Crystal structures of the diastereomeric 2-chloro-3-methyl-l-(2-methyl- phenyl)-l-phenyl-l-butenes, С4Н4(СбН5)(С7Н7)С1СНз

ζ. Kristallogr. NCS 213 (1998) 717-719

717

© by R. Oldenbourg Verlag, München

Crystal structures of the diastereomeric 2-chloro-3-methyl-l-(2-methyl- phenyl)-l-phenyl-l-butenes, С4Н4(СбН5)(С7Н7)С1СНз

к . Peters, E.-M. Peters

Max-Planck-Institut für Festkörperforschung, Heisenbergstraße I, D-70506 Stuttgart, Germany U. M. Doht and H. Quast

Universität Würzburg, Institut für Organische Chemie, Arn Hubland, D-97074 Würzburg, Germany

Received April 27, 1998, CSD-No. 409298 and CSD-No. 409299

Source of material: Mixtures of equal amounts of the diastere- omeric title compounds were prepared, according to ref. 1, by chlorination of 3-methyl-l-(2-methylphenyl)-l-phenyl-1-butene (£:Z = 1:3, carbon tetrachloride solution, 268 К - 278 К) with an excess of chlorine followed by thermal dehydrochlorination at 423 К - 443 К of the colorless intermediate 1,2-dichloride {0.5h - Ih) and distillation at 0.1 Torr. Partial separation of the dias- tereomers was achieved by careful distillation of the 1 : 1 mixture through a 60 cm Spaltrohr colurrm (bath temp. 4 1 8 K 1 2 K / 0 . 1 Torr) which afforded fractions with maximal 66% of the Ζ dias- tereomer (bp 377 К - 378 К / 0.1 Torr) and maximal 98% of the

tions of the enriched fractions eventually furnished the pure diastereomers as colorless crystals, each in 27% yield, mp of the

320 К.

The crystal structures of the title compounds provide unequivocal proof of their configurations which is more difficult to obtain on the basis of spectroscopic evidence. Both diastereomers are chiral by virtue of the presence of a helical axis. The stereographic projections exhibite the enatiomers with M, E (Figure 2) and P, Ζ configuration (Figure 1 ). In both diastereomers the isopropyl group at C2 adopts a conformation in which the H-C3 bond lies in the plane of the double bond.

65-1

As shown by the Newman projections (above), the planes of the aromatic rings are twisted strongly relative to the plane of the double bond. This twisting is more pronounced for the Ζ diastereomer than for the E diastereomer. Furthermore, the planes of the o-tolyl rings are displaced farther from the plane of the double bonds (£ diaste- reomer: 78.7°, Ζ diastereomer: 88.1°) than those of the phenyl rings

of the corresponding diastereomeric 2-bromo compounds are repor- ted in ref 2.

1. Ζ Diastereomer

C14

Fig. 1. Molecule plot of the P, Ζ diastereomer of С4Н4(СбН5)(С7Н7)С1СНз.

CisHigCl, orthoriiombic, Pca2\ (No. 29), a =27.636(6) Â,

¿>=6.272(1) Â, с =8.809(2) Â, V=1526.9Â^ Z=4, =0.045, ÄwfFJ =0.043.

Table 1. Parameters used for the X-ray data collection

Crystal: colorless prism, size 0.45 χ 0.45 χ 0.65 mm Wavelength: Mo Ka radiation (0.71073 Â)

μ: 2.30 cm"'

Difiractometer: SYNTEXP3

Scan mode: Wyckoff

'^measunmetu'· 293 К 55°

ЩЬк1)т1чие·· 1341 Criterion for Fo: F o > 3 a ( F „ ) iHparam)reimeir. 171

Program: S^ÍF,I,XTL·plus

718

Table 2. Final atomic coordinates and displacement parameters (in Â^) Table 2. (Continued)

