Crystal structure of S,S'-4,4'-diphenyl ether

Z. Kristallogr. NCS 215 (2000) 557-559

© by Oldenbourg Wissenschaftsverlag, München

557

Crystal structure of S,S'-4,4'-diphenyl ether

2,5-bis(trimethylsilyl)thiophenium bis(triflate), C ³ 2H480S2Si4(CF ³ S03)2

E. Horn*'

, S.-Z. Zhang

and N. Furukawa

1 University of Tsukuba, Tsukuba Advanced Research Alliance Center and Department of Chemistry, Tsukuba, Ibaraki 305-8577, Japan

" Rikkyo University, Department of Chemistry, 3-34-1 Nishi-Ikebukuro, Tosima-ku, Tokyo 171-8501, Japan Received April 9, 2000, CCDC-No. 1267/437

OI ¿a, C12 CI3

Table 1. Data collection and handling.

Abstract _

C34H

8F607S

Si

, triclinic, PI (No. 2), a = 15.703(2) A,

P = 104.29(1)°,y= 112.50(1)°, V= 2345.5 A

, Z

Source of material

The title compound was prepared from 2,5-bis(trimethyl- silyl)thiophene S-oxide on treatment with 0.5 molar equivalent of diphenyl ether in the presence of trifluoromethanesulfonic anhy- dride in dry dichloromethane at 233 K. This structure analysis is part of a study of S-aryl thiophenium compounds [1]. Single crys- tals of the compound were obtained by slow recrystallization from chloroform at room temperature.

Discussion

5-Alky 1 thiophenium salts and their reactivities have been known since 1964 [2-4], However, to date S-aryl benzo-bisthiophenium salts and S-aryl monocyclic thiophenium salts are still rare [5], Recently, we have successfully prepared S-[4-(2,6-dimethyl- phenylselenide)-3,5-dimethyl-phenyl]dibenzothiophenium salt [6] in one step, and reported here is the first crystal structure ex- ample of a 5-aryl monocyclic thiophenium salt. The structure rep- resented by the ORTEP plot (30% probability ellipsoids) excludes the two triflate counter ions per molecule for simplicity.

The average O—C bond distance of 1.385(7) A and the C(14)- 0 ( 1 )-C( 17) bond angle of 118.6(4)° are normal. The sulfur atoms are the locations of the positive charges, and the atoms are in a py- ramidal environment with the S—C bond distances in the range of 1.776(6) A to 1.792(6) A and C - S - C bond angles range from 95.1(3)° to 107.6(3)°. All the other bond distances and bond an- gles are in the normal range.

Crystal: colorless, prismatic,

size 0.2 x 0.3 x 0.7 mm Wavelength: Mo Ka radiation (0.7107 Ä)

3.36 cirf1

Diffractometer, scan mode: Rigaku AFC7R, <o/29

29max: 60°

N(hkl)measured, N(hkl)unique: 14109, 13671

Criterion for I

Programs: SIR92 [7], teXsan [8], DIFABS [9], ORTEP-II [10]

Table 2. Atomic coordinates and displacement parameters (in Ä2).

* Correspondence author (e-mail: horn@rikkyo.ne.jp)

Atom Site Occ. X y z l/iso

F(4) 2i 0.52(2) 0.617(1) 0.304(1) 1.297(2) 0.199(9) F(5) 2 i 0.52 0.693(1) 0.223(1) 1.266(2) 0.148(6) F(6) 2 i 0.52 0.755(1) 0.317(1) 1.447(2) 0.177(7) F(7) 2i 0.48 0.800(2) 0.273(1) 1.381(2) 0.20(1) F(8) 2i 0.48 0.649(1) 0.242(1) 1.284(2) 0.161(7) F(9) 2 i 0.48 0.712(1) 0.3372(9) 1.443(1) 0.118(5) 0(5) 2 i 0.44(1) 0.811(1) 0.3462(9) 1.140(2) 0.113(6) 0(6) 2 i 0.44 0.675(1) 0.389(1) 1.136(2) 0.126(7) 0(7) 2 i 0.44 0.847(1) 0.456(1) 1.324(2) 0.148(7) 0(8) 2 i 0.56 0.854(2) 0.395(1) 1.264(2) 0.211(9) 0(9) 2i 0.56 0.766(1) 0.4641(9) 1.274(1) 0.159(6) O(10) 2 i 0.56 0.727(1) 0.350(1) 1.095(2) 0.180(7)

