ζ . Kristallogr. NCS 213 (1998) 601-602
601
© by R. Oldenbourg Verlag, München
C r y s t a l s t r u c t u r e o f l - t r i m e t h y l s i l y l o x y - 3 , 5 , 5 - t r i m e t h y l c y c l o h e x a n e - r - l ^ - 3 - d i c a r b o n i t r i l e , ( C H 3 ) 3 ( C N ) 2 [ O S i ( C H 3 ) 3 ] C 6 H 6
K. Peters, E.-M. Peters
Max-Planck-Institut für Festkörperforschung. Heisenbergstraße 1, D-70506 Stuttgart. Germany
C. A. ЮаиЬеП and H. Quast
Universität Würzburg, Institut für Organische Chemie, A m Hubland, D-97074 Wiirzburg, Germany
Received February И , 1998, CSD-No. 409225
С32
С52
Source of material: The title compound was prepared by the addition of trimethylsilyl cyanide, which was employed as sol- vent, and l,5,5-trimethyl-3-oxocyclohexane-l-carbonitrileinthe presence of 0.67 equivalents of the 18-crown-6/potassium cyanide complex. Sublimation of the crude product at 323 К bath temperature/10"^ Torr and recrystallization from diethyl ether afforded coarse, colorless crystals, mp 392 К - 393 К, in 73%
yield (see ref 1).
The structure of the compound reveals the trans relationship between the nitrile groups. Of the two possible conformations of the ketone precursor, that with the nitrile group in the axial position is strongly preferred. Furthermore, axial attack of the cyanide at the carbonyl group of the less stable conformation meets severe steric hindrance by two methyl groups. Therefore, the observed diastereoselectivity is interpreted in terms of an exclusive equatorial attack of the cyanide at the more stable conformation of the ketone.
C14H24N2OSÌ, monoclinic, P2ila (No. 14), a =12.923(8) Â, b =10.290(5) Â, с =12.631(7) Â, β =91.86(5)°, V=1678.8 Â^
Ζ =4, R(F) =0.052, Rv^F) =0.054.
Table 1. Parameters used for the X-ray data collection
Crystal: colorless plate, size 0.75 χ 0.75 χ 0.35 mm Wavelength: Mo Ka radiation (0.71073 λ )
μ: 1.40 cm"'
Difftactometer: Siemens P3
Scan mode: ω
293 К
20iiuut: 55°
Щтшщиг:
2858Criterion for Fo. f o > 3 o ( F „ )
ί^(ραΓαηι),φκ<Γ·
164Program: SHELXTL-plus
Table 2. Final atomic coordinates and displacement parameters (in Â^)
Atom Site
X У
ζ ί/i«,H(2A)
4e
0.5020(2) 0.7066(2) 0.4184(3) 0.08 H(2B)4e
0.4206(2) 0.6000(2) 0.4463(3) 0.08 H(4A)4e
0.4304(2) 0.9139(2) 0.3172(3) 0.08 H(4B)4e
0.3112(2) 0.9160(2) 0.2902(3) 0.08 H(6A)4e
0.5391(2) 0.7392(2) 0.2177(3) 0.08 H(6B)4e
0.4777(2) 0.6510(2) 0.1363(3) 0.08 H(12A)4e
0.3828(3) 0.1651(3) 0.2924(4) 0.08 H(12B)4e
0.3524(3) 0.2621(3) 0.3819(4) 0.08 H(12C)4e
0.4647(3) 0.2642(3) 0.3383(4) 0.08 H(13A)4e
0.4113(3) 0.2620(3) 0.0698(4) 0.08 H(13B)4e
0.4967(3) 0.3580(3) 0.1132(4) 0.08 H(13C)4e
0.4022(3) 0.4110(3) 0.0453(4) 0.08 H(14A)4e