Atom Site ^X У ^{г í/iso} Atom Site X V ; t/iso

H(3) Aa 0.7113(1) 0.3264(7) 0.4065(6) 0.08 Н(14) 4а 0.6655(2) 0.745(1) -0.0634(7) 0.08 H(4A) Λα 0.7263(2) -0.0357(8) 0.4172(8) 0.08 Н(15) 4а 0.6324(2) 0.409(1) -0.1014(7) 0.08 H(4B) 4a 0.7275(2) -0.0189(8) 0.5947(8) 0.08 Н(16) 4а 0.6115(1) 0.1944(8) 0.1073(6) 0.08 H(4C) Aa 0.7685(2) 0.0873(8) 0.4977(8) 0.08 Н(17А) 4а 0.7514(2) 0.4318(8) 0.6286(8) 0.08 H(7) 4a 0.4627(1) 0.3968(8) 0.5596(6) 0.08 Н(17В) 4а 0.7098(2) 0.3287(8) 0.7246(8) 0.08 H(8) 4a 0.4327(2) 0.0977(9) 0.4404(6) 0.08 Н(17С) 4а 0.6994(2) 0.5310(8) 0.6253(8) 0.08 H(9) 4a 0.4838(2) -0.124(1) 0.2996(7) 0.08 Н(18А) 4а 0.5868(2) 0.5572(8) 0.5717(7) 0.08 H(IO) 4a 0.5670(2) -0.0438(8) 0.2859(6) 0.08 Н(18В) 4а 0.5453(2) 0.5264(8) 0.6911(7) 0.08 H(12) 4a 0.6531(2) 0.6739(8) 0.3913(6) 0.08 Н(18С) 4а 0.5368(2) 0.6705(8) 0.5482(7) 0.08 H(13) 4a 0.6738(2) 0.8814(8) 0.1791(7) 0.08

Table 3. Final atomic coordinates and displacement parameters (in Â^)

Atom Site X y ζ í/ll U22 ί/зз Ui2 Uli {/23

Cl 4a 0.63126(4) 0.0494(2) 0.6533 0.0629(6) 0.0876(8) 0.0630(7) -0.0132(6) -0.0029(8) 0.0227(9) C(l) 4a 0.6168(1) 0.2758(7) 0.4037(6) 0.045(2) 0.057(3) 0.047(2) 0.001(2) -0.000(2) -0.001(2) C(2) 4a 0.6498(1) 0.2090(7) 0.5010(6) 0.048(2) 0.058(3) 0.054(3) -0.006(2) 0.003(2) 0.008(3) C(3) 4a 0.7039(1) 0.2544(7) 0.4999(6) 0.046(2) 0.081(3) 0.058(3) -0.011(2) -0.009(2) 0.014(3) C(4) 4a 0.7346(2) 0.0541(8) 0.5015(8) 0.053(3) 0.104(4) 0.104(5) 0.009(3) 0.001(3) 0.018(4) C(5) 4a 0.5643(1) 0.2231(7) 0.4165(6) 0.043(2) 0.054(3) 0.049(3) 0.004(2) -0.004(2) 0.004(2) C(6) 4a 0.5338(2) 0.3549(7) 0.5002(6) 0.061(3) 0.062(3) 0.047(3) 0.003(2) -0.001(2) 0.004(3) C(7) 4a 0.4844(1) 0.3039(8) 0.5060(6) 0.047(3) 0.094(4) 0.060(3) 0.012(3) 0.003(2) 0.005(3) C(8) 4a 0.4665(2) 0.1315(9) 0.4328(6) 0.050(3) 0.104(4) 0.068(4) -0.008(3) 0.004(3) 0.008(4) C(9) 4a 0.4967(2) -0.001(1) 0.3505(7) 0.059(3) 0.087(4) 0.078(4) -0.017(3) -0.006(3) -0.010(4) C(10) 4a 0.5457(2) 0.0458(8) 0.3437(6) 0.051(2) 0.073(3) 0.067(3) -0.004(3) 0.006(2) -0.006(3) C(ll) 4a 0.6307(2) 0.4104(8) 0.2695(6) 0.042(2) 0.055(3) 0.054(3) 0.008(2) -0.001(2) 0.005(2) C(12) 4a 0.6489(2) 0.6185(8) 0.2906(6) 0.059(3) 0.063(3) 0.065(3) 0.003(3) -0.001(3) 0.010(3) C(13) 4a 0.6614(2) 0.7396(8) 0.1667(7) 0.067(3) 0.069(3) 0.075(4) -0.003(2) 0.005(3) 0.016(4) C(14) 4a 0.6562(2) 0.661(1) 0.0232(7) 0.058(3) 0.100(5) 0.072(4) 0.005(3) 0.004(3) 0.033(4) C(15) 4a 0.6374(2) 0.461(1) 0.0000(7) 0.065(3) 0.120(5) 0.044(3) 0.008(3) 0.001(3) 0.013(4) C(I6) 4a 0.6245(1) 0.3344(8) 0.1237(6) 0.057(3) 0.077(3) 0.058(4) 0.005(2) -0.004(3) -0.001(3) C(17) 4a 0.7174(2) 0.4005(8) 0.6314(8) 0.068(3) 0.116(4) 0.091(5) -0.033(3) -0.013(4) 0.010(4) C(18) 4a 0.5524(2) 0.5442(8) 0.5852(7) 0.088(4) 0.083(4) 0.085(4) 0.002(3) 0.019(3) -0.016(4)

