 -75h 5 1 -4 U 2 J 8 4 1 5 1 -3 276 2 7 1 5 1 - L 403 341 5 1 -1 332 -250 5 1 L 17c> - 1 5 3 5 1 1 264 - 2 4 4 t, 1 I 1?2 LO(>

5 o -4 i h n - i e r

5 0 2 502 > 5 0

2 i - i t \ 40 h r

5 1 J 4 3 6 4 3 Y -J 1 4 515 - 5 9 1 5 1 5 6d0 -741 5 1 6 5 1 7 5 1 8 5 1 9 s 1 lU 5 1 11 5 1 1 3 5 2 - 1 3 5 2 -17 5 z - 1 6 5 z -15 5 2 - 1 4 5 2 - 1 3 5 2 -12 5 2 - 1 1 5 2 -10 5 z - Y 5 2 -u 2 2 - I 5 2 -6 2 L - 5 s 2 -4 s 2 - 3 5 2 -2 5 2 - 1 5 2 0 5 2 1 5 2 2 !I 2 .3 5 2 4 5 2 5 5 2 6 5 2 1 5 2 8 5 2 3 5 2 10 5 2 1 1 5 2 I:, 2 3 - 1 s 5 3 - 1 4 2 3 - 1 3 2 3 -12 5 3 - 1 1 5 3 -1u s 3 -0 5 3 - L J 2 3 - 1 5 3 - ( I 'j 3 - 5 5 3 - 4 5 j - 3 5 3 - 2 5 3 - 1 5 3 0 5 3 1 5 3 2 ' 5 3 3 5 3 4

L r 4 36 1 307

74 1 Y 2 134 1 6 1 164 136 45

19'3 21 1 153 22d L07 251 154 75

2 2 0 2 3 0 b R ' ) 2 1 3 30G 193 25 1 2 Y 3 5 7 1 153 367 1 6 Y

92

110 24 u

30 1413 114 199 757 21 1 l 5 ( b 266 (04 53i 140 32 7 3 7 2 1 5 ? l l r i 5 2 i 1 4 4 138 72 1 352

'1 9 1 4 2 i h l l 2 2 2

a 3

14 r 3 38

-/YB 1 1 v /24 104

- 1 4 3 -155

132 53

- 2 C h -197

144 203 17'2

- 2 3 0 145

- 5 1 z 3 u 2 2 8

-h9Z 144 2 9 7 2 14

-542 -3 12

>I36 148

-371 -IS<)

1 C') -35 1 16 2 5 1 - 4 4

-124 106

- 1 8 7 2 3 0

-313 144 2 52

- 1 8 3 -514 - 105

310 - J 1 0 - 164 - 1 2 2

4 3 9 c 3 %

- 1 2 E 117

-.:55 57

1 6 2 . '44

-,?z'i

h k 1 10(Fo[ 5 3 6 198 5 3 7 250 5 3 Y 263 5 3 '1 144 5 3 11; I61 5 3 11 129 t, 3 I ? 6 5 5 4 - 1 1 2 U l 5 4 -1- 54'1 5 4 - 4 130 5 4 --r 1 7 1 > 4 - 1 212 2 4 - 6 M L 5 4 - 5 292 2 4 -4 3 t > ? 5 4 - 3 5 I L 5 4 - L 398 5 4 - 1 2 2 3 5 4 u 19) 2 4 1 526 5 4 2 2 3 0 5 4 3 ' IV 5 4 2 LMH 5 4 6 194 7 4 7 112 5 4 d 5') 5 4 Y 200 5 4 l U 185 5 4 1 1 2 5 0 5 5 -10 26Y 5 2 - Y 5 6 1 5 5 - 8 2 7 1

5 5 - 6 1 1 3 2 5 -> 61) 5 5 - 5 116 5 5 - 1 104 5 5 LI 2 6 0 Z 5 I 1 3 1 5 5 2 136 5 5 3 2 0 H 5 5 5 135 2 5 1 345 5 5 t( 1 5 8 5 5 9 217 5 5 1L 6 4 5 6 -lH 2 0 3 5 6 -12 94 5 6 -14 5 4 0 5 6 - 1 3 71 2 6 -10 705 5 6 - b 412 5 b - 3 102 5 6 -4 471 5 6 - 3 7 4 1 5 b -2 328 5 6 -1 355 5 6 U 5 5 6 5 6 I ' 10 5 6 3 7'1 5 6 7 Y 5 3 6 6 2 2 3 5 6 10 L 3 b 5 6 11 101 5 6 1 2 2'30 5 7 -14 2 2 ' ) 5 7 -13 1411 5 7 -lL 1YL 5 7 - 1 C 165 5 7 - I 394 2 7 - R 2 8 1 5 7 -7 LYl 5 7 - 5 152 5 7 -4 156 5 7 - 5 2 ? 0 5 7 -2 I26 > 7 - 1 M l 5 7 0 3 0 5 5 7 L 1 Y h 5 7 3 125 5 7 4 #57

5 7 0 1411 5 7 I Z l U

5 8 - 1 5 250 5 8 - 1 4 9<) 5 8 -5 3 3 3 5 8 -4 143 5 8 - 3 4 5 5 Z 8 -,' Y 2 5 8 3 166

5 3 5 131 3 8 6 01

5 (r s; 1 3 1 5 Y - 1 5 146 5 Y -14 1 7 1 5 Y -12 216 5 9 -1c 21? 5 '9 -3 233

5 5 - r 107

s 7 5 4 1 7

5 a - t i 7'21

-J 8 4 115

5 d r 10%

10Fc 1 7 0

- 2 5 5 - 2 1'1

17 7 2 7 6

-130 3

217 -2 7.1 -115

132 1 6 1

- 1 C 6 -?ah

9 3 h 444

- 3 a n - 2 3 1 i 1'1 140

- ( C ' ) - 1 3 3 - 2 [ i h -224

H l 54

- 2 3 1 1 i 4 c 1 Y

- 2 4 8 Z6 1 L6h

- 1 8 8 - 8 3

10 117 - 98

- 2 s 1 R I

124 -?C? 113

- 1 4 3 3 C J 51

1 I8 - 2 5 4 4 1 - 2 6

- 2 7 b -443

- 1 3 417

-235 - i L l J

3 7 5 5 2 5 119

- h l l C 8

-215 241 -ah

- 2 ? 6 2 5 0 17fa

-166 113 4 32

-285 -.30<9 175

2 1 5 103

- 1 or, 3 1 3

-203 -156 340

-117 - 179 -271 205 L O 4

146 -440 -66 1t:9 - 3 1 1 3 5

- 1 1 3 -71

t ? t * 12h 1 3 1

-125 1 R7

- 1 2 6

- 5 5 r

-251

3 r2

296

h k 1 10IFol 1OFC 5 9 - I 207 14h 2 Y -6 117 2 5 3 5 9 --, I B O -783 5 9 - 4 237 - 2 1 6 2 9 - 3 4 1 - h % 5 Y - 2 128 1 2 9 5 Y L 7lJ P4 5 Y 1 3 - 7 2 'J 2 l i d -272 L, 9 3 1 3 1 170 5 Y 4 3 1 * > 166 5 9 5 87 -49 5 Y (I 2 6 3 -237 5 10 - 4 94 17

5 1U -5 L V 7 176 2 10 -4 l3h - 1 2 3 5 1; - 3 119 -106 z 1c - 2 1 3 1 125 5 10 - 1 3 2 i 3 1 9 5 10 II 154 - 1 4 1 5 LO 1 199 -203

