supporting information - wiley-vch · 2004. 10. 13. · spectrometer accessory attached to an hp...
TRANSCRIPT
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Supporting Information
for
Angew. Chem. Int. Ed. 200461152
© Wiley-VCH 200469451 Weinheim, Germany
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1
Electrophilic double-sandwiches formed by interaction of Cp2Fe and Cp2Ni with
the tridentate Lewis acid [o-C6F4Hg]3
Mason R. Haneline and François P. Gabbaï*
[*] Prof. Dr. François P. Gabbaï
Chemistry Department
Texas A&M University 3255 TAMU
College Station, Texas 77843-3255
Fax: (1) 979-845-4719
E-mail: [email protected]
SUPPLEMENTARY INFORMATION
♦ Experimental Section (4 pages)
♦ Crystal data and structure refinement for 2 (8 pages)
♦ Crystal data and structure refinement for 3 (8 pages)
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2
Experimental Section
General. Due to the toxicity of the mercury compounds discussed in these studies extra
care was taken at all times to avoid contact with solid, solution, and air-borne particulate
mercury compounds. The studies herein were carried out in well-aerated fume hood;
however, a glovebox was used to manipulate the air sensitive compound nickelocene.
Atlantic Microlab, Inc., Norcross, GA, performed the elemental analyses. Nickelocene
was purchased from TCI America and used as provided. The remainder of commercially
available starting materials and solvents were purchased from Aldrich Chemical and were
used as provided. Compound 1 was prepared according to the published procedure
outlined by Sartori and Golloch.1
13C MAS NMR: 13C MAS NMR spectra were measured with a Bruker 4 mm CPMAS
probe at 100.6 MHz and referenced externally to glycine (carbonyl peak at 176.3 ppm).
In addition to simple Bloch decay 13C spectra, 13C spectra were measured with 19F
decoupling and separately with 1H decoupling. {1H} 13C and {19F}13C CPMAS spectra
also were measured (Figure 1).
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3
UV/Vis: Diffuse reflectance visible spectra were recorded on a Labsphere reflectance
spectrometer accessory attached to an HP 8453 UV-Vis spectrometer. The diffuse
reflectance spectra of 3 and nickelocene were analyzed by deconvolution using the
Peakfit program. Both spectra were analyzed on the basis of the four main transitions.
Table showing the results of the deconvolution:
Cp2Ni 3 � peak eight fwhm � peak
height fwhm
3A2g→3E1g: 426 nm 22.8 117 426 nm 22.8 117
3A2g→3E2g 589 nm 4.5 152 589nm 4.5 153
3A2g→3E1g 695 nm 48.3 302 715 nm 42.8 244
3A2g→1E1g 525 nm 1.0 80 525 nm 20.2 122
fwhm = full width at half maxima; peak height in arbitrary unit
Figure 1. Solid-state NMR spectra of compound 2.
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Single-Crystal X-ray Analysis. X-ray data for 2 and 3 were collected on a Bruker
Smart-CCD diffractometer using graphite-monochromated Mo Kα radiation (=0.71073
Å). Specimens of suitable size and quality were selected and mounted onto a glass fiber
with superglue and collected at room temperature. The structures were solved by direct
methods, which successfully located most of the non-hydrogen atoms. Subsequent
refinement on F2 using the SHELXTL/PC package (version 6.1) allowed location of the
remaining non-hydrogen atoms.
Magnetic Analysis. Magnetic susceptibility and magnetization measurements were
carried out with a Quantum Design SQUID magnetometer MPMS-XL. DC magnetic
measurements were performed with an applied field of 1000 G in the 2-300 K
temperature range. Data were corrected for the diamagnetic contributions calculated
from the Pascal constants.2 The data was satisfactorily modeled based on the equations
outlined by Baltzer.3 The Hamiltonian is sHsDH Bzrr ⋅⋅⋅+−= gµ]ˆ[ˆ 322 where D is the
zero-field-splitting parameter and g is the g tensor with parallel and perpendicular
elements. At low magnetic fields (D > µBgH) the magnetic susceptibility elements are
)(
)(22||
|| 21
2kTD
kTDB
e
e
kT
Ng−
−
+=
µχ and )(
)(22
2112
kTD
kTDB
e
e
D
Ng−
−⊥
⊥ +−= µχ . The approximation
)2( ||31 ⊥+= χχχiso can be made for isotropic powders. Thus using these equations a D
value of 37.651 cm-1 and a g of 2.0894 were obtained.
