Ch.Amort,B.BildsteinandK.Wurst* H Br N Ni·C H Crystalstructureof[1 R ,7,7-trimethylbicyclo[2.2.1]heptan-2,3-bis(2,6-diisopropylphen-1-yl)imine]nickeldibromide]—toluene(1:1),C

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Crystal structure of [1R,7,7-trimethylbicyclo[2.2.1]heptan-2,3-bis(2,6- diisopropylphen-1-yl)imine]nickeldibromide]—toluene (1:1),

C 34 H 48 Br 2 N 2 Ni · C 7 H 8

Ch. Amort, B. Bildstein and K. Wurst*

University of Innsbruck, Institut of General, Inorganic and Theoretical Chemistry, Innrain 52a, A-6020 Innsbruck, Austria Received February 18, 2003, accepted and available on-line May 23, 2003; CCDC-No. 1267/1026

Abstract

C

41

H

56

Br

2

N

2

Ni, orthorhombic, P2

1

2

1

2

1

(No. 19), a = 10.121(2) Å, b = 17.115(2) Å, c = 22.835(2) Å, V = 3955.5 Å

³

, Z = 4, R

gt

(F) = 0.037, wR

ref

(F

²

) = 0.086, T = 218 K.

Source of material

The Ni-complex was obtained from 1R-camphorchinon-N,N ¢ - bis(2,6-diisopropylphenyl)diimine [1] and (dimethoxyethane)- nickeldibromide.

Experimental details

The chiral compound crystallizes in the chiral space group P2

1

2

₁

2

₁

and the absolute structure was determined by the method of Flack (Flack parameter x = 0.025(15)).

Discussion

In the asymmetric unit is one molecule of the complex and one molecule of the solvent toluene. The Ni(II) cation has a distorted tet- rahedral coordination with bond distances of 2.027(5) Å and 2.033(5) Å for Ni—N bonds and 2.294(2) Å and 2.328(2) Å for

Ni—Br bonds. The smallest and greatest bond angle is Ð N1–Ni2–N2 with 82.8(2) ° and Ð Br1–Ni1–Br2 with 123.5(1) ° . The double bonds of the imino groups are located between N1–C1 and N2–C2 with bond distances of 1.272(8) Å and 1.274(8) Å. The solvent toluene is slightly disordered and was refined without hydrogen atoms.

Z. Kristallogr. NCS

218

(2003) 187–188 187

© by Oldenbourg Wissenschaftsverlag, München

Crystal: brown prism, size 0.35 × 0.5 × 0.65 mm Wavelength: MoK_aradiation (0.71073 Å)

m: 25.40 cm^–1

Diffractometer, scan mode: Bruker P4,w

2q^max: 40.98°

N(hkl)measured,N(hkl)unique: 3773, 3310 Criterion forIobs,N(hkl)gt: Iobs> 2s(Iobs), 2759 N(param)refined: 416

Programs: SHELXS-97 [2], SHELXL-97 [3], SHELXTL [4]

Table 1.Data collection and handling.