5 1 1 - 1 1 144 @ l 2 1 l - l U 101 1111 5 1 1 - t 208 -200 '1 1 1 -7 17r 1 4 1 5 11 - b Y 4 -64 5 1 1 -2 164 - 1 4 0 5 11 -4 128 - 7 2 5 1 1 - 3 2 2 6 210 5 11 -1 276 125

5 11 L 96 -111 5 11 3 I 3 4 1 2 4 5 11 4 L O O 8 6 2 11 5 1 3 1 -11'1 5 11 I 1 4 3 116 5 12 - 2 1 4 h 1 5 7 5 12 U 317 - 2 9 5 2 13 - I 157 1 6 3 > 13 - 5 1 2 4 - 1 1 1 5 1 3 z 1 3 7 - 1 4 4 5 14 - 5 1 4 ' ) - 1 4 0 6 0 - 2 U 4'1 - 1 5 6 U - I t , 6 1 41 6 0 -16 40 -48 6 0 -14 j U 7 ->U7 6 U - l L j b l 3 5 8 b Ll -1U 1 3 A - 1 4 6

6 0 - b 796 - 9 1 5 (r 0 - 4 4 6 6 J d l 6 O - 2 1 2 1 - 1 4 7 h L L 2h4 -,'HC 6 0 1 1 1 1 317 h 0 4 4 0 1 - h 4 G 6 L' h 4 1 3 i 7 2 6 G b 1 4 9 - 1 4 4 6 b 10 2 0 9 2 0 1 6 0 12 145 -13h h U 14 5l - 1 d 4 1 - 1 9 8 0 - 1 0 0 6 1 - 1 d V 2 15 6 1 - 1 1 2 2 1 2 1 5 h 1 - 1 b 45 -74 6 1 - 1 r 290 - , ' i f 6 1 -14 186 165 h 1 - 1 5 182 1 4 4 .6 1 - 1 ~ 7 1 - 1 1 b 1 - b 137 76. 6 1 - 7 1 6 4 - 1 4 3 6 1 -6 27?1 - / 7 $ 6 1 -5 537 ->h3 6 1 -4 3 0 3 1 7 1 6 1 - 3 8 2 2 ' i O Y t 1 - 2 2 1 2 -zut , 6 1 - 1 301 -7110 6 1 < 2 3 7 2>7 6 1 1 2 1 3 Li!? h 1 L -51') - 3 1 1 6 1 3 4 2 1 -445 6 1 Y 184 1 5 % 6 1 6 9V i'? h 1 7 h0 4 0 6 1 I 1 2 4 - # L 6 1 1( I 5 fsh 6 1 I 1 6 5 ';Y 6 2 -1 'J 12') - 1 2 3 6 2 - 1 4 43 - 4 ) 6 2 - 1 i l d 4 1 5 ) 6 2 - 1 2 4 1 -5 6 2 - 1 1 4 2 A - 4 C b 6 L - I 582 573 6 2 - 3 272 / 7 + 6 2 - 1 452 -477

6 2 - 5 4A6 4 2 9

6 2 - 3 3 1 3 -291 6 2 -2 5 1 ' I

6 L - 1 242 l6i)

I, i c - r 1 6 4 -175

5 10 J 8 3 -Leo

5 11 I 2 1 s - 1 5 7

6 o - h 707 i r r

tJ 2 -(, 3 r 4'1

0 2 -4 213 177

Publ

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1970

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J. Chem. SOC. (A), 1970

h k 1 lOlFol 1OFc 6 2 0 Z O H - 1 t ' R 6 2 L 1 3 6 12M 6 2 C 61, Y L 6 2 3 4 0 3 - 4 3 5 6 2 4 2 b l -19Y 6 L 5 3cdl i 6 U 6 L h It, R i 6 2 7 30d -308

6 2 Y 175 LC6 6 2 LO 1 3 4 15R 6 2 11 125 - 1 0 2 6 3 -16 1 7 1 - 1 4 4 6 3 -14 197 170 6 3 -12 4R2 -462 6 3 -11 143 1 2 5

6 3 - M 113 122 6 3 -7 1 3 0 - 1 1 0 6 3 -6 239 -23b 6 3 - 4 357 3IY 6 3 - 3 6 4 - 5 4 6 3 -2 4 3 4 - 4 0 1 6 5 - 1 131 129 6 3 0 932 l ( r 3 2 6 3 1 5 1 - 4 3 6 3 L 554 - 6 2 2

6 3 7 I l l -? ' I 6 3 8 142 6 7 6 3 I2 110 - 1 h 8 6 3 14 193 - 1 5 5 6 4 -11 266 - 2 3 R 6 4 -10 185 1 6 0 6 4 -7 105 1 8 5 6 4 -8 514 - 5 3 4 6 4 - 4 397 -526 6 4 -3 82 -70

4 4 - I 73 -69 6 4 0 222 2 3 3 5 4 1 356 36M 6 4 3 L I Z -215 6 4 4 106 32 6 4 5 161 143 6 4 6 214 -210 6 4 1 3 1 2 - 3 3 8 6 4 9 162 176 6 4 10 10') -123 6 5 -11 1 1 4 40 6 5 -10 85 - 1 1 3 6 5 -8 124 IO!, 6 5 - 7 89 35 6 5 -5 87 6 6 6 5 - 4 8 4 q 3 6 5 -3 592 -581 6 5 - L 281 - 2 7 1 6 5 -1 612 6 3 3 6 5 0 175 152 6 5 1 255 -251 6 5 2 92 -82 6 5 3 100 192 6 5 4 1 5 2 - 1 6 2 6 5 3 257 -272 6 5 6 'Jd 7H 6 5 9 183 164 6 6 -11 223 2 1 3 6 6 -10 196 170 6 b -8 1 7 Y - 1 4 7 6 6 -7 Y O -119 6 b --h 117 Hh 6 6 -5 166 -125 6 6 - 4 2 C R - 1 5 3 6 6 - 3 82 - 6 0 6 6 -1 12R 9 - h 6 6 -I 99 -101 6 b L 5 1 l i ) 7 4 6 6 L 207 -747 6 b + 117 b l b '6 4 192 223 6 6 6 34tJ - 5 h C 6 6 8 191 1 8 0 6 6 10 1 7 2 - 1 R l 6 7 -7 113 -86 6 7 - b L I h 2 3 1 6 7 - 5 1 0 4 l a 2 6 7 - 4 1 4 0 -139 6 7 - 5 L2h - 1 b O 6 7 - 1 20'1 C 2 3

6 7 I 198 -1V7 6 7 2 I d 1 21 '1 6 7 3 I58 I81 6 7 4 190 -182 6 7 I 1 2 0 - 5 6 6 8 -10 160 1 3 4 b M - ' I C C l - 2 4 6 6 M - I 300 32Y 6 8 -!I 1 3 1 - 1 1 2 6 M -4 L d 4 - 1 6 3 b 8 - 3 1 7 3 I 3

6 2 8 4 4 - r v

6 3 - i c 131 i p n

6 3 b a3 -ha

t. 4 -2 3 h a 3 5 5

6 7 t 105 -15

6 ti -2 l a 1 1 2 4

h k l h 8 - 1 6 6 2 6 8 3 6 8 4 b M > 6 8 7 6 8 Y 6 Y - 9 6 Y --b 6 9 - 5 6 9 -4 6 Y -2 6 9 - 1 6 Y J 6 9 2 6 9 4 6 10 -')