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Figure 2. Magnetic data for compound 3. Diamonds represent experimental data points. The black line is the model based on the Hamiltonian in the inset.
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Crystal structure data for 2:1 trimeric perfluoro-o-phenylene mercury ferrocene adduct, 2.
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Table 1. Crystal data and structure refinement for compound 2.
Identification code fsad
Empirical formula C46 H10 F24 Fe Hg6
Formula weight 2277.93
Temperature 293(2) K
Wavelength 0.71073 Å
Crystal system Monoclinic
Space group C2/m
Unit cell dimensions a = 10.456(2) Å α= 90°.
b = 19.496(4) Å β= 110.51(3)°.
c = 12.312(3) Å γ = 90°.
Volume 2350.8(8) Å3
Z 2
Density (calculated) 3.218 Mg/m3
Absorption coefficient 19.947 mm-1
F(000) 2016
Crystal size 0.24 x 0.15 x 0.15 mm3
Theta range for data collection 1.77 to 23.33°.
Index ranges -10
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Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103)
for compound 2. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
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x y z U(eq)
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Hg(1) 6449(1) 4078(1) 6203(1) 62(1)
Hg(2) 4869(1) 5000 7908(1) 56(1)
Fe(1) 10000 5000 10000 34(1)
F(2) 3551(10) 3920(6) 9091(9) 104(3)
F(3) 3370(13) 2544(7) 8972(12) 155(5)
F(4) 4464(17) 1858(5) 7627(14) 180(6)
F(5) 5866(14) 2519(5) 6480(11) 136(4)
F(8) 7973(10) 3609(8) 4547(9) 128(4)
F(9) 9095(11) 4315(9) 3206(10) 170(6)
C(1) 4825(12) 3955(6) 7853(11) 59(3)
C(2) 4128(14) 3591(8) 8440(13) 77(4)
C(3) 4043(17) 2893(10) 8372(18) 102(6)
C(4) 4580(20) 2533(8) 7725(18) 111(6)
C(5) 5322(17) 2889(8) 7133(15) 96(5)
C(6) 5444(12) 3590(7) 7149(11) 67(3)
C(7) 7344(11) 4646(8) 5222(10) 71(4)
C(8) 7940(14) 4313(12) 4543(13) 97(5)
C(9) 8546(13) 4665(12) 3888(12) 125(12)
C(19) 8907(12) 4662(7) 8401(10) 74(4)
C(20) 8336(13) 4429(7) 9194(12) 73(4)
C(21) 7976(17) 5000 9693(17) 81(6)
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Table 3. Bond lengths [Å] and angles [°] for compound 2.