H(l) 2 i 1.0548 0.8560 1.2083 0.077

H(2) 2 i 1.0859 0.9720 1.0357 0.082

H(3) 2i 0.9626 0.8596 0.5814 0.200

H(4) 2i 1.0392 0.9135 0.5040 0.200

H(5) 2 i 1.0429 0.8275 0.5663 0.200

H(6) 2 i 1.1154 1.0693 0.8592 0.186

H(7) 2 i 1.0993 1.0799 0.7001 0.186

H(8) 2 i 1.0120 1.0220 0.7564 0.186

H(9) 2 i 1.2491 0.9309 0.7455 0.256

H(10) 2 i 1.2503 1.0203 0.6915 0.256

H(ll) 2 i 1.2674 1.0105 0.8509 0.256

H(12) 2 i 0.8709 0.5812 1.0280 0.121

H(13) 2i 0.9402 0.5594 0.9573 0.121

H(14) 2 i 0.9168 0.5152 1.0897 0.121

H(15) 2i 1.1350 0.5894 1.2352 0.110

H(16) 2 i 1.1547 0.6319 1.1000 0.110

H(17) 2 i 1.1950 0.6913 1.2431 0.110

H(18) 2 i 1.0646 0.7350 1.3728 0.157

H(19) 2 i 0.9533 0.6993 1.3005 0.157

H(20) 2i 0.9990 0.6350 1.3707 0.157

H(21) 2i 1.0182 0.6240 0.6997 0.071

H(22) 2 i 0.8582 0.5209 0.5545 0.077

H(23) 2i 0.7238 0.6686 0.7025 0.072

H(24) 2 i 0.8819 0.7724 0.8471 0.066

H(25) 2i 0.7325 0.4891 0.7996 0.061

H(26) 2 i 0.6232 0.3604 0.8822 0.059

5 5 8 S,S'-Diaryl-2,5-bis-trimethylsilyl)thiophenium bis(triflate)

Table 2. Continued.

Atom Site Occ. x y z t/iso

H(27) 2 i 0.4304 0.2869 0.4776 0.068

H(28) 2 i 0.537 0.4186 0.3972 0.077

H(29) 2 i 0.4251 0.2521 1.0806 0.079

H(30) 2 i 0.521 0.1575 1.0577 0.082

H(31) 2 i 0.2041 0.3308 0.6551 0.131

H(32) 2 i 0.2657 0.2891 0.5996 0.131

H(33) 2 i 0.1986 0.2368 0.6910 0.131

H(34) 2 i 0.4744 0.4796 0.8857 0.113

H(35) 2/ 0.4474 0.4463 0.7274 0.113

H(36) 2 i 0.3873 0.4908 0.7808 0.113

H(37) 2i 0.3541 0.3771 1.0683 0.157

Table 2. Continued.

Atom Site Occ. x y z U,^m

H(38) 2 i 0.2642 0.3905 0.9757 0.157

H(39) 2 i 0.2576 0.295 1.0029 0.157

H(40) 2i 0.4666 -0.0256 0.8379 0.131

H(41) 2 i 0.4249 -0.013 0.6834 0.131

H(42) 2 i 0.5129 -0.0409 0.7224 0.131

H(43) 2 i 0.6557 0.1099 1.009 0.123

H(44) 2i 0.7087 0.0974 0.9007 0.123

H(45) 2 i 0.7145 0.1916 0.9426 0.123

H(46) 2i 0.6271 0.1162 0.5923 0.121

H(47) 2 i 0.5391 0.1443 0.5559 0.121

H(48) 2 i 0.6407 0.2114 0.6442 0.121

Table 3. Atomic coordinates and displacement parameters (in Ä2).