6 10 - 3 6 10 -7 6 10 -6 6 1U -5 6 10 -4 6 10 - 3 6 10 I 6 10 2 6 1 0 6 6 I 1 - b 6 I 1 -4 6 I 1 -3 6 I 1 -1 6 I 1 L 6 12 -6 6 12 h 6 13 - 4 6 13 - 3 6 13 0 7 0 - 1 E 7 0 -16 7 0 -14 7 0 -12 7 0 -10

7 0 -6 7 0 - 4 r o o 7 0 2 7 0 4

7 0 12 7 1 - 2 0 7 1 - 1 1 7 I -10 7 1 - 1 2 7 1 -14 7 1 - 1 5 7 1 - 1 2 7 1 -11 7 1 -10 7 1 -9 7 1 - 8 7 1 - I 7 1 -6 7 1 - > 7 1 - 3 7 1 - 2 7 1 -1 7 1 0 7 1 1 7 1 2 7 1 6 7 1 1 7 1 J 7 1 Y 7 1 1 u 7 1 11 7 1 12 7 L -1') 7 2 -17 7 2 -16 I 2 - 1 5 7 2 -14 7 2 -13 7 L -12 7 2 -11 7 2 -10 7 2 -9 7 2 -8 7 2 - 7 7 2 - 2 7 2 - 2 7 z - 4 7 2 - 3 7 2 - 2 7 2 -1 7 2 11 7 2 1 7 2 7 7 2 3 7 c . t 7 2 6 7 2 2 7 2 1!

7 0 -a

1 0 6

100 16 I L M2 1 5 0 222 2uu 7 0 Y

Y O 2 5 2

J b 33 I 23

15CJ 3 b ti 5 1 3 111 I55 234 185 3 u 5 13'1 95

15.2 16 7

1 6 1 8 2 76

3 3 7 30Y 1 3 5 2 1 8

R 'I 155 205 137 1 7 L 252 7 4 0 197

6 5 231 3 8 4

a5

5 5 4 158 161 315 202

4 4 1 0 3 117 45

1 6 b 4 4 161 2 52 125 135 494 44 3

4 2 5 h l I 1 I 2 29 1 1 5 7 I c 2

57 I 1

192 165 42

242 12.2 1 1 4

6 5 1 4 ? 2 0 5 6 5

1 5 1 1 3 9 Yd

305 361 763 41 191 152 244 16U 340 230 4 2 1 2 > 1 1 3 ( > 7 5 2 3u L 2 I 6 ? 7 2 2 4 2 151

4 1

5 7 8

1OFc - ? 4

-222 2 R I t59

- ? 5 b 1 h3

- I 1 1 126 2 2 6

-114 -31.9 - 3 Y 11'1

- 2 3 1 3 7 5

- 1 4 2 - 1 4 i l

2 4 7 1 2 V

- 3 1 5 - 1 4 6

94 I h I

- 1 6 d - R c J 15.2

- 7 5 3 40

- 3 0 9 1 0Y

- 1 9 Y 8 5

111 1 5 3 1 5 4 165

- 3 0 0 2 7 3

-106 7 7

-184 -375 hO2 I80

-128 3 3 4

-172 - 7 5 I 00

- I C 4 37

- 1 4 4 b b

- 2 2 4 - 1 0 5 -155

5 7 2 - 4 7 1 -1,3c1

4 LO (1 2 2

- 1 e r 2 I 5

- 1 2 4 1 R 4 4 h 7

- 2 1 6 - 1 5 2

17 269 - 4 6

-1 19 90

1 5 1 - ? 2 4

-h7 1 6 (; 170 - 9 3

- 2 75 J 64 2 4 4 -<I0 I h7

-155 - 196

1 3 5 2 3 7

-4'15 -44 I

2 J 1 I 4 4

a >

I 3a

- 2 2 2 - 1 2 4

TABLE 2 (Continued) A k E lOlFol 7 2 Ic, L O / 7 2 I 1 54 7 3 -15 1 1 2 7 3 -12 3 4 3 7 3 - 1 1 1 3 i 7 3 - l U 4 0 6 7 3 - Y 114 7 3 -8 4 5 1 7 3 - I 407 7 3 - 6 603 7 3 - 5 7 2 7 3 - 4 2 1 h I 3 - 3 H5 7 3 - 2 4 3 1 7 3 - I 1'15 7 3 0 5 2

7 3 2 254 7 3 3 3 2 2 7 3 5 109 7 5 6 3 3 2 7 3 r 107 I 3 ti 2 3 c 7 3 1b 1 5 9 7 3 12 1 2 0 7 4 - 1 2 2 2 4 I 4 - 1 1 1 t I 7 4 - I d 87 7 4 -Y I57

7 4 -2 304 7 4 -3 4 2 1 7 4 -2 3b7 7 4 - 1 689 1 4 0 4 4 2 7 4 1 279 1 4 7 264

7 4 5 5H2 I 4 7 1 4 3 7 > - 1 1 3 1 3 7 5 - 7 2 0 5 1 5 - M I61 7 5 - I 1 5 4 7 5 - b 158 7 5 -5 2 2 1 7 5 - 4 370 7 5 - 3 335

7 5 0 1 0 5 7 2 3 14t' 7 5 4 2 7 1 7 'J 2 148 7 5 1 143 1 6 - 1 2 1 5 4 7 6 - I 78 7 6 - 6 ?4h 7 6 - 4 4 0 2 7 h -2 404 7 6 0 401

7 3 I L a b

r 4 -6 I Y I

r 4 3 119

7 5 - I L y r

r 6 2 4 ~ r r 6 4 173 7 7 -11 1 R l 7 7 -Y 163 7 7 - 8 19) 7 7 - 7 3 6 3 7 7 --5 2 9 7 7 7 - 5 245 7 7 -4 124 7 7 - 3 771 1 I - 1 424 1 1 0 77 7 7 L I31 7 7 3 1 8 3 7 7 'I 1 5 6 1 7 7 LUO 1 I Y 169 7 8 -,> I 3 L 7 8 - I 2.27 7 6 -6 7 7 7 M - 5 770 7 d -2 219 7 b - 1 , 3 3 1 7 8 0 1>0 7 M I s13 7 d 2 Y O 7 8 3 1 8 2 7 b 'I I10 7 9 - 1 L ? 3 I 7 Y - d 465 7 9 - 7 1 1 5 7 41 - 6 429 7 9 -4 2 4 ' , 7 <I -2 1.26 i 9 > 1 8 4

7 1 0 - 4 ZJ>

7 I 0 -4 9 0 7 10 - 3 I h 2 7 10 -1 I86 f 1 C - I 1 3 2 7 10 2 2I1

7 9 LO^

10Fc l ? 4 -95

c 4 - 535

1 3 L 4 1 3

- I 14 -405 - 3 77

34 6 - > ( I

-272 1 %

3 e 7

4 h /

- 2 4 2 344

- 1 12 -31 3 - 13'4

I 3 0 - l ? d

I 2 9 /GO 14 I tit

-145 - 1 6 7

2 b 7 - 4 I8

3 7 2 b63

-45I - J 3 9

1 7 7 L 5 Y

-37v 124 321

-214 - 1 4 9

12Y 125

- 2 2 b - 3 4 1

3Y3 -2 I 3 -120

#' 3 I 247

- 2 6 1 1 1 4 1 5 7 3 6

- 2 2 b -4 00

4 1') -551

t>cc - 1 h')