_____________________________________________________
Hg(1)-C(6) 2.055(14)
Hg(1)-C(7) 2.086(13)
Hg(1)-C(19) 3.217(11)
Hg(1)-Hg(1)#1 3.4157(16)
Hg(1)-C(20) 3.583(13)
Hg(2)-C(1) 2.039(12)
Hg(2)-C(1)#2 2.039(12)
Hg(2)-C(21) 3.222(18)
Hg(2)-C(20) 3.587(13)
Fe(1)-C(20) 2.010(11)
Fe(1)-C(20)#3 2.010(11)
Fe(1)-C(20)#4 2.010(11)
Fe(1)-C(20)#2 2.010(11)
Fe(1)-C(19) 2.011(11)
Fe(1)-C(19)#2 2.011(11)
Fe(1)-C(19)#3 2.011(11)
Fe(1)-C(19)#4 2.011(11)
Fe(1)-C(21)#4 2.016(17)
Fe(1)-C(21) 2.016(17)
F(2)-C(2) 1.326(18)
F(3)-C(3) 1.37(2)
F(4)-C(4) 1.324(19)
F(5)-C(5) 1.35(2)
F(8)-C(8) 1.37(2)
F(9)-C(9) 1.36(2)
C(1)-C(2) 1.388(19)
C(1)-C(6) 1.439(19)
C(2)-C(3) 1.36(2)
C(3)-C(4) 1.32(3)
C(4)-C(5) 1.42(3)
C(5)-C(6) 1.37(2)
C(7)-C(8) 1.37(2)
C(7)-C(7)#2 1.38(3)
C(8)-C(9) 1.37(3)
C(9)-C(9)#2 1.31(5)
C(19)-C(19)#2 1.32(3)
C(19)-C(20) 1.39(2)
C(20)-C(21) 1.386(19)
C(21)-C(20)#2 1.386(19)
C(6)-Hg(1)-C(7) 174.8(5)
C(6)-Hg(1)-C(19) 95.9(4)
C(7)-Hg(1)-C(19) 84.9(4)
C(6)-Hg(1)-Hg(1)#1 91.0(3)
C(7)-Hg(1)-Hg(1)#1 86.6(3)
C(19)-Hg(1)-Hg(1)#1 159.1(3)
C(6)-Hg(1)-C(20) 73.3(4)
C(7)-Hg(1)-C(20) 107.2(4)
C(19)-Hg(1)-C(20) 22.7(3)
Hg(1)#1-Hg(1)-C(20) 153.3(2)
C(1)-Hg(2)-C(1)#2 176.2(7)
C(1)-Hg(2)-C(21) 91.6(3)
C(1)#2-Hg(2)-C(21) 91.6(3)
C(1)-Hg(2)-C(20) 73.3(4)
C(1)#2-Hg(2)-C(20) 109.4(4)
C(21)-Hg(2)-C(20) 22.7(3)
C(20)-Fe(1)-C(20)#3 112.8(8)
C(20)-Fe(1)-C(20)#4 180.0(7)
C(20)#3-Fe(1)-C(20)#4 67.2(8)
C(20)-Fe(1)-C(20)#2 67.2(8)
C(20)#3-Fe(1)-C(20)#2 180.000(4)
C(20)#4-Fe(1)-C(20)#2 112.8(8)
C(20)-Fe(1)-C(19) 40.4(6)
C(20)#3-Fe(1)-C(19) 113.5(5)
C(20)#4-Fe(1)-C(19) 139.6(6)
C(20)#2-Fe(1)-C(19) 66.5(5)
C(20)-Fe(1)-C(19)#2 66.5(5)
C(20)#3-Fe(1)-C(19)#2 139.6(6)
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C(20)#4-Fe(1)-C(19)#2 113.5(5)
C(20)#2-Fe(1)-C(19)#2 40.4(6)
C(19)-Fe(1)-C(19)#2 38.3(8)
C(20)-Fe(1)-C(19)#3 113.5(5)
C(20)#3-Fe(1)-C(19)#3 40.4(6)
C(20)#4-Fe(1)-C(19)#3 66.5(5)
C(20)#2-Fe(1)-C(19)#3 139.6(6)
C(19)-Fe(1)-C(19)#3 141.7(8)
C(19)#2-Fe(1)-C(19)#3 180.000(4)
C(20)-Fe(1)-C(19)#4 139.6(6)
C(20)#3-Fe(1)-C(19)#4 66.5(5)
C(20)#4-Fe(1)-C(19)#4 40.4(6)
C(20)#2-Fe(1)-C(19)#4 113.5(5)
C(19)-Fe(1)-C(19)#4 180.000(4)
C(19)#2-Fe(1)-C(19)#4 141.7(8)
C(19)#3-Fe(1)-C(19)#4 38.3(8)
C(20)-Fe(1)-C(21)#4 139.7(5)
C(20)#3-Fe(1)-C(21)#4 40.3(5)
C(20)#4-Fe(1)-C(21)#4 40.3(5)
C(20)#2-Fe(1)-C(21)#4 139.7(5)
C(19)-Fe(1)-C(21)#4 112.5(7)
C(19)#2-Fe(1)-C(21)#4 112.5(7)
C(19)#3-Fe(1)-C(21)#4 67.5(7)
C(19)#4-Fe(1)-C(21)#4 67.5(7)
C(20)-Fe(1)-C(21) 40.3(5)
C(20)#3-Fe(1)-C(21) 139.7(5)
C(20)#4-Fe(1)-C(21) 139.7(5)
C(20)#2-Fe(1)-C(21) 40.3(5)
C(19)-Fe(1)-C(21) 67.5(7)
C(19)#2-Fe(1)-C(21) 67.5(7)
C(19)#3-Fe(1)-C(21) 112.5(7)