2. 3 f , £ D í a s t e r e o i i i e r

глС9 C18H19CI, monocUnic, P2\lc (No. 14), a =12.478(2) Â,

b =9.942(2) Â, с =12.632(3) Â, β =97.41(3)°, V=1554.0 Â^

Ζ =4, R(F) =0.059, R^F) =0.060.

Table 4. Parameters used for the X-ray data collection

Crystal: colorless prism, size 0.45 χ 0.55 χ 1.25 mm Wavelength: Mo Ka radiation (0.71073 λ )

μ: 2.30 cm-' Diffractometer: SYNTEX P3

Scan mode: Wyckoff

'^measurement' 2 9 3 К

29inax: 55°

щтшчяие·· 1758 Criterion for Fo. fo > 3 a(Fo)

^(param)refined· 172

Program: SHELXTL-pIus

Fig. 2. Molecule plot of the M, E diastereomer of С4Н4(СбН5)(С7Н7)С1СНз.

Diastereomers С4Н4(СбН5)(С7Н7)С1СНз

719

Table 5. Final atomic coordinates and displacement parameters (in Â^) Table 5. (Continued)

Atom Site ДГ v f/iso Atom Site X V ^•7 fiso

H(3) 4e 0.7149(3) 01156(4) 07385(3) 0.08 H(I4) 4e 0.7858(5) 0.7147(5) 0.3537(4) 0.08 H(4A) 4e 0.6744(4) -0.1005(5) 0.6761(4) 0.08 H(15) 4e 0.6350(4) 0.7015(5) 0.4437(4) 0.08 H(4B) 4e 0.7545(4) -0.0301(5) 0.6077(4) 0.08 H(16) 4e 0.6175(4) 0.5213(5) 0.5618(4) 0.08 H(4C) 4e 06312(4) -0.0398(5) 0.5642(4) 0.08 H(17A) 4e 0.5428(3) 0.0326(5) 0.7622(4) 0.08 H(7) 4e 09219(5) 0.4468(5) 0.9410(4) 0.08 H(17B) 4e 0.4969(3) 0.0987(5) 0.6530(4) 0.08 H(8) 4e 1.0702(5) 0.3117(7) 0.9277(5) 0.08 H(17C) 4e 0.5408(3) 0.1896(5) 0.7505(4) 0.08 H(9) 4e 1.0709(4) 0.1631(6) 0.7882(5) 0.08 H(I8A) 4e 07557(4) 0.5334(5) 0.8705(4) 0.08 H(IO) 4e 0.9283(3) 0.1663(5) 0.6453(4) 0.08 H(I8B) 4e 06812(4) 0.4277(5) 0.8048(4) 0.08 H(I2) 4e 0.9032(3) 0.3765(4) 0.4988(3) 0.08 H(I8C) 4e 0.7357(4) 0.5426(5) 0.7456(4) 0.08 H(I3) 4e 0.9165(4) 0.5506(5) 0.3786(4) 0.08

Table 6. Final atomic coordinates and displacement parameters (in Â^)