~ ' 0 6 -189 >21 3 5 7

- 2 4 L - 2 1 I

I ? h i 3 0

- 3 I 5 - 5 1 - '% 7 2 C L

- I r4'1

- L I B 132 2 1 1 57

- 2 5 3 135

- 3 1 4 -161

3 14 1 6 1

- 2 3 3 1,!2

jV6 -120 - 3 3 8

2 2 1 - Y Y

P 4 174 - 1 4

1 3 3 1 1 4

- I t ? ( , - 32

-167

- I flrJ

I r4

- 2 1 1

A k I lOlFol r 11 - 1 17-1 1 11 -5 190 7 12 I 1 70 7 I 3 -9 I77 I 13 - I 113 ti 0 -20 123 8 0 -18 l a 1 8 0 - 1 h 4 1 8 0 - 1 4 2 3 3 8 0 -12 173

LI 0 - d 341 8 0 -6 6 3 1

a o - 1 0 325

8 0 u 4 7 9 n c: z 140

a o 8 2 8 5 8 0 6 182

u 0 1u 114 8 L 12 24 ' ) 8 1 - l Y 90 8 1 -10 4 0 H 1 -17 122 U 1 -16 1 9 ) 8 1 - 1 5 2 3 5 8 1 - 1 4 4 5 8 1 -13 LYY 8 1 - 1 2 67 8 1 - I 1 229 H 1 -1U 300 8 1 --'I 2 3 6 8 1 -8 IM d 1 - 1 1 2 d 8 1 - 6 111 8 1 - 3 1 3 3 8 1 -1 110 8 1 - 1 267 8 i 1 2 2 r M 1 L zao 8 1 3 3 0 9 8 1 4 141) 8 I 5 L O U 8 1 n ' ) L 8 L - 1 7 1 3 2

M 2 -14 1 4 2 tl 2 - 1 3 1 3 )

8 L - 1 1 134

8 2 - 3 127 M 2 - U 32d M 2 - 7 5 4 5 8 2 -I 2 8 8 8 2 - 5 3 4 3 M 2 - 4 6 5 8 2 -3 402 8 2 -2 120 & 2 -1 2 J 2 8 L L 1 1 4 8 2 L 1 4 0

Y 2 -15 141

a c -12 ~ h ( ,

tl L - I U icln

8 2 4 i 4 r 8 2 5 1 7 1 8 L b 66 8 2 7 177 0 2 R 161 8 2 Y 220 8 1 10 6Y 8 2 1 1 109 8 3 - 1 6 2 1 i 8 3 - 1 4 261 8 3 -1.' 447 8 3 -11 8 2 8 3 - 1 0 211 8 3 - 1 8 s M 3 - I 126 U 3 - 6 190 8 3 - 2 1 4 h 8 3 - 4 15i

M 3 - 2 3 6 3 M 3 -1 Y < ) 8 3 u 302 8 5 1 87 a 3 L 2 5 0 8 3 3 ' I 0 8 3 4 2 7 2 8 3 b L L V 8 3 10 6 1 8 4 -13 1 7 ' ) 8 4 - 1 1 3 1 3

8 4 263 M 4 - I 2 5 i u 4 - b 91

a 3 - 3 25t1

a 4 - i t , 1 3 %

a 4 - > 337 a 4 - 4 131

a 4 -1 JW, R 4 - 3 L ' I I

8 4 c, 152 8 4 2 l 8 J 8 4 I < 9 4 b 2 - 1 3 2 3 )

10Fc - 1 ?h

1 I 3 84

155 - I Ot'

1 3 3 - L 3 9

7 I -,*74

L 4 l i 06

- > J Z 13 h 6

- 5 3 i 13'1

-1CI / H >

-7 I 6

73 - '1 (1

-143 I81 > L 6 - ? c1

- 2 76 7 1

2 1 5 -?W - 2 1 1

'1 * I I L 3 - 2 V -120

$ 5 215

- 194 2 3 1

-142 -205

- d 7 1 1 7

-158 - 101: - 1 2 2 - 2 2 5

1 C 6 ' 6 1 -9M

- 3 L 9 3 0 1 i* f I ti

- J 3 0 - 5 ( : 'I I t :

- 1 3 0 -176

1 4 2 l 3 h - 0 0

-172 - P '1 I s 5

- : 02 - 4 4 12'J *' I 3

-i45 4 12 31

- ? I I I tu

- 1'16 - 179 - 1 5 5 - c L 1 h 0

<J

- I 3 6 Ro

2 4 3 '+(I

- 2 '+ 4 1'1.2 - 7 7

- 1 ( 1 112

- 1 4 3 -,I76

I ' ) h -7 9

- 3 1 s 113 I' 9 0

- 53h 1 3 8 761

-1L'3 L 3 5

I r?

?nk

12'J

1 r 4

h k l M !I -I2 8 5 - 1 1 R 5 -10 8 5 - 4 0 5 -8 8 5 -6 u 5 -5 (1 5 - 3 R 5 - 1 8 5 1 8 5 3 8 5 2 8 h - C 8 6 -6 8 b -> ti 6 - 4 8 6 - 3 8 6 -2 H 6 - 1 t 3 6 b 8 - 5 2 8 7 -11 M I - (J d 7 -M & 7 -7 8 7 - h 8 I - 2 u 7 -1 8 7 - L 8 7 0 8 1 1 M 7 Z M d - 1 1

8 8 -& ti & -7 M 8 -L)

tl b - 3 M 8 - 2 B d h M 9 - I 8 Y -3 8 9 - L 8 9 0 R IC - & 8 10 - 7 R 10 - 5 8 11 - U 8 1 1 -I,

8 I 1 - I 9 0 - A i Y l J -1L: 9 0 -16 Y U -14 9 0 -10 Y 0 - u 9 L - 1 , Y 0 -4 v 0 - 2 Y 0 3 9 0 2 Y O 4

Y U " Y u 1c1 v 1 -LU 9 I -1') 9 1 -It, Y 1 - 1 7 Y 1 - 1 6 9 1 - 1 3 Y 1 -14 '3 1 - 1 5 9 1-12 Y 1 - 1 1 9 1 -1u 9 1 -9 Y 1 -6

v 1 -6 Y 1 -I, Y 1 - 4 Y 1 - 3 9 1 -2 9 1 - 1 9 1 0 Y I 1 ' I 1 3 9 1 4 9 1 5 9 1 1 ? l t i 3 1 4 Y 1 10 Y 1 1 1 9 L -17 9 2 - 1 6 Y 2 - 1 5 Y 2 -14 9 2 - 1 3 9 2 - 1 1 Y L - 1 u

a 8 -'3

9 0 6

Y 1 - I

lOlFol lOFc 1 3 5 I ? L 3 1 4 -303

313 232 -226 ,303 69 1 1

277 252 124 - 1 3 2

8 1 I > ( , 2 4 2 - 1 4 2 2 8 3 2 6 3 I84 -2<1 '# 216 1.41 396 4 C t , 4 4 8 - 4 4 2 121> 1 4 2 I l h I 1 6 1 4 6 - I 4 4 l d - 4 2 4 / 6 4 -124