C(19)#4-Fe(1)-C(21) 112.5(7)
C(21)#4-Fe(1)-C(21) 180.0
C(2)-C(1)-C(6) 119.4(12)
C(2)-C(1)-Hg(2) 120.2(10)
C(6)-C(1)-Hg(2) 120.3(9)
F(2)-C(2)-C(3) 119.1(15)
F(2)-C(2)-C(1) 120.0(13)
C(3)-C(2)-C(1) 120.9(17)
C(4)-C(3)-C(2) 122.2(17)
C(4)-C(3)-F(3) 117.9(19)
C(2)-C(3)-F(3) 120(2)
C(3)-C(4)-F(4) 122.5(19)
C(3)-C(4)-C(5) 118.3(16)
F(4)-C(4)-C(5) 119(2)
F(5)-C(5)-C(6) 119.0(17)
F(5)-C(5)-C(4) 117.9(17)
C(6)-C(5)-C(4) 123.0(17)
C(5)-C(6)-C(1) 116.2(13)
C(5)-C(6)-Hg(1) 121.1(12)
C(1)-C(6)-Hg(1) 122.7(9)
C(8)-C(7)-C(7)#2 118.3(12)
C(8)-C(7)-Hg(1) 119.6(14)
C(7)#2-C(7)-Hg(1) 122.1(4)
C(7)-C(8)-C(9) 122(2)
C(7)-C(8)-F(8) 119.2(17)
C(9)-C(8)-F(8) 119.1(16)
C(9)#2-C(9)-F(9) 120.2(13)
C(9)#2-C(9)-C(8) 120.0(13)
F(9)-C(9)-C(8) 120(2)
C(19)#2-C(19)-C(20) 109.1(8)
C(19)#2-C(19)-Fe(1) 70.8(4)
C(20)-C(19)-Fe(1) 69.8(7)
C(19)#2-C(19)-Hg(1) 110.7(3)
C(20)-C(19)-Hg(1) 93.6(7)
Fe(1)-C(19)-Hg(1) 162.3(6)
C(21)-C(20)-C(19) 107.5(13)
C(21)-C(20)-Fe(1) 70.1(9)
C(19)-C(20)-Fe(1) 69.9(7)
C(21)-C(20)-Hg(1) 118.1(11)
C(19)-C(20)-Hg(1) 63.6(7)
Fe(1)-C(20)-Hg(1) 133.1(6)
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C(21)-C(20)-Hg(2) 63.7(9)
C(19)-C(20)-Hg(2) 101.8(8)
Fe(1)-C(20)-Hg(2) 127.8(6)
Hg(1)-C(20)-Hg(2) 59.87(18)
C(20)-C(21)-C(20)#2 106.9(18)
C(20)-C(21)-Fe(1) 69.6(9)
C(20)#2-C(21)-Fe(1) 69.6(9)
C(20)-C(21)-Hg(2) 93.7(10)
C(20)#2-C(21)-Hg(2) 93.7(10)
Fe(1)-C(21)-Hg(2) 150.4(9)
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Symmetry transformations used to generate equivalent atoms:
#1 -x+1,y,-z+1 #2 x,-y+1,z #3 -x+2,y,-z+2
#4 -x+2,-y+1,-z+2
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Table 4. Anisotropic displacement parameters (Å2x 103) for compound 2. The anisotropic
displacement factor exponent takes the form: -2π2[ h2 a*2U11 + ... + 2 h k a* b* U12 ]
______________________________________________________________________________
U11 U22 U33 U23 U13 U12
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Hg(1) 49(1) 73(1) 55(1) -10(1) 7(1) 5(1)
Hg(2) 41(1) 61(1) 59(1) 0 11(1) 0
Fe(1) 26(1) 41(1) 35(1) 0 12(1) 0
F(2) 100(7) 129(7) 100(6) 12(5) 56(6) -2(5)
F(3) 143(10) 139(10) 182(11) 64(8) 56(9) -45(8)
F(4) 226(14) 61(6) 258(17) 13(8) 91(13) -30(7)
F(5) 164(10) 75(6) 165(10) -21(6) 53(8) 7(6)
F(8) 84(6) 195(12) 96(7) -63(7) 20(5) 33(7)
F(9) 78(7) 350(19) 88(7) -50(9) 39(6) 10(9)
C(1) 44(6) 52(6) 71(8) 9(6) 6(6) 6(5)
C(2) 60(8) 74(9) 82(9) 13(7) 5(7) -12(7)
C(3) 74(11) 88(12) 129(15) 35(11) 16(10) -16(9)
C(4) 109(14) 54(9) 151(17) 31(10) 24(12) -24(9)
C(5) 91(11) 66(9) 117(13) -20(9) 18(10) 2(8)
C(6) 48(7) 61(7) 70(8) 0(6) -5(6) -4(6)
C(7) 34(6) 132(11) 44(6) -12(6) 9(5) 4(6)