Atom Site X У г t/ll 1/22 Í/33 Un l/i3 Í/23

CI 4e 0.58151(9) 0 77?7(1) 0.48794(9) 0.0836(8) 0.118(1) 0.0929(8) -0.0131(7) -0.0066(6) 0.0007(7) C d ) 4e 0.7516(3) 0.3169(4) 0.6167(3) 0.060(2) 0.066(3) 0.075(3) 0.004(2) 0.017(2) -0.006(2) C(2) 4e 0.6765(3) 0.2208(4) 0.6044(3) 0.068(2) 0.081(3) 0.076(3) 0.001(2) 0.011(2) -0.010(2) C(3) 4e 0.6618(3) 0.1066(4) 0.6769(3) 0.077(3) 0.084<3) 0.088(3) -0.015(2) 0.006(2) -0.002(3) C(4) 4e 0.6826(4) -0.0286(5) 0.6270(4) 0.115(4) 0.094(4) 0.118(4) -0.015(3) 0.008(3) 0.006(3) C(5) 4e 0.8390(3) 0.3114(4) 0.7095(3) 0.063(2) 0.069(3) 0.078(3) -0.013(2) 0.014(2) -0.002(2) C(6) 4e 0.8382(4) 0.3931(4) 0.7968(4) 0.089(3) 0.072(3) 0.089(3) -0.014(3) 0.020(3) 0.002(3) C(7) 4e 0.9233(5) 0.3917(5) 0.8787(4) 0.126(4) 0.109(4) 0.087(3) -0.042(4) -0.008(3) 0.005(3) C(8) 4e 1.0088(5) 0.3083(7) 0.8734<5) 0.094(4) 0.145(6) 0.112(4) -0.054(4) -0.024(3) 0.048(4) C(9) 4e 1.0111(4) 0.2237(6) 0.7879(5) 0.064(3) 0.138(5) 0.134(5) 0.001(3) 0.007(3) 0.049(4) C(10) 4e 0.9271(3) 0.2247(5) 0.7057(4) 0.066(3) 0.103(3) 0.102(3) 0.004(3) 0.010(2) 0.015(3) C ( l l ) 4e 0.7580(3) 0.4300(4) 0.5414(3) 0.062(2) 0.070(3) 0.078(3) 0.005(2) 0.010(2) -0.010(2) C(12) 4e 0.8466(3) 0.4423(4) 0.4869(3) 0.070(3) 0.072(3) 0.094(3) 0.005(2) 0.016(2) 0.001(3) C(13) 4e 0.8552(4) 0.5458(5) 0.4172(4) 0.094(3) 0.087(3) 0.102(3) -0.004<3) 0.027(3) 0.004<3) C(14) 4i 0.7789(5) 0.6418(5) 0.4022(4) 0.123(4) 0.079(3) 0.099(3) -0.002(3) 0.010(3) 0.011(3) C(15) 4e 0.6900(4) 0.6335(5) 0.4548(4) 0.111(4) 0.082(4) 0.127(4) 0.034(3) 0.010(3) 0.009(3) C(16) 4e 0.6795(4) 0.5275(5) 0.5244(4) 0.086(3) 0.098(4) 0.107(3) 0.027(3) 0.032(3) 0.011(3) C(17) 4e 0.5504(3) 0.1062(5) 0.7146(4) 0.093(3) 0.133(4) 0.111(4) -0.029(3) 0.028(3) 0.008(3) C(18) 4e 0.7448(4) 0.4823(5) 0.8055(4) 0.154(5) 0.094(4) 0.102(3) -0.014(4) 0.037(3) -0.024(3)

References

I. Doht, U. M.: 1,2-Disubstituierte 2-Halogenstyrole. - Synthese und Stereo- chemie der 1,2-Eliminierung zu Alienen. Dissertation, Universität Würz- burg, Germany 1986.

2. Peters, K.; Peters, E.-M.; Doht, U. M.; Quast, H.: Ciystal structures of the diastereomeric 2-bromo-3-methy 1-1 -(2-iiiethylphenyl)-1 -phenyl- 1-bute- nes. С4Н4(СбН5)(С7Н7)В1СНз. Ζ. Kristallogr. NCS 213 (1998) 720-722.

3. Sheldrick, G. M.: Program Package SHELXTL-plus. Release 4.1.

Siemens Analytical X-Ray Instruments Inc., Madison (WIS3719), USA 1990.