H(4A) 4a 1.0399 1.1343 0.4150 0.066

H(4B) 4a 0.9804 1.0564 0.3872 0.066

H(5A) 4a 0.9144 1.1256 0.3073 0.075

H(5B) 4a 0.9770 1.2031 0.3345 0.075

H(6) 4a 1.1167 1.1793 0.2503 0.054

H(8A) 4a 1.2658 1.0950 0.4457 0.078

H(8B) 4a 1.3495 1.0358 0.4073 0.078

H(8C) 4a 1.2191 1.0071 0.4391 0.078

H(9A) 4a 1.3571 1.0762 0.2739 0.095

H(9B) 4a 1.4323 1.1181 0.3260 0.095

H(9C) 4a 1.3884 1.1667 0.2703 0.095

H(10A) 4a 1.1622 1.2301 0.3798 0.113

H(10B) 4a 1.2687 1.2605 0.3344 0.113

H(10C) 4a 1.3140 1.2121 0.3900 0.113

H(13) 4a 1.1670 1.0934 0.0357 0.063

H(14) 4a 0.9492 1.1216 0.0159 0.072

H(15) 4a 0.7940 1.1110 0.0884 0.065

H(17) 4a 1.2993 1.0234 0.1690 0.051

H(18A) 4a 1.4493 0.9949 0.0943 0.101

H(18B) 4a 1.3483 1.0263 0.0468 0.101

H(18C) 4a 1.3148 0.9500 0.0832 0.101

H(19A) 4a 1.4512 1.1231 0.1435 0.093

H(19B) 4a 1.3192 1.1590 0.1693 0.093

H(19C) 4a 1.3449 1.1600 0.1008 0.093

H(20) 4a 0.8431 1.0432 0.2341 0.060

H(21A) 4a 0.6232 1.0123 0.2061 0.124

H(21B) 4a 0.7248 0.9616 0.1695 0.124

H(21C) 4a 0.6560 1.0351 0.1404 0.124

Table 2.Atomic coordinates and displacement parameters (in Å²)

.

Atom Site x y z Uiso

_____________

* Correspondence author (e-mail: klaus.wurst@uibk.ac.at)

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References

1. Amort, Ch.: Hochaktive Iminchelat-Metallkomplexe (Fe, Co, Ni...) mit Pyrrolsubstituenten zur Polymerisation von Olefinen. PhD Dissertation, University of Innsbruck, Austria 2000.

Ni(1) 4a 1.1039(1) 0.90339(5) 0.23252(4) 0.0516(7) 0.0275(5) 0.0320(6) –0.0003(5) –0.0042(6) –0.0009(4) Br(1) 4a 0.88604(9) 0.86370(5) 0.24611(4) 0.0547(5) 0.0564(5) 0.0632(6) –0.0149(5) –0.0114(5) –0.0011(4) Br(2) 4a 1.2530(1) 0.83631(5) 0.17600(4) 0.0916(8) 0.0668(6) 0.0641(6) 0.0160(7) 0.0231(6) –0.0113(5) N(1) 4a 1.0867(5) 1.0199(3) 0.2187(3) 0.024(4) 0.033(4) 0.028(4) –0.001(3) –0.001(3) 0.012(3) N(2) 4a 1.1686(5) 0.9388(4) 0.3125(2) 0.039(4) 0.030(4) 0.023(4) 0.004(3) –0.005(3) 0.006(3) C(1) 4a 1.1133(8) 1.0580(4) 0.2650(3) 0.040(5) 0.031(5) 0.025(5) 0.000(4) –0.006(4) –0.002(4)

C(2) 4a 1.1583(7) 1.0126(4) 0.3182(3) 0.029(5) 0.028(5) 0.033(5) 0.002(4) 0.002(4) 0.003(4)