Atom Site X y z Uu U22 U33 U12 C/13 t/23

S(l) 2i 1.0703(1) 0.76872(9) 0.8963(2) 0.0456(8) 0.0420(8) 0.0571(9) 0.0128(6) 0.0069(7) 0.0030(6) S(2) 2 i 0.4380(1) 0.2261(1) 0.7369(2) 0.0454(8) 0.0480(8) 0.0487(8) 0.0088(6) 0.0075(6) 0.0102(6) S(3) 2i 0.7312(2) 0.8748(1) 0.7880(2) 0.096(2) 0.066(1) 0.087(1) 0.021(1) 0.006(1) 0.000(1) S(4) 2 i 0.7656(2) 0.3849(2) 1.2213(2) 0.094(2) 0.100(2) 0.081(1) 0.037(1) 0.021(1) 0.004(1) Si(l) 2 i 1.1062(1) 0.9425(1) 0.7394(2) 0.063(1) 0.064(1) 0.079(1) 0.0110(9) 0.004(1) 0.027(1) Si(2) 2i 1.0309(1) 0.6600(1) 1.1552(2) 0.070(1) 0.060(1) 0.062(1) 0.0265(9) 0.0204(9) 0.0161(9) Si(3) 2 i 0.3402(1) 0.3449(1) 0.8335(2) 0.071(1) 0.080(1) 0.076(1) 0.037(1) 0.026(1) 0.023(1) Si(4) 2 i 0.5662(1) 0.1105(1) 0.7858(2) 0.053(1) 0.056(1) 0.074(1) 0.0176(9) 0.0118(9) 0.0088(9) F(l) 2 i 0.7906(6) 1.0105(4) 0.6624(7) 0.222(8) 0.108(5) 0.136(5) -0.031(5) -0.018(5) 0.035(4) F(2) 2 i 0.6502(5) 0.9209(4) 0.5620(7) 0.151(6) 0.150(6) 0.144(5) 0.053(5) -0.049(5) 0.012(4) F(3) 2 ⁱ 0.7654(6) 0.8885(6) 0.5548(7) 0.189(7) 0.259(9) 0.111(5) 0.061(7) 0.054(5) -0.009(5) O(l) 2 ⁱ 0.6949(3) 0.5318(3) 0.5410(4) 0.071(3) 0.064(3) 0.050(2) -0.016(2) -0.004(2) 0.015(2) 0(2) 2 ⁱ 0.6946(5) 0.9265(5) 0.8593(7) 0.154(6) 0.135(6) 0.158(6) 0.068(5) 0.073(5) -0.030(5) 0(3) 2 ⁱ 0.6686(4) 0.7861(4) 0.7377(6) 0.125(5) 0.070(4) 0.108(5) 0.002(3) 0.001(4) -0.007(3) 0(4) 2i 0.8294(4) 0.8894(4) 0.8470(6) 0.095(4) 0.092(4) 0.128(5) 0.047(3) -0.038(4) -0.027(4) C(l) 21 1.0494(4) 0.7612(4) 1.0627(6) 0.052(3) 0.051(3) 0.049(3) 0.019(3) 0.005(3) 0.002(3) C(2) 2; 1.0592(5) 0.8405(4) 1.1065(6) 0.074(4) 0.054(4) 0.057(4) 0.024(3) 0.008(3) -0.004(3) C(3) 21 1.0760(5) 0.9055(4) 1.0096(8) 0.072(4) 0.041(3) 0.079(5) 0.018(3) 0.002(4) -0.003(3) C(4) 2/ 1.0788(4) 0.8782(4) 0.8868(7) 0.049(3) 0.039(3) 0.067(4) 0.006(3) -0.001(3) 0.007(3) C(5) 2 i 1.029(1) 0.8780(7) 0.579(1) 0.22(1) 0.116(8) 0.075(6) -0.008(8) 0.013(7) 0.016(6) C(6) 2 i 1.080(1) 1.0406(7) 0.768(1) 0.25(1) 0.105(8) 0.133(9) 0.093(9) 0.052(9) 0.058(7)