C(8) 46(8) 172(18) 62(9) -28(10) 6(7) 10(10)
C(9) 46(8) 270(40) 65(8) -24(10) 22(7) -2(10)
C(19) 48(7) 116(10) 48(6) -26(6) 4(5) -3(6)
C(20) 53(7) 69(8) 77(8) -1(7) -2(7) -25(6)
C(21) 35(9) 140(20) 77(12) 0 24(9) 0
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Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3)
for compound 2.
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x y z U(eq)
________________________________________________________________________________
H(19) 9254 4370 7918 89
H(20) 8198 3949 9361 88
H(21) 7534 5000 10276 97
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Crystal structure data for 2:1 trimeric perfluoro-o-phenylene mercury nickelocene adduct, 3.
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Table 1. Crystal data and structure refinement for compound 3.
Identification code fsad
Empirical formula C46 H10 F24 Hg6 Ni
Formula weight 2280.79
Temperature 293(2) K
Wavelength 0.71073 Å
Crystal system Monoclinic
Space group C2/m
Unit cell dimensions a = 10.554(2) Å α= 90°.
b = 19.509(4) Å β= 109.21(3)°.
c = 12.299(3) Å γ = 90°.
Volume 2391.2(8) Å3
Z 2
Density (calculated) 3.168 Mg/m3
Absorption coefficient 19.700 mm-1
F(000) 2020
Crystal size 0.51 x 0.25 x 0.24 mm3
Theta range for data collection 1.75 to 23.27°.
Index ranges -11
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Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103)
for compound 3. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
________________________________________________________________________________
x y z U(eq)
________________________________________________________________________________
Hg(1) 3578(1) 5920(1) 3835(1) 81(1)
Hg(2) 5177(1) 5000 2129(1) 71(1)
Ni(1) 0 5000 0 45(1)
F(2) 6470(10) 6081(6) 909(9) 136(4)
F(3) 6618(13) 7461(7) 1025(12) 201(6)
F(4) 5504(18) 8156(7) 2333(17) 259(9)
F(5) 4103(13) 7475(5) 3548(12) 175(5)
F(8) 2018(11) 6383(9) 5489(10) 163(6)
F(9) 841(11) 5684(9) 6786(10) 230(8)
C(1) 5197(10) 6049(5) 2185(9) 71(4)
C(2) 5886(10) 6398(8) 1568(9) 100(6)
C(3) 5971(12) 7109(8) 1622(12) 149(9)
C(4) 5367(15) 7471(5) 2293(14) 148(9)
C(5) 4677(13) 7122(7) 2909(11) 127(7)
C(6) 4592(10) 6411(7) 2855(8) 75(4)
C(7) 2664(13) 5359(8) 4834(10) 86(5)
C(8) 2052(16) 5687(15) 5480(15) 124(8)
C(9) 1432(15) 5333(13) 6142(14) 150(17)
C(21) 2126(16) 5000 370(20) 98(8)
C(19) 1197(14) 5358(8) 1657(12) 101(6)
C(20) 1789(14) 5596(10) 872(15) 104(5)
________________________________________________________________________________
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Table 3. Bond lengths [Å] and angles [°] for compound 3.