Y 1 131, 256 - 2 h e 99 I ' r

14J -144 98

134 174 l l t l - 1 5 4 I51 I01 Z7H - / < J R 190 18.2 7 1 8 " 3 4 1 2 4 -114

89 -150 172 l t ! 7 190 1 5 1 3 6 3 -174 44(1 4 2 2 252 - 2 4 1 177 - 1 3 3 1 4 1 6 6

7 1 - 4 3 128 -66 2 l h -.") 7 18'3 1 I l l

123 - 1 2 4 201 *'(I'' 32 - 7 9 13L1 '>H

3 6IJ

21 -14 64 - 7 1

j6Ci 17C1 143 - 1 3 5 3 3 I - 3 3 1 106 I21

4 1 - 9 8 232 - 1 3 7 3 d O 3 1'2 J 9 3 - 4 1 3 4 4 1 4 3 7 1 7 i -172 14Y L55

J'I - 1 Ofi L O O - 4 I 1 0 9 - 1 1 0 198 -17b 1 8 4 164 172 lf>>

8 U - b 5 1 1 1 - 1 7 4 96 , , 3

1 2 1 - 1 1 4 45 - 7 7

131 173 l0M - 1 2 J 106 -<I0

2 3 d 132 2Cl 1 4 H 246 -227 1 b 1 -117 2 1 4 2 4 1 352 114 173 - 1 4 7 3Y4 - 3 h 4 2 4 2 2 6 1

4'1 - 3 2 101 J 7 2 2 3 - 2 7 1 121 - 1 3 7 17') 1 7 4 I30 - L 3 3 7 0 1 - L > l I17 1 1 5 103 1 1 1

4 d 4 1 8 3 l ( I

150 - 1 3 7 / l I - , ' I 7 316 3 1 1 174 -1I5

321 1 3 5

2 0 2

7 1 8 5

Publ

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View Article Online

Inorg. Phys. Theor.

h k 1 10[FoI 1OFc 9 2 -7 125 1 1 6 9 2 -d 2)J2 2 5 Y 9 2 -6 217 - 1 6 3 Y 2 - 5 147 -136 ' 9 2 - 4 8'1 1oz 4 2 -2 235 ZZC, 9 2 -1 3 8 1 -j53 4 2 U 143 -133 9 2 1 3 h ' > 371 Y 2 3 224 -221 '3 ,! 4 . i o ! i - 1 4 i i '1 2 5 319 2 0 6 9 2 h Y h 8'1 < I z 7 104 5 2 'I 3 - 1 6 146 -13.0 Y 3 - 1 3 1 3 5 -164 ' I 3 -12 1(>5 166 9 3 -11 1 3 1 1 5 4 Y 3 -1c: 163 -192 v 3 -7 94 82 3 3 -7 301 -296 9 3 -6 30'1 -325 ' 3 3 -'j ?I1> 8 1 9 3 - 4 362 327 9 3 -3 8 9 -3c j 3 3 0 1 4 9 1 4 5 y 3 1 1 1 2 1 0 4 Y 3 3 9 3 1cs '3 3 4 131 -107 4 3 h 130 1 6 1 3 3 !1 1 7 4 -135 9 4 -13 253 2 4 3 Y 4 -12 158 -134 9 4 -11 303 -316 Y 4 -10 221 938 9 4 -5 133 1 2 2 9 4 - 4 120 ti4 4 4 -2 22'1 - 2 4 d 9 4 0 55 -22 9 4 1 241 2 5 1 3 5 -9 267 ;!46 3 5 -8 17ir 1 6 2 4 5 -7 301 -;!76 3 5 -6 '31 -129 9 5 -5 ; ! 8 h 2t:7 -1 5 -3 2 3 7 -213 9 5 - L 185 -1R6 9 5 0 7P 6 b 9 5 0 159 92 3 6 -14 1 2 6 1 4 1 '1 (I -16 323 310 Y 6 -7 70 - b 5 9 6 -ti 198 -182 3 6 -7 270 2 3 1

3 6 0 1 5 5 l E 4 Y 6 2 81 -145 9 7 -13 163 -131 0 7 -0 1'37 L P Z 9 7 -8 1 5 7 -147

9 6 -1 4-r 40

h k 1 lopol l0Fc '1 7 - I 135 -113 3 7 - h 203 171 9 '7 -5 2 0 8 232 9 7 -4 127 -92 4 7' -3 210 -174 9 7 -2 127 147 L) 7 0 154 - 1 5 1 1) 3 - 5 ) 1 2 h -112

9 8 -3 103 -71 3 8 - 2 112 -1C,4 9 9 - 1 0 1 0 0 64 9 9 -8 122 - h 3 9 Y -6 212 2 1 1 9 9 -4 8'3 -117 9 9 -2 1 4 2 1 2 5 9 9 0 147 - l 3 2 9.. lij -10 Y O -101 9 10 -'I 104 -87 9 1 1 -9 90 -86

10 0 -20 3 7 -1.33 10 0 -11;- 118 1 4 2 10 0 -12 136 165 10 0 -10 367 -369 1 0 0 -6 40 5 4 1 0 0 -t> 1 3 5 -140 10 0 -4 538 5E2 1 0 0 -2 515 -524 1 0 0 0 180 1 7 3 1 0 0 2 4 7 20 10 ti 4 66 7 4 10 0 3 47 - 1 1 2 10 1 -18 12H 1 3 3 1 0 1 -17 152 14Y 1 0 1 - 1 5 1 7 3 -174 10 1 -14 129 129 1 0 1 L 1 3 144 12'1 10 1 -1% . 1 1 2 -105 10 1 - 1 1 17.5 -15'3 1 0 1 - l C 111 1 0 6 10 1 -9 7 9 51 1 0 1 -7 112 -126 10 1 -6 178 -273 10 1 -5 1 6 7 * 1 5 0 1 0 1 -2 h4 - B L 1 0 1 -1 2 3 5 -221 10 1 0 2 2 4 231 10 1 1 247 247 I0 1 2 4 b -54 10 1 3 193 -189 1 0 1 4 ' 16 so 10 1 5 152 130 1 0 1 7 101 -104 10 1 8 4 4 t,C 1 0 3 9 60 68 10 2 -12 1 1 7 1 2 6 1 0 2 -9 2 5 A 2 3 3 1 0 2 -u 130 -135 i c 2 -7 396 - I t f i ' r

3 0 2 -5 300 312

v a - i 13s 117

TABLE 2 (Continued) h k 2 lOlFo1 lOFc

10 2 -4 3 2 6 3.41 10 2 - 3 192 -183 1 0 2 - 2 1 9 5 -173 10 2 -1 2 4 3 ' 210 1 0 2 1 229 -216 lil 2 Z 96 -86 10 2 3 6fl 6 4

10 3 -14 108 2 0 5 10 3 -12 134 -113 10 3 -10 240 2 4 4 1 0 3 -8 3 4 6 -321

10 3 -6 132 1 4 3 10 3 - 5 110 1 0 3 10 3 -4 65 4 2 10 3 -3 93 -104 1 0 3 - Z 130 -122 1 0 3 -1 1CA -30

10 3 2 1 7 4 -166 1 0 3 4 2 5 9 2 4 5 10 3 s 90 S f l 10 3 6 212 -217 10 3 8 137 1 2 1 1 0 4 -8 136 -118 10 4 - 1 37(1 - 3 6 3 10 4 -6 211 2 1 1 1 0 4 -5 265 302 1 0 4 -4 1 7 2 -160 10 4 -1 1 3 5 1313 1 0 5 -13 2 1 1 -226 10 5 -11 174 170 1 0 5 -19 111) 1 0 4 10 5 -'J 300 -232 1 0 5' -7 223 755 10 5 -2 1 4 9 - 1 3 2 1 0 5 0 153 144