C(7) 2 i 1.2333(7) 0.981(1) 0.760(1) 0.079(7) 0.35(2) 0.21(1) 0.07(1) 0.065(8) 0.19(1)

C(8) 2/ 0.9275(6) 0.5680(5) 1.0443(9) 0.084(6) 0.074(5) 0.117(7) 0.008(4) 0.012(5) 0.034(5) C(9) 2 i 1.1420(6) 0.6408(5) 1.1871(9) 0.089(6) 0.090(6) 0.108(6) 0.051(5) 0.017(5) 0.027(5) C(10) 2 i 1.0094(9) 0.6854(7) 1.319(1) 0.19(1) 0.146(9) 0.098(7) 0.084(8) 0.079(7) 0.044(6) C ( l l ) 2 i 0.9563(4) 0.7015(3) 0.7823(6) 0.047(3) 0.037(3) 0.047(3) 0.009(2) 0.009(3) 0.003(2) C(12) 2 i 0.9536(4) 0.6327(4) 0.7007(6) 0.063(4) 0.050(4) 0.059(4) 0.017(3) 0.017(3) 0.000(3) C(13) 2 i 0.8643(5) 0.5755(4) 0.6202(6) 0.083(5) 0.041(3) 0.052(4) 0.011(3) 0.011(3) -0.001(3) C(14) 2 i 0.7836(5) 0.5889(4) 0.6250(6) 0.058(4) 0.050(4) 0.044(3) -0.001(3) 0.005(3) 0.014(3) C(15) 2 i 0.7880(4) 0.6589(4) 0.7036(6) 0.045(3) 0.065(4) 0.058(4) 0.013(3) 0.007(3) 0.011(3) C(16) 2/ 0.8761(4) 0.7167(4) 0.7842(6) 0.052(4) 0.051(3) 0.054(4) 0.015(3) 0.011(3) 0.003(3) C(17) 2 i 0.6404(4) 0.4610(4) 0.5945(6) 0.051(3) 0.046(3) 0.048(3) 0.003(3) 0.006(3) 0.008(3) C(18) 2 i 0.6658(4) 0.4453(4) 0.7301(5) 0.046(3) 0.048(3) 0.042(3) 0.006(3) 0.001(2) 0.004(2) C(19) 2 ⁱ 0.6053(4) 0.3732(4) 0.7763(5) 0.049(3) 0.050(3) 0.040(3) 0.015(3) 0.005(2) 0.007(2) C(20) 2 i 0.5213(4) 0.3180(3) 0.6833(6) 0.046(3) 0.041(3) 0.047(3) 0.010(2) 0.008(2) 0.008(2) C(21) 2/ 0.4961(4) 0.3321(4) 0.5477(6) 0.051(3) 0.053(3) 0.044(3) 0.004(3) 0.000(3) 0.005(3) C(22) 2 i 0.5559(4) 0.4052(4) 0.5027(6) 0.064(4) 0.056(4) 0.043(3) 0.002(3) 0.000(3) 0.010(3) C(23) 2 ⁱ 0.4076(4) 0.2714(4) 0.8699(6) 0.051(3) 0.059(4) 0.054(4) 0.015(3) 0.017(3) 0.014(3) C(24) 2 i 0.4388(5) 0.2394(4) 0.9843(6) 0.079(5) 0.069(4) 0.053(4) 0.029(4) 0.025(3) 0.019(3) C(25) 2 i 0.4925(5) 0.1866(4) 0.9715(7) 0.081(5) 0.066(4) 0.058(4) 0.031(4) 0.013(3) 0.027(3) C(26) 2 i 0.5043(4) 0.1754(4) 0.8476(6) 0.051(3) 0.047(3) 0.060(4) 0.015(3) 0.010(3) 0.017(3) C(27) 2 ⁱ 0.2405(6) 0.2945(6) 0.676(1) 0.076(5) 0.117(7) 0.125(7) 0.044(5) 0.004(5) 0.032(6) C(28) 2i 0.4221(6) 0.4534(5) 0.8033(9) 0.119(7) 0.069(5) 0.104(6) 0.042(5) 0.037(5) 0.023(4) C(29) 2 i 0.2997(8) 0.3533(7) 0.989(1) 0.18(1) 0.17(1) 0.124(8) 0.116(9) 0.097(8) 0.063(7) C(30) 2 i 0.4825(6) -0.0061(5) 0.753(1) 0.094(6) 0.062(5) 0.167(9) 0.022(5) 0.044(6) 0.002(5) C(31) 2 i 0.6741(6) 0.1297(6) 0.9261(9) 0.081(6) 0.122(7) 0.104(6) 0.055(5) -0.001(5) 0.005(5) C(32) 2 i 0.5970(6) 0.1503(6) 0.6254(9) 0.109(7) 0.114(7) 0.095(6) 0.048(6) 0.046(5) 0.019(5) C(33) 2 i 0.7412(9) 0.9227(8) 0.644(1) 0.15(1) 0.133(9) 0.085(7) -0.058(7) 0.051(7) -0.054(7) C(34) 2 i 0.721(1) 0.298(1) 1.329(1) 0.19(2) 0.27(2) 0.075(8) -0.09(2) -0.032(9) -0.02(1)