C(3) 4a 1.1799(8) 1.0729(4) 0.3652(3) 0.060(6) 0.026(5) 0.025(5) 0.006(4) –0.012(4) –0.007(4) C(4) 4a 1.0393(9) 1.1009(5) 0.3802(4) 0.082(8) 0.043(6) 0.041(5) 0.019(5) 0.003(5) –0.007(5) C(5) 4a 0.9942(9) 1.1483(5) 0.3246(4) 0.089(8) 0.036(6) 0.061(6) 0.023(5) –0.029(6) –0.012(5) C(6) 4a 1.1132(9) 1.1409(4) 0.2827(3) 0.065(6) 0.034(5) 0.036(5) 0.006(5) –0.011(5) 0.001(4) C(7) 4a 1.2314(9) 1.1423(4) 0.3258(3) 0.083(7) 0.028(5) 0.039(5) –0.001(5) –0.029(6) 0.000(5) C(8) 4a 1.261(1) 1.0506(4) 0.4193(3) 0.076(6) 0.046(5) 0.035(5) 0.001(6) –0.012(5) –0.012(4) C(9) 4a 1.365(1) 1.1242(5) 0.2963(4) 0.080(8) 0.050(6) 0.059(6) –0.025(6) –0.015(6) 0.012(5) C(10) 4a 1.245(1) 1.2182(4) 0.3607(4) 0.121(9) 0.037(5) 0.069(7) –0.009(6) –0.043(7) –0.006(5) C(11) 4a 1.0473(8) 1.0551(4) 0.1636(3) 0.045(6) 0.022(4) 0.025(5) –0.001(4) –0.007(5) 0.001(4) C(12) 4a 1.1433(8) 1.0629(4) 0.1203(3) 0.058(7) 0.035(5) 0.021(5) –0.005(4) –0.012(5) –0.001(4) C(13) 4a 1.104(1) 1.0880(5) 0.0655(3) 0.063(7) 0.052(6) 0.042(6) –0.016(5) 0.002(6) 0.005(5) C(14) 4a 0.974(1) 1.1052(5) 0.0535(4) 0.093(9) 0.055(6) 0.032(6) –0.010(6) –0.029(6) 0.009(5) C(15) 4a 0.8823(9) 1.0982(5) 0.0968(4) 0.046(6) 0.060(6) 0.057(6) 0.005(5) –0.014(6) 0.017(5) C(16) 4a 0.9146(9) 1.0726(4) 0.1534(3) 0.049(7) 0.036(5) 0.028(5) 0.004(4) –0.005(5) 0.004(4) C(17) 4a 1.2896(8) 1.0507(5) 0.1310(3) 0.051(7) 0.043(5) 0.032(5) –0.004(5) –0.003(4) 0.002(4) C(18) 4a 1.3566(9) 1.0010(5) 0.0846(4) 0.060(7) 0.087(7) 0.054(6) 0.000(6) 0.011(5) 0.007(5) C(19) 4a 1.3575(8) 1.1306(5) 0.1367(4) 0.049(6) 0.066(6) 0.072(6) –0.006(6) –0.008(5) 0.011(5) C(20) 4a 0.8060(8) 1.0664(5) 0.1979(3) 0.048(6) 0.053(6) 0.050(6) 0.010(5) –0.012(5) 0.003(4) C(21) 4a 0.6919(9) 1.0140(6) 0.1765(5) 0.044(6) 0.116(9) 0.089(8) –0.005(6) –0.015(6) 0.040(7) C(22) 4a 0.755(1) 1.1480(6) 0.2123(4) 0.101(8) 0.097(8) 0.065(7) 0.053(8) –0.002(6) 0.008(6) C(23) 4a 1.2143(8) 0.8873(4) 0.3587(3) 0.039(6) 0.032(5) 0.026(5) 0.001(4) –0.005(4) 0.003(4) C(24) 4a 1.3467(8) 0.8659(4) 0.3583(3) 0.059(7) 0.020(4) 0.036(5) –0.001(5) –0.018(5) 0.004(4) C(25) 4a 1.3921(9) 0.8154(5) 0.4014(4) 0.055(6) 0.044(6) 0.061(6) –0.005(5) –0.020(6) 0.002(5) C(26) 4a 1.307(1) 0.7858(5) 0.4431(4) 0.087(9) 0.035(5) 0.057(7) 0.005(6) –0.040(7) 0.018(5) C(27) 4a 1.177(1) 0.8075(5) 0.4422(3) 0.089(8) 0.048(6) 0.029(5) –0.010(6) –0.010(5) 0.008(5) C(28) 4a 1.1254(9) 0.8577(4) 0.3997(3) 0.062(7) 0.031(5) 0.029(5) –0.014(5) –0.014(5) 0.002(4) C(29) 4a 1.4502(8) 0.8929(4) 0.3139(4) 0.052(6) 0.040(5) 0.049(5) 0.011(5) –0.002(5) 0.002(5) C(30) 4a 1.5142(9) 0.8232(5) 0.2821(4) 0.078(7) 0.055(6) 0.071(6) 0.007(5) 0.006(5) –0.009(6) C(31) 4a 1.5581(9) 0.9433(5) 0.3423(4) 0.065(7) 0.058(6) 0.091(7) –0.004(5) –0.017(6) –0.011(6) C(32) 4a 0.9796(9) 0.8756(5) 0.3999(3) 0.059(7) 0.062(7) 0.031(5) –0.010(5) 0.005(5) 0.009(5) C(33) 4a 0.898(1) 0.7993(5) 0.3907(4) 0.068(7) 0.063(6) 0.075(6) –0.023(6) –0.012(6) 0.024(5) C(34) 4a 0.932(1) 0.9152(5) 0.4561(4) 0.068(8) 0.089(7) 0.061(6) –0.014(6) 0.014(5) 0.012(6)

