Supporting Information

for

Angew. Chem. Int. Ed. 200461152

© Wiley-VCH 200469451 Weinheim, Germany

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: gabbai@mail.chem.tamu.edu

SUPPLEMENTARY INFORMATION

♦ Experimental Section (4 pages)

♦ Crystal data and structure refinement for 2 (8 pages)

♦ Crystal data and structure refinement for 3 (8 pages)

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).

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.

4

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.

5

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.

6

Crystal structure data for 2:1 trimeric perfluoro-o-phenylene mercury ferrocene adduct, 2.

7

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

8

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.

________________________________________________________________________________

x y z U(eq)

________________________________________________________________________________

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)

________________________________________________________________________________

9

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)

10

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)

11

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)

_____________________________________________________________

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

12

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

______________________________________________________________________________

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

______________________________________________________________________________

13

Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3)

for compound 2.

________________________________________________________________________________

x y z U(eq)

________________________________________________________________________________

H(19) 9254 4370 7918 89

H(20) 8198 3949 9361 88

H(21) 7534 5000 10276 97

________________________________________________________________________________

14

Crystal structure data for 2:1 trimeric perfluoro-o-phenylene mercury nickelocene adduct, 3.

15

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

16

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)

________________________________________________________________________________

17

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)

18

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)

19

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

20

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)

______________________________________________________________________________

21

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.