1 0 6 -10 2 1 0 ZC2 1 0 6 -8 1 6 6 -153 10 6 -6 252 2 0 3 10 6 - 4 346 -326 10 6 -2 160 1 5 7 10 6 0 150 -147 1 0 7 -11 1 4 1 142 10 7 -10 214 - 2 1 9 10 7 -9 316 - 2 4 s 10 7 -0 9 5 t13 10 7 -5 156 1 0 1 10 7 -2 94 2 h 10 7 0 90 - 7 3 10 8 -8 9 3 -Il!1

L O 8 - 7 180 172 10 8 -6 163 1 8 0 10 0 -3 1 6 3 1 6 5 1 0 8 -1 1 6 8 -237 1 0 9 -10 122 -119 10 9 -9 9 B -45 1 0 9 0 126 -120

10 3 -16 111 - e 7

10 3 --I 9 2 -56

10 3 0 102' 141

10 s 1 211 -170

h k I 1O[F0I 10Fc 1 0 10 -9 150 -145 1 0 10 it 1 0 0 96 11 0 -18 49 4 3 1 1 0 -16 4 3 h7 11 0 -14 170 1 P 3 11 0 -12 3 2 3 -330 11 0 -10 272 2 8 4 11 0 -t? 203 -219 1 1 0 -6 67 92 11 0 -4 132 -120 1 1 0 - 2 .96 8 1

11 0 6 1 0 3 -90 11 1 -18 4 4 r 2 5 I 1 1 - 1 7 6 3 -P,3 11 1 - 1 5 182 1 3 1 1 1 1 - 1 3 115 -117 I 1 1 -12 1 2 6 92 11 1 -11 S h -35 11 1 -3 1 2 9 -92 11 1 -6 4 6 -1 11 1 -5 250 217 1 1 1 -4 113 - 1 c s 1 1 1 -3 17.3 -174 11 1 -2 723 2 3 5 11 1 -1 240 2 1 5 11 1 0 7 3 -62 1 1 1 1 2 1 6 -214 11 1 2 6 5 P,7 11 1 3 7 4 lG3 1 1 1 4 6 4 -76 1 1 2 -15 9 3 97 11 2 -14 4 9 9 h 11 2 -13 117 -123 1 1 2 -12 157 -175 11 2 -11 214 2 2 8 11 2 -10 176 I 6 9 11 2 -f3 2 2 3 -226 11 2 -8 235 -144 11 2 -7 205 2 5 2 1 1 2 -6 49 b 8

11 z -2 8 1 24 1 1 2 0 92 22 11 2 3 49 9(> 11 3 -16 1 1 9 1 2 7 11 3 -14 6 4 -38 11 3 7 1 2 161 164 1 1 3 -I1 5 6 - 3 Y 11 3 -0 1 6 3 -149 11 3 -6 201 107 1 1 3 -4 260 .-?65 11 3 -2 1 7 6 11 3 - - I h 6 -66 11 3 0 2 0 5 -199 1 1 3 2 1 4 2 1 5 2 11 4 -15 1 2 7 1 4 0 11 4 -14 110 -119 11 4 -11 1 5 6 121 1I: 4 -10 1 2 3 ,109 11 4 -') 213 -218

i i o (i i i 4 i c d

11 z -5 1 8 1 -179

h k 1 101Fol 10Fc 11 4 -8 1 Y 9 215 1 1 4 -7 234 2 0 1 11 4 0 9 0 -5 11 5 -? 1 6 5 167 11 6 -12 1 0 3 205 11 6 -10 1 8 5 -176 11 7 -13 1 4 0 1 0 7 11 7 -11 50 -72 11 7 -9 127 -125 11 7 - I 161 1 4 2 11 8 -10 1 3 5 -17Y 1 2 0 -16 105 l ' l& 12 0 -14 1 0 3 -124 1 2 0 - 1 2 271i 2 0 5 12 0 -10 157 -160 1 2 0 -11 4 6 - f , 3 12 0 -4 244 -219 12 0 -2 132 1'15 1 2 0 0 91 -PO 12 1 - L ! J 6 3 17 1 2 1 -14 79 -60 1 2 1-13 H 9 -115 1 2 1 - 1 2 135 1 3 5 1 2 1 - 1 1 220 224 12 1 - 3 215 -219

1 2 1 -6 i13 - 1 1 1 1 2 1 -4 6 5 '31 1 2 1 0 4 8 ' - 4 5 1 2 2 -1s 200 -1'31 12 2 -13 1 8 3 1 3 3 1 2 2 - h 70 1 2 6 1 2 2 -5 4 9 - / I 12 2 -4 49 - 4 8 12 2 -3 155 1 4 6 1 2 2 -2 104 1.3% 12 2 -1 155 - 2 2 4 12 3 -14 A5 - 1 1 9 12 3 -12 1 9 6 1'15 1 2 3 -10 1 2 1 -123 1 2 3 -ti 124 130 1 2 3 -6 1 4 6 - l h 8 1 2 3 -4 65 9 2 1 2 3 0 flh -80 12 3 2 196 1i;o 12 4 -16 12% -141 1 2 5 -7 221 -2C6 12. 6 "0 13.r 1 4 ' 1 13 0 -12 114 138 1 3 0 -10 I0 - 9 0 13 0 -B 83 !)7 13 0 - 5 1 3 0 -162 33 0 - . . 4 40 4 2 13 0 0 5 7 - 4 3 1 3 1 - 5 1 4 8 -148 1 3 3 -16 2 -t?h 13 3 - 8 103 Y Y 13 3 -6 ,119 -123 13 3 - 4 100 . 100 13 3 -2 11'3 -144 1 3 3' 0 136 126

1 2 1 - 'r 113 cia

TABLE 3 Positional and vibrational parameters. The numerals in parentheses are lo4 times the estimated standard deviations of

The vibrational parameters, 02, are mean square vibration amplitudes (in A) relative to the positional parameters. the crystallographic axes

X

0-2878( 1) 0*0780(9) 0.0654 (9)

-0.0585(9) -0*0448(9)

-0*1528(10) 0.0532( 11)

0.5016( 10) 0*5862(9) 0-6499( 11) 0*5426(9) 0*3403( 11) 0*5687( 10) 0.201 7 (8) 0.0844( 7)

0*4929(9) 0.3990( 8) 0.43 84 (9) 0.1827 (7)

- 0.0 1 87 (7) 0*3639(7) 0-5699( 8) 0.0763(9) 0.6991 (9)

- 0.0868(9)

Y 0*0864( 1) 0.2701 (7) 0-2543 (8) 0.1623( 9) 0*0508( 8)

- 0*0968( 9) - 0*0109(8) -0.0216(10)

0-0657(9) 0-0060( 10)

- 0*0525(9) -0*0871(10) - 0.1316(9)

- 0.0022( 7) - 0.1064( 8)

- 0*0232(7) - 0*1528( 8)

0-2094( 8)

0.1676(7)

0.2 192 (6) 0.3276(6)

- 0.01 37( 7) -0.0989(7)

0*0803(8) 0*2621(8)

z 103U5, 103Ueza 0*2189( 1) 26 29 0.1 242 (6) 38 14 0.2 181 (6) 32 32

0-1556( 6) 24 26 0.1 123( 7) 38 38 0*0879(6) 33 29

0-2040( 6) 26 35

0.1 667( 7) 34 39 0-2429( 7) 20 43 0.33 76 (8) 43 33 0.3705( 7) 26 35 0*3799(8) 44 39

0-2897(5) 32 37

0.0639( 6) 35 39

0*4463( 6) 41 37

0.4401 (7) 37 29

0*1688(5) 27 24

0.2471 (6) 36 30 0-3323( 6) 36 26

0.1 137 (4) 35 27 0.061 7(5) 33 41 0*1332(5) 36 50 0.1430 (6) 42 52 0*4264(5) 67 59 0*4544( 6) 53 54

* W represents a water molecule.