C(35) 4a 1.479(2) 1.304(1) 0.4652(8) 0.31(3) 0.21(2) 0.15(2) –0.12(2) –0.08(2) –0.02(2)

C(36) 4a 1.523(3) 1.234(1) 0.471(1) 0.35(4) 0.05(1) 0.24(3) –0.13(2) –0.22(3) 0.08(2)

C(37) 4a 1.451(2) 1.205(1) 0.5297(9) 0.18(2) 0.11(1) 0.15(2) –0.04(1) –0.06(1) –0.03(1)

C(38) 4a 1.513(2) 1.131(2) 0.5396(8) 0.14(2) 0.21(2) 0.10(1) –0.08(2) 0.01(1) –0.04(2)

C(39) 4a 1.611(3) 1.090(2) 0.503(1) 0.27(3) 0.27(3) 0.13(2) –0.15(3) –0.08(2) 0.10(2)

C(40) 4a 1.661(3) 1.116(2) 0.447(2) 0.24(4) 0.16(2) 0.60(7) –0.03(2) –0.27(4) –0.01(4)

C(41) 4a 1.609(2) 1.183(2) 0.443(1) 0.11(2) 0.22(3) 0.20(2) –0.07(2) –0.00(2) –0.06(2)

Table 3.Atomic coordinates and displacement parameters (in Å²).

Atom Site x y z U11 U22 U33 U12 U13 U23

H(22A) 4a 0.6847 1.1443 0.2409 0.132

H(22B) 4a 0.7223 1.1725 0.1770 0.132

H(22C) 4a 0.8269 1.1791 0.2283 0.132

H(25) 4a 1.4818 0.8011 0.4021 0.064

H(26) 4a 1.3378 0.7510 0.4718 0.072

H(27) 4a 1.1195 0.7880 0.4713 0.066

H(29) 4a 1.4047 0.9253 0.2842 0.056

H(30A) 4a 1.5787 0.8423 0.2541 0.102

H(30B) 4a 1.4465 0.7937 0.2617 0.102

H(30C) 4a 1.5576 0.7898 0.3104 0.102

Table 2.Continued

.

H(31A) 4a 1.6210 0.9596 0.3127 0.107

H(31B) 4a 1.6033 0.9131 0.3722 0.107

H(31C) 4a 1.5181 0.9891 0.3601 0.107

H(32) 4a 0.9609 0.9111 0.3667 0.060

H(33A) 4a 0.8048 0.8116 0.3910 0.103

H(33B) 4a 0.9180 0.7628 0.4220 0.103

H(33C) 4a 0.9217 0.7761 0.3534 0.103

H(34A) 4a 0.8376 0.9255 0.4532 0.109

H(34B) 4a 0.9786 0.9641 0.4616 0.109

H(34C) 4a 0.9482 0.8811 0.4893 0.109

Table 2.Continued

.

2. Sheldrick, G. M.: SHELXS-97, Program for Crystal Structure Solution, University of Göttingen, Germany 1997.

3. Sheldrick, G. M.: SHELXL-97, Program for Crystal Structure Refine- ment, University of Göttingen, Germany 1997.

4. Sheldrick, G. M.: Program package SHELXTL Version 5.1, Bruker Ana- lytical X-Ray Instruments Inc, Madison (WI 53719), USA 1997.

188 C

34

H

48

Br

2

N

2

Ni · C

7

H

8