0.1922(3) 0.2812(4) 0.1609(5) 0.08 H(14B)4e
0.1903(3) 0.4319(4) 0.1427(5) 0.08 H(14C)4e
0.1745(3) 0.3753(4) 0.2562(5) 0.08 H(32A)4e
0.4207(3) 0.8842(3) 0.5059(4) 0.08 H(32B)4e
0.3422(3) 0.7850(3) 0.5525(4) 0.08 H(32C)4e
0.3013(3) 0.9086(3) 0.4919(4) 0.08 H(51A)4e
0.2617(3) 0.6855(3) 0.1779(4) 0.08 H(51B)4e
0.3064(3) 0.7164(3) 0.0668(4) 0.08 H(51C)4e
0.2426(3) 0.8221(3) 0.1258(4) 0.08 H(52A)4e
0.3814(3) 0.9748(3) 0.1062(4) 0.08 H(52B)4e
0.4517(3) 0.8723(3) 0.0514(4) 0.08 H(52C)4e
0.4935(3) 0.9474(3) 0.1520(4) 0.08602
(CH3)3(CN)2[OSi(CH3)3lC6H6ТаЫе 3. Final atomic coordinates and displacement parameters (in À^)
Atom Site X y ζ Un Un t/33 Un Um U2}
Si 4e 0.35115(5) 0.37102(6) 0.21879(5) 0.0602(4) 0.0568(5) 0.0601(5) 0.0066(4) -0.0002(4) -0.0067(4) О 4e 0.3689(1) 0.5189(1) 0.2657(1) 0.043(1) 0.0525(9) 0.091(1) -0.0024(7) -0.0028(8) -0.0102(9) C(l) 4e 0.4560(2) 0.5976(2) 0.2895(2) 0.038(1) 0.053(1) 0.071(1) 0.0009(9) 0.0002(9) -0.002(1) C(2) 4e 0.4388(2) 0.6648(2) 0.3954(2) 0.047(1) 0.060(1) 0.060(1) -0.001(1) -0.0044(9) 0.003(1) C(3) 4e 0.3530(2) 0.7673(2) 0.3896(2) 0.053(1) 0.057(1) 0.060(1) 0.004(1) 0.003(1) -0.006( 1 ) C(4) 4e 0.3715(2) 0.8620(2) 0.2982(2) 0.058(1) 0.051(1) 0.080(2) 0.004(1) 0.003(1) 0.003(1) C(5) 4e 0.3911(2) 0.8027(2) 0.1893(2) 0.058(1) 0.063(1) 0.063(1) -0.003(1) 0.001(1) 0.011(1) C(6) 4e 0.4740(2) 0.6967(2) 0.2021(2) 0.050(1) 0.067(1) 0.001(1) 0.001(1) 0.001(1) 0.013(1) C(10) 4e 0.5516(2) 0.5167(2) 0.3034(2) 0.047(1) 0.057(1) 0.095(2) 0.001(1) 0.002(1) -0.002(1) N ( l l ) 4e 0.6251(2) 0.4569(2) 0.3132(2) 0.054(1) 0.077(2) 0.161(2) 0.014(1) -0.001(1) 0.001(2) C(12) 4e 0.3932(2) 0.2505(3) 0.3205(3) 0.098(2) 0.071(2) 0.121(2) -0.009(2) -0.009(2) 0.020(2) C(13) 4e 0.4247(3) 0.3477(4) 0.0973(2) 0.106(3) 0.127(3) 0.085(2) -0.005(2) 0.015(2) -0.036(2) C(14) 4e 0.2100(2) 0.3640(3) 0.1914(2) 0.075(2) 0.088(2) 0.084(2) -0.023(2) -0.013(1) -0.003(2) C(30) 4e 0.2502(2) 0.7054(2) 0.3800(2) 0.052(1) 0.065(1) 0.067(1) 0.010(1) 0.007(1) 0.007(1) N(31) 4e 0.1695(2) 0.6609(2) 0.3786(2) 0.058(1) 0.090(2) 0.103(2) 0.007(1) 0.008(1) 0.016(1) C(32) 4e 0.3548(2) 0.8440(3) 0.4950(2) 0.099(2) 0.089(2) 0.076(2) 0.009(2) 0.005(2) -0.019(2) C(51) 4e 0.2906(2) 0.7510(3) 0.1348(2) 0.074(2) 0.095(2) 0.069(2) 0.007(2) -0.012(1) 0.011(1) C(52) 4e 0.4341(2) 0.9101(3) 0.1186(2) 0.100(2) 0.090(2) 0.091(2) -0.008(2) 0.007(2) 0.030(2)
References
1. Klaubert, C. A. : Zur Synthese von Di- und Tetracyan-1,5-dimethy Isemi- bullvalenen. Dissertation, Universität Würzburg, Germany 1987.
2. Sheldríck, G. M.: Program Package SHELXTL-plus. Release 4.1.
Siemens Analytical X-Ray Instruments Inc., Madison (WI53719), USA 1990.
