Znorg. Chem. 1993, 32, 2972-2974
2972
Synthesis and Structural Characterization of a Homoleptic Bismuth Arenethiolate David A. Atwood,l* Alan H. Cowley,**l* Robert D. Hernandez,l* Richard A. Jones,*J* Lora L. Rand,l* Simon C. Bott,lb and Jerry L. Atwoodlb Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, Texas 78712, and Department of Chemistry, The University of Alabama, Tuscaloosa, Alabama 35487 Received January 14, 1993
Table I. Crystallographic Data for Bi(SAr'), (1; Ar' = 2,4,6-t-BusCsH2) color Y, deg orange v,A3 Cd-hBiSs formula 1941.6 fw d(calc), g cm-3 0.31 X 0.08 X 0.98 2 cryst dimens, mm cryst syst triclinic radiation spacegroup P1 tot. no. of reflcns no. of tot. reflcns a, A 17.214(2) obsd b, A 17.742(2) u test c, A 20.984(2) R ' a,deg 99.335( 8) RWb fl, deg 114.264(9)
'R = IJpd- (FJZlFd.
91.981(9) 5775(5) 1.202 4
Mo Ka 10 603 5033 Fo > W F o ) 0.0582 0.0604
Rw = [;(IF4 - pJ)2/ZGF,z]1/2.
Introduction Current interest in bismuth thiolates derives in part from their utility as fungicides? antitumor agents? vulcanizationcatalysts: and analytical reagent^.^ Although homolepticBi(II1) compounds of the genre Bi(SR)3 have been prepared previously,6 X-ray structural data are available only for bidentate SN (pyridinethiolate)' and SS (dithiocarbamate) ligands.* Herein we report the preparation and X-ray crystal structure of [Bi(SAr')3] (1; Ar' = 2,4,6-?-Bu3CsHz). To our knowledge, this represents the first X-ray structural information on a monodentate tris thiolate of Bi(II1).
Experimental Section General Procedures. All manipulations were performed under a dry, oxygen-free dinitrogen or argon atmosphere using standard Schlenk techniques or in a Vacuum Atmospheres HE-493 drybox. The solvents toluene, hexane, and diethyl ether were freshly distilled from sodium/ benzophenoneprior to use. IH NMRspectra were recorded on a General Electric QE 300 instrument operating at 300.17 MHz and are referenced to Me& (0.0 ppm). The CsDs solvent was dried over 4 A molecular sieves prior to use. Mass spectra (E1 and CI) were recorded on a Bell and Howell 21491 instrument and elemental analyses were determined on a Perkin-Elmer 2400 analyzer. A solution of tert-butyllithium in THF was purchased from Aldrich and titrated prior to use. The BiCl3 was procured commercially (Aldrich) and the thiol, HSC6H2(2,4,6-tBu3) was prepared as described in the literat~re.~ Preparationof Li(sC&(2,4,&t-B113)). Oneequivalent of t-BuLi (0.36 mmol, 0.16 mL of 2.24 M solution in THF) was added via cannula to a stirred solution of HSC6Hz(2,4,6-1-Bu3)(0.10 g, 0.36 "01) in 50 mL of THF at -78 OC. The clear solution was allowed to warm to 25 OC, stirred for an additional 2 h, and then used in the following preparation. Preparation of Bi(SC&(2,4,6-t-B~~))3(1). Three equivalents of LiSC6H2(2,4,6-t-Bug)(8.4 mL, 11.9 M solution in THF) were added to a stirred solution of BiCl3 (0.030 g, 0.10 mmol) in 50 mL of THF at -78 OC. The dark orange reaction mixture was allowed to warm slowly to 25 OC and then stirred at this temperature for 12 h. The solvent and volatiles were removed under reduced pressure and the resulting orange residue was extracted with hexane (40 mL). The white precipitate (tested positive for LiCI) was filtered off and the filtrate was concentrated in vacuo to a volume of 20 mL. Cooling of this solution to -20 OC (24 h) produced 0.08 g (77% yield) of orange crystalline 1. Mp: 105-1 10 OC dec. IH NMR (CsD6,25 OC, 300.15 MHz): 6 7.54 (6 H, s, m-H ring), 1.63 (54 H, s, o-t-Bu), 1.29 (27 H, s, p-r-Bu). Anal. Calcd for CSJ-I~IBiS,: C, 62.26; H, 8.42. Found: C, 62.02; H, 8.21. MS (E1 and CI): m/e 554, [(2,4,6-r-Bu,CsH2)2Sz]+. (1) (a) The University of Texas at Austin. (b) The University of Alabama. (2) Klafitke, T.; Gowik, P. Z . Naturforsch. 1987, BIZ, 940. (3) Kepi-Maier, P.; Klapbtke, T. Inorg. Chim. Acta 1988, 152, 49. (4) Lemiszka, T.; Minchler, L.; Cottle, D. L. US.Patent 2,992,202. (5) Suprunovich, V. I.; Vashchenko, S. T. Zh. Anal. Khim. 1982,37, 632. ( 6 ) (a) Gilman, H.; Yale, H . L. J . Am. Chem. Soc. 1951, 73, 2880. (b) Weiber, M.; Baudis,U. Z . Anorg. Allg. Chem. 1976,423,47. (c) Janzen, A. F.; Vaidya, 0.C.; Willis, C. J. J. Inorg. Nucl. Chem. 1981,43,1469. (7) Block, E.; Ofori-Okai,G.; Kang, H.; Wu, J.; Zubieta, J. Inorg. Chem. 1991, 30, 4784. (8) Raston, C. L.; White, A. H. J. Chem. SOC.,Dalton Trans. 1976, 791. ( 9 ) Rundel, W. Chem. Ber. 1968, 101, 2956.
0020-1 6691931 1332-2972$04.00/0
b Figure 1. ORTEP view of molecule A of compound 1.
Flgure 2. View emphasizing the geometry around Bi for molecule A of compound 1. X-ray CrystaIStmchwof 1. Crystalsof 1suitable for X-ray diffraction experiments were grown from hexane solution at -20 OC over a 2-week period. Details of the crystal data and a summary of intensity data collection parameters for 1 are presented in Table I. The crystals were mounted in thin-walled glass capillaries and sealed under argon. The unit cell parameters were obtained by centering 25 reflections having 28 values >35O. The triclinic space group Pi was established on the basis of systematic absences. The data were collected on an Enraf-Nonius CAD-4 diffractometer (25 OC) in the +h,hk,+l quadrant with 28 values between 2 and 40° in a manner described previously.10 The intensity standards indicated a