S,S'-Diaryl-2,5-bis-trimethylsilyl)thiophenium bis(triflate) 5 5 9

Acknowledgment. This work was supported by the Research Fund of the Tsukuba Advanced Research Alliance (TARA) project of the University of Tsukuba.

References

1. Zhang, S.-Z.; Sato, S.; Horn, E.; Furukawa, N.: Synthesis and Structure of S-Arylthiophenium Salts from Thiophene Monooxide Derivatives. Con- gress of Heterocyclic Chemistry, Hachioji, Japan, Abstracts (1998) 102.

2. Brumlik, G. C.; Kosak, A. I.; Pitcher, R.: The Synthesis of S- Methylthiophenium Ion. J. Amer. Chem. Soc. 86 (1964) 5360.

3. Acheson, R. M.; Harrison, D. R.: The Synthesis, Spectra, and Reaction of Some S-Alkylthiophenium Salts. J. Chem. (1970) 1764.

4. Heldeweg, R. F.; Hogeveen, H.: Synthesis and Some Properties of S- Alkylthiophenium Ions. Tetrahedron Lett. (1974) 75.

5. Kitamura, T.; Yamane, M.; Furuki, R.; Taniguchi, H. Shiro, M.: Prepara- tion and Crystal Structure of a Parent 1 -Arylbenzo[b]thiophenium Triflate and Its Derivatives. Chem. Lett. (1993) 1703.

6. Zhang, S.-Z.: Doctoral Dissertation, Department of Chemistry, The Uni- versity of Tsukuba, Japan, 2000.

7. Altomare, G.; Cascarano, G.; Giaccovazzo, C.; Guagliardi, A.; Burla, M.

C.; Polidori, G.: SIR92 - a program for automatic solution of crystal struc- tures by direct methodes. J. Appl. Crystallogr. 27 (1994) 435-436.

8. teXsan. Single Crystal Structure Analysis Software. Version 1.7. Molecu- lar Structure Corporation., 3200 Research Forest Drive, The Woodlands, TX 77381, USA 1995.

9. Walker, N.; Stuart. D.: An Empirical Method for Correcting Diffractometer Data for Absorption Effects. Acta Crystallogr. A39 ( 1983) 158.

10. Johnson, C. K.: ORTEP-II. Report ORNL-5138, Oak Ridge National Lab- oratory, Tennesse, USA 1976.