_____________________________________________________
Hg(1)-C(6) 2.089(9)
Hg(1)-C(7) 2.102(14)
Hg(1)-C(19) 3.204(12)
Hg(1)-Hg(1)#1 3.3996(17)
Hg(1)-C(20) 3.565(16)
Hg(2)-C(1) 2.048(9)
Hg(2)-C(1)#2 2.048(9)
Hg(2)-C(21) 3.237(17)
Hg(2)-C(20) 3.590(16)
Ni(1)-C(19) 2.131(12)
Ni(1)-C(19)#3 2.131(12)
Ni(1)-C(19)#2 2.131(12)
Ni(1)-C(19)#4 2.131(12)
Ni(1)-C(21)#3 2.138(17)
Ni(1)-C(21) 2.138(17)
Ni(1)-C(20)#3 2.176(13)
Ni(1)-C(20) 2.176(13)
Ni(1)-C(20)#2 2.176(13)
Ni(1)-C(20)#4 2.176(13)
F(2)-C(2) 1.321(13)
F(3)-C(3) 1.344(13)
F(4)-C(4) 1.343(15)
F(5)-C(5) 1.332(15)
F(8)-C(8) 1.36(3)
F(9)-C(9) 1.35(2)
C(1)-C(2) 1.3900
C(1)-C(6) 1.3900
C(2)-C(3) 1.3900
C(3)-C(4) 1.3900
C(4)-C(5) 1.3900
C(5)-C(6) 1.3900
C(7)-C(8) 1.34(2)
C(7)-C(7)#2 1.40(3)
C(8)-C(9) 1.39(3)
C(9)-C(9)#2 1.30(5)
C(21)-C(20) 1.418(18)
C(21)-C(20)#2 1.418(18)
C(19)-C(20) 1.39(2)
C(19)-C(19)#2 1.39(3)
C(6)-Hg(1)-C(7) 175.4(5)
C(6)-Hg(1)-C(19) 94.8(4)
C(7)-Hg(1)-C(19) 85.8(4)
C(6)-Hg(1)-Hg(1)#1 90.5(3)
C(7)-Hg(1)-Hg(1)#1 87.4(3)
C(19)-Hg(1)-Hg(1)#1 159.5(3)
C(6)-Hg(1)-C(20) 72.0(4)
C(7)-Hg(1)-C(20) 108.3(4)
C(19)-Hg(1)-C(20) 22.9(3)
Hg(1)#1-Hg(1)-C(20) 152.3(3)
C(1)-Hg(2)-C(1)#2 176.4(6)
C(1)-Hg(2)-C(21) 91.1(3)
C(1)#2-Hg(2)-C(21) 91.1(3)
C(1)-Hg(2)-C(20) 71.8(4)
C(1)#2-Hg(2)-C(20) 109.6(4)
C(21)-Hg(2)-C(20) 23.2(3)
C(19)-Ni(1)-C(19)#3 180.0(8)
C(19)-Ni(1)-C(19)#2 38.2(9)
C(19)#3-Ni(1)-C(19)#2 141.8(9)
C(19)-Ni(1)-C(19)#4 141.8(9)
C(19)#3-Ni(1)-C(19)#4 38.2(9)
C(19)#2-Ni(1)-C(19)#4 180.0(8)
C(19)-Ni(1)-C(21)#3 116.9(7)
C(19)#3-Ni(1)-C(21)#3 63.1(7)
C(19)#2-Ni(1)-C(21)#3 116.9(7)
C(19)#4-Ni(1)-C(21)#3 63.1(7)
C(19)-Ni(1)-C(21) 63.1(7)
C(19)#3-Ni(1)-C(21) 116.9(7)
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C(19)#2-Ni(1)-C(21) 63.1(7)
C(19)#4-Ni(1)-C(21) 116.9(7)
C(21)#3-Ni(1)-C(21) 180.0
C(19)-Ni(1)-C(20)#3 142.3(6)
C(19)#3-Ni(1)-C(20)#3 37.7(6)
C(19)#2-Ni(1)-C(20)#3 116.2(6)
C(19)#4-Ni(1)-C(20)#3 63.8(6)
C(21)#3-Ni(1)-C(20)#3 38.4(5)
C(21)-Ni(1)-C(20)#3 141.6(5)
C(19)-Ni(1)-C(20) 37.7(5)
C(19)#3-Ni(1)-C(20) 142.3(6)
C(19)#2-Ni(1)-C(20) 63.8(6)
C(19)#4-Ni(1)-C(20) 116.2(6)
C(21)#3-Ni(1)-C(20) 141.6(5)