1O3uaa3 33 34 27 32 36 39 36 49 38 48 37 48 34 33 34 41 49 40 37 31 38 40 70 38 54

103U2,~

2 -7

1 0 2

-4 -3

7 4 3 3 2

-1 0 1

- 5 7 5

-6 6 6 0

15 -9 -8

1OSUa,, 11 15 10 10 13 14 12 21 11 17 7

23 12 10 13 16 17 15 16 16 9

16 33 28 20

1O3OSOs 0 5

- 1 -1 10

-6 -3 12 11 12

- 2 -1

5

-1 - 7 12

-1 -1

1 14

-11 -9

6 8

0 Y

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390 J. Chem. SOC. (A), 1970 the reciprocal lattice to a resolution of 0.95 A (= h/2 sin Om,,) while the remainder extend in some regions to about 0.7 A.

Solution of the Structure and Refinement.-The cobalt atom position was found from Patterson projections and con- firmed in a three-dimensional Patterson series. The other atoms (except hydrogen) were found from a Patterson superposition function, using the four cobalt atoms in the unit cell as origins, and from the three-dimensional electron- density series phased by cobalt. Refinement by difference- Fourier series reduced R to 0.27. Ten cycles of least- squares refinement followed using the block-diagonal approximation during which anisotropic vibration para- meters were introduced, first for cobalt and then for the other atoms, and then the contributions of twelve hydrogen atoms were included in the structure-factor calculation. A difference electron-density series computed before this last

II

factors is summarised in Table 1 and the values are given in Table 2.

RESULTS AND DISCUSSION

The molecule is illustrated in Figure 1 (a) ; positional and vibrational parameters are given in Table 3.

Each cobalt atom is approximately octahedrally co- ordinated to two nitrogen atoms and an oxygen atom of each histidine group, one of which is D- and the other L-histidine. The imidazole groups are cis to each other; the molecule has no symmetry and the relation of the histidine groups to each other is quite different from that in the other metal histidine complexes we have studied (see Figure 1) .l>

FIGURE 1 One molecule of bis(histidino)cobalt with the structure described here (a) is compared with the previously determined structure of bis-(L-histidino)cobalt (b). In (a) the histidine group I is in the D- and 11 in the L-configuration.

step ( R 0.15) showed a number of peaks attributable to hydrogen atoms and no other significant features. Dia- mand's SFLS program was used and all the preceding calculations were done on an Atlas Computer. Subse- quently the refinement was transferred, and the later part repeated, with the full-matrix program XFLS 6 on an IBM 360/67 computer, where it converged in four more cycles, with the results described later and R 0.11. Re- flections were given weights appropriate to a(F,) = 1 for (F,I < 20 and o(F,) = 0*051F01 for greater values of IFol. The atomic scattering factors were taken from ref. 7 and that for cobalt was corrected for anomalous dispersion. The data in Table 1 refer to calculations treating all the atoms as neutral ; an alternative refinement assuming Co2+ and 0 4 - for all the carboxylate oxygens was tried but led to no difference in the agreement indices.

The agreement of observed and calculated structure

6 W. R. Busing, K. 0. Martin, and H. A. Levy, ORFLS, A Fortran Crystallographic Least-Squares Program, Oak Ridge National Laboratory, Oak Ridge, Tennessee, 1962.

' International Tables for X-Ray Crystallography,' vol. 111, Kynoch Press, Birmingham, 1962, pp. 202 and 215.

Bond lengths and angles are given in Table 4. With one exception we do not consider that any of the values within one histidine group are significantly different from those for the other histidine group or from their expected values; 8 7 9 C(ll)-C(l2)-C(l3) is 6" greater than C(l)-C(2)-C(3), a difference which may be associated with the conf ormational differences described later, although neither bond angle is outside the range occurring in other metal histidine complexes. However, there are small but significant differences in the bond lengths to cobalt and in the conformations of the two groups, differences similar to, but larger than those found in bis-(L-histidino) cobalt. The differences in conformation are illustrated in Figure 2, and can be seen in the con- formation angles in Table 4(e). Also, while the atoms of each imidazole group are coplanar (to within 0.02 A, i.e. within the limits of error of the positions), the cobalt

8 R. E. Marsh and J. Donohue, Adv. Protein Chem., 1967, 22,

9 H. C. Freeman, Adv. Protein Chem., 1967, 22, 258. 235.

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Inorg. Phys. Theor. atom is 0.11 A from the plane of imidazole 11, but 0.74 tf from the plane of imidazole I. The carboxy-group of histidine 11 is involved in only one hydrogen bond (3 A as illustrated in Figure 2(a); the conformation of this histidine group is very like those in bis-(DL-histidino)- nickel, and like one of the two in bis-(L-histidino)cobalt. The carboxy-group of histidine I is involved

TABLE 4

(b) Bond angles (") N( l)-Co-N(2) N( l)-C0-0( 1) N (2)-C0-0 ( 1) N( l)-Co-N( 11) N( l)-Co-N( 12) N (2)-Co-N ( 12) N (2)-C0-0 (1 1) N(11)-Co-O(1) O(1)-co-O(l1) O( 1)-C( 1)-O(2) C(2)-C(l)-O(l) C(2)-C( 1)-O(2)

C(l)-C(2)-C(3)

C( 2)-C( 3)-C( 4)

C(l)-C(2)-N(l)

N ( 1 )-C ( 2)-C (3)

N (2)-C (4)-C (3) C ( 3) -C (4) -C (6) N (2)-C (4)-C (6) C( 4)-C( 6)-N (3) C ( 6)-N ( 3)-C( 5) N( 3)-C( 5)-N( 2) C (5)-N (2)-C (4)

87.9 76-2 84-6 99.7 98.3

100.3 93-0 91.9 95-0

125-4 116.1 118.4 111.5 106-7 110.6 113.7 123.0 127-1 109.8 105-2 107-7 112.1 105-1

Co-N( 11) CO-N ( 1 2) co-O(l1) C( 1 1)-C( 12) C( 12)-C(13) C( 13)-C(14) C( 14)-C( 16) C( 14)-N(12) C( 15)-N( 12) C(15)-N( 13) C( 16)-N(13) C( 12)-N(l1) C(l1)-O(11) C( 11)-O( 12)

N(ll)-Co-N( 12) N( 1 l)-C0-0( 11) N ( 12)-C0-0 ( 1 1) N( l)-C0-0( 11) N(2)-Co-N( 11) N( 12)-C0-0( 1)

O( 1 1)-C( 1 1)-0 ( 12) C( 12)-C( 11)-O( 11) C( 12)-C( 11)-O( 12) C( 1 1)-C( 12)-N( 11) C(ll)-C(l2)-C(13) N( ll)-C(12)-C( 13)