C(21)-Ni(1)-C(20) 38.4(5)
C(20)#3-Ni(1)-C(20) 180.0(8)
C(19)-Ni(1)-C(20)#2 63.8(6)
C(19)#3-Ni(1)-C(20)#2 116.2(6)
C(19)#2-Ni(1)-C(20)#2 37.7(5)
C(19)#4-Ni(1)-C(20)#2 142.3(6)
C(21)#3-Ni(1)-C(20)#2 141.6(5)
C(21)-Ni(1)-C(20)#2 38.4(5)
C(20)#3-Ni(1)-C(20)#2 115.4(10)
C(20)-Ni(1)-C(20)#2 64.6(10)
C(19)-Ni(1)-C(20)#4 116.2(6)
C(19)#3-Ni(1)-C(20)#4 63.8(6)
C(19)#2-Ni(1)-C(20)#4 142.3(6)
C(19)#4-Ni(1)-C(20)#4 37.7(6)
C(21)#3-Ni(1)-C(20)#4 38.4(5)
C(21)-Ni(1)-C(20)#4 141.6(5)
C(20)#3-Ni(1)-C(20)#4 64.6(10)
C(20)-Ni(1)-C(20)#4 115.4(10)
C(20)#2-Ni(1)-C(20)#4 180.000(1)
C(2)-C(1)-C(6) 120.0
C(2)-C(1)-Hg(2) 118.2(8)
C(6)-C(1)-Hg(2) 121.7(8)
F(2)-C(2)-C(1) 122.6(12)
F(2)-C(2)-C(3) 117.4(12)
C(1)-C(2)-C(3) 120.0
F(3)-C(3)-C(4) 118.6(14)
F(3)-C(3)-C(2) 121.4(14)
C(4)-C(3)-C(2) 120.0
F(4)-C(4)-C(3) 117.5(15)
F(4)-C(4)-C(5) 122.5(15)
C(3)-C(4)-C(5) 120.0
F(5)-C(5)-C(4) 119.3(13)
F(5)-C(5)-C(6) 120.7(13)
C(4)-C(5)-C(6) 120.0
C(5)-C(6)-C(1) 120.0
C(5)-C(6)-Hg(1) 117.9(8)
C(1)-C(6)-Hg(1) 122.1(8)
C(8)-C(7)-C(7)#2 118.5(14)
C(8)-C(7)-Hg(1) 120.1(15)
C(7)#2-C(7)-Hg(1) 121.3(4)
C(7)-C(8)-F(8) 120(2)
C(7)-C(8)-C(9) 122(3)
F(8)-C(8)-C(9) 118.3(18)
C(9)#2-C(9)-F(9) 120.6(12)
C(9)#2-C(9)-C(8) 119.9(15)
F(9)-C(9)-C(8) 119(2)
C(20)-C(21)-C(20)#2 110(2)
C(20)-C(21)-Ni(1) 72.3(9)
C(20)#2-C(21)-Ni(1) 72.3(9)
C(20)-C(21)-Hg(2) 92.5(11)
C(20)#2-C(21)-Hg(2) 92.5(11)
Ni(1)-C(21)-Hg(2) 152.3(10)
C(20)-C(19)-C(19)#2 109.5(10)
C(20)-C(19)-Ni(1) 72.9(8)
C(19)#2-C(19)-Ni(1) 70.9(4)
C(20)-C(19)-Hg(1) 93.3(9)
C(19)#2-C(19)-Hg(1) 110.0(3)
Ni(1)-C(19)-Hg(1) 165.2(7)
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C(19)-C(20)-C(21) 105.3(17)
C(19)-C(20)-Ni(1) 69.4(8)
C(21)-C(20)-Ni(1) 69.4(9)
C(19)-C(20)-Hg(1) 63.8(8)
C(21)-C(20)-Hg(1) 118.0(13)
Ni(1)-C(20)-Hg(1) 132.9(7)
C(19)-C(20)-Hg(2) 101.8(11)
C(21)-C(20)-Hg(2) 64.2(10)
Ni(1)-C(20)-Hg(2) 128.2(7)
Hg(1)-C(20)-Hg(2) 60.0(2)
_____________________________________________________________
Symmetry transformations used to generate equivalent atoms:
#1 -x+1,y,-z+1 #2 x,-y+1,z #3 -x,-y+1,-z
#4 -x,y,-z
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Table 4. Anisotropic displacement parameters (Å2x 103) for compound 3. The anisotropic
displacement factor exponent takes the form: -2π2[ h2 a*2U11 + ... + 2 h k a* b* U12 ]
______________________________________________________________________________
U11 U22 U33 U23 U13 U12
______________________________________________________________________________
Hg(1) 64(1) 104(1) 68(1) -5(1) 14(1) 16(1)
Hg(2) 53(1) 92(1) 66(1) 0 17(1) 0
Ni(1) 39(2) 56(2) 44(2) 0 18(1) 0
F(2) 118(8) 182(11) 131(9) 30(7) 71(7) 13(7)
F(3) 211(13) 178(12) 237(15) 97(11) 103(12) -24(10)
F(4) 299(19) 91(9) 390(20) 55(12) 113(17) 10(11)
F(5) 197(12) 89(7) 232(14) -11(8) 61(10) 31(8)
F(8) 101(8) 273(16) 107(8) -74(10) 24(6) 58(10)
F(9) 107(9) 500(20) 105(8) -54(11) 63(7) 19(11)
C(1) 54(8) 65(9) 81(10) 21(8) 4(8) -4(7)
C(2) 96(13) 74(12) 127(16) 45(11) 30(11) 11(10)
C(3) 106(16) 180(30) 150(20) 109(19) 33(14) 20(16)
C(4) 142(19) 100(18) 210(30) 46(17) 69(17) 26(15)
C(5) 127(17) 86(16) 160(20) 16(14) 35(15) 26(13)
C(6) 74(10) 78(11) 67(10) 12(8) 16(8) 15(8)
C(7) 65(9) 159(16) 37(7) 1(7) 18(7) 1(8)
C(8) 52(11) 260(30) 60(11) -40(15) 16(9) 14(14)
C(9) 60(10) 340(50) 67(10) -6(14) 40(8) -2(13)
C(21) 19(10) 190(30) 86(17) 0 15(10) 0
C(19) 68(9) 174(19) 62(9) -43(9) 21(8) -29(9)
C(20) 67(11) 131(15) 109(14) -41(11) 20(10) -48(10)
______________________________________________________________________________
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Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3)
for compound 3.
________________________________________________________________________________
x y z U(eq)
________________________________________________________________________________
H(21A) 2574 5000 -216 117
H(19) 876 5647 2163 122
H(20) 1969 6074 724 125 ___________________________________________________________________________
1 Sartori, P.; Golloch, A. Chem. Ber. 1968, 101, 2004-2009. 2 Theory and Applications of Molecular Paramagnetism; Boudreaux, E. A., Mulay, L. N.,
Eds; John Wiley & Sons: New York, 1976. 3 Baltzer, P.; Furrer, A.; Hulliger, J.; Stebler, A. Inorg. Chem. 1988, 27, 1543-1548.