N( 12)-C(14)-C(13) C( 13j-C( 14)-C( 16) N ( 12)-C( 14)-C( 16) C ( 14)-C ( 16)-N( 13) C( 16)-N ( 13)-C( 15) N(13)-C( 15)-N(12) C(15)-N( 12)-C(14)

C( 12)-c(13)-c(14)

(c) Estimated standard deviations Co-N, co-0 0-01 A Angles a t Co Other bonds 0.015 Other angles

in four

2-141 2-077 2.067 1.51 1.51 1.49 1-33 1.38 1.30 1.34 1.37 1.49 1-29 1-23

84.1 78.6 90.3

171.0 170.6 172.6

124.2 118.6 117.2 109.7 112.3 110.2 114.3 121.7 127.1 11 1.2 105-0 108.0 111.3 104.6

0.4" 0.6"

(d) Hydrogen bonds and short intermolecular contacts (<3.3 A) involving nitrogen and oxygen atoms. The italic letters are used to identify the contacts in Figure 2. Contacts >3A are rather long for hydrogen bonds, but hydrogen atoms are available in every case

u N ( l ) . . . O(W1) 3.16 i%

b N( l ) . . * O(12II) 3.02 G N(3) - . - O(l1) 2.82 d O(2) - - . O(WlII1) 2.88 e O(2) - . - O(W1IV) 2.77 f O(2) - * - 0(W2v11) 2.88 g N(11) * * * O(12II) 3.28 h N(11) * 0(W2LI 3.26 j N(13) - * - O(W2 ) 2.69 k O(11) - * * O(W2V) 2-79 K' O( 12) * * O(W2V) 2.99

Roman numerals as superscripts refer to the equivalent positions, relative to the reference molecule a t x, y, z :

1 -x, -y, - 2 v l - x x , - ; + y , * - z I1 l - x x , & + y , 4 - 2 VI 1 - x , -y , 1 - 2

I11 -x, & + y , & - 2 VII -1 + x , ; - y , - * + z IV x > 3 - y . - 8 + 2

TABLE 4 (Continued) (e) Dihedral angles ("), between the planes of

O M , C(1), C(2) and C(1), C(2), N(1) 0(12), C(11), C(12) andC(11), C(12), -167 I)1

167

-51 x1 - 120" C(11), C(12), C(13) and C(12), C(13), 58 x1 - 120"

N(11)

C(14)

N(12)

C(1), CP) , C(3) and C(2), C(3), C(4)

C(2), C(3), C(4) and C(3), C(4), N(2) -41 xZl C(12), C(13), C(14) andC(13), C(14), 15 X2l

* The signs, and symbols I), x, correspond to those used by Lakshminarayanan et al., who have tabulated data on amino-acid conformations (A. V. Lakshminarayanan, V. Sasisekharan, and G. N. Ramachandran, in ' Conformation of Biopolymers,' ed. G. N. Ramachandran, vol. 1, Academic Press, London, 1967, 61). f The second member of each pair is for a histidine group in the D-configuration, hence the change of sign.

strong hydrogen bonds which seem to favour a twist of this group [mainly a twist around C(3)-C(4)] as shown in Figure 2(b) and also to account for the lengthening of the Co-O(1) and Co-N(2) bonds. Thus the histidine group accommodates itself not only to the metal ion to which it is co-ordinated, but to some extent, to potential hydrogen bonding groups in the environment.

It does not seem necessary for the metal ion to lie exactly in the imidazole plane, displacements between 0 and 0.38 A have been observed in other complexes of Co2+, Ni2+, and Zn2+, corresponding to angles of 0-10" between the N(2)-M bond and the imidazole ~ l a n e , l - ~ while in bis(histidino)cadmium lo the cadmium ion is 1-15A from the imidazole plane and the N-Cd bond makes an angle of 30" with it. So the present observ- ations of N-Co bonds making angles of 20.9 and 2.9" with their respective imidazole planes fall within the previ- ously observed range. The flexibility of the system would suggest that the bonds have considerable ionic character.

The thermal vibration parameters (Table 3) also show that the carboxy-group of histidine I is more rigidly held by the hydrogen-bond system than that of histidine 11; the mean-square vibration amplitudes of the oxygens are 0.034 and 0.048 Hi2 respectively. The remaining atoms of histidine I all have slightly lower vibration parameters than those of histidine 11, but the contrast between the two groups is much less; the average values are 0.035 and 0.040 Hi2 respectively.

The packing of molecules in the lattice is illustrated in Figure 3 and involves a number of hydrogen bonds. N(13)-H - * - O(W2) is particularly short, 2.69 A ; O(W2) is in an ideal position for this hydrogen bond, being within 0.25 A of the plane of the imidazole ring and almost on the bisector of the C-N-C angle [see Figure 2 (b)]. Both oxygens of the carboxy-group of histidine 11 may be involved in a bifurcated hydrogen bond to another O(W2), k and k' in Figure 2 and Table 4(d); the distances are comparable to those in violuric acid monohydrate,ll but as Donohue emphasises in a recent

lo R. Candlin and M. M. Harding, J . Chem. SOC. (A) , 1967, 421. 11 B. M. Craven and Y. Mascarenhas, Acta Cryst., 1964, 17,

407; B. M. Craven and W. J. Takei, Acta Cryst., 1964, 17, 415.

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392 J. Chem. SOC. (A), 1970

C'\, \

\

(a 1 (b) N1)b FIGURE 2 Projection of each histidine group on the mean plane of its imidazole ring to show the small differences in the cobalt

co-ordination and in the orientation of the carboxy-group in relation to the hydrogen-bonding environment. The mirror image of histidine I, which is actually D- , is shown (right) for easier comparison with histidine 11 (left) which is in the L-con- figuration. Hydrogen bonds <3.0 A are shown as broken lines, longer ones as dotted lines, and they can be identified in Table 4(d) by the italic letters, a, b, c, etc.

FIGURE 3 b-Axis projection showing the arrangement of molecules in the lattice. The cobalt atoms of molecules shown in full lines Only the hydrogen bonds shorter than 3 A around one are near y = 0 or 1 ; the others (broken lines) are near y = 0.5.

molecule are shown, as dotted lines

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Inorg. Phys. Theor. 393 discussion,12 determination of the hydrogen position is necessary to establish such a bond. Imidazole rings of neighbouring molecules lie in parallel planes across the centres of symmetry at O,O,O and *,O,&; their separations are 3.61 and 3-50 A respectively. The shortest inter- molecular distances, other than the hydrogen bonds listed, are 3.28 A [C(6) O(l1) at - x , -y, -23 and 3.24 [C( l l ) . O(W2) at 1 - x , -8 + y, Q - 23; in

la J. Donohue, in ' Structural Chemistry and Molecular Biology,' ed. A. Rich and N. Davidson, Freeman, San Francisco, 1968, p. 443.

both cases a neighbouring atom to the carbon is involved in a short hydrogen bond.

We thank the S.R.C. for financial assistance, Dr. H. A. Long for the preparation of crystals, and Dr. R. Diamand for his least-squares refinement programme. The com- putations were done on the Atlas Computer of the S.R.C. (at Chilton, Berks.) and an IBM 360/67 at Newcastle University, and we thank these establishments and the Edinburgh Regional Computing Centre for their co- operation.

[9/820 Received, May 16th, 19691

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