J. Am. Chem. Soc., 1996, 118(13), , DOI: /ja

Transcription

1 J. Am. Chem. Soc., 996, 8(3), , DOI:0.02/ja Terms & Conditions Electronic Supporting Information files are available without a subscription to ACS Web Editions. The American Chemical Society holds a copyright ownership interest in any copyrightable Supporting Information. Files available from the ACS website may be downloaded for personal use only. Users are not otherwise permitted to reproduce, republish, redistribute, or sell any Supporting Information from the ACS website, either in whole or in part, in either machinereadable form or any other form without permission from the American Chemical Society. For permission to reproduce, republish and redistribute this material, requesters must process their own requests via the RightsLink permission system. Information about how to use the RightsLink permission system can be found at Copyright 996 American Chemical Society

2 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page I L Formula FW Spwo pup System irefections (*) 20r aa via CIA Pr Y VIA3 z F(000) DRIMg asl-3 Crystal size/fam.(mo-k.ya 4 6 C4HBiCtS3 C6HU BiAs PnMu orthorxxaabic P2 k monoclinic (22) (25) (9) 8.875(4) 2.263(5) 7.582(2) 92529(9) 8.250(9) (4) (6) 2832(3) x0.5xO.O 0.2x0.5x PI triclinic 25 ( ) (2) 6.625(2) (3) 90=05(2) 07.84(3) 05.8() 74.9(6) x0.005x (Ct Ka) C H 4 cn2s P2 monoclinic (2) (3) 9.206(3) 9.76(2) 90 7.() (4) x0.Sx Scondary abs. max. actinction 0e4fndex ange of A, k. I Reflections L E E-8 0,8;0,3;0,0 0,8;0,7; s " E-6 0,0;-8,7;-, ,0;0,0;,-0,0 222 Unqeectices Nelections Paramstoned (>3.00 C(I)) 47 unit (I>3.00(I)) 94 a Weight (>3m000)) 209 unit (>2.00 0()) 62 (a ) R Goodness of fit Mini max. features in fins differncema pfoa s Absolute structwe / / (2) Diffractonter Riaku AFC5R Emaf-Nonius CAN RigsD4 AF5R Riakn AFC5R *= F 2o)

3 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 2 2-chloro-, 3, 6-trithia-2-bismocane 4 Bil CIA C2A S2A Ci / S2/ C2 C* S2AX' CiAX C2A*

4 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 3 Table Fractional ic positional parameters and equivalent isotropic temperature factors (A2) for C 4 H 8 BiCIS 3 with e.s.d.s in parentheses. x y s Beq Bi() (8) (8) 4.70(2) Cl() 0.567(6) (5) 8.7(2) S() (7) (5) 6.6(2) 0.22(8) (4) (4) 7.6() C() 0.59(3) 0.636() 0.655(2) 7.2(6) 0.265(3) 0.59(2) 0.548(2) 9.(6) H() H(2) H(3) H(4) Beq = X_2(UnI(aa-)2 + U 22 (bb) 2 + U 33 (b6) 2 + 2Ut 2 aa-bb* cosy + 2U 3 aa*cc" cos)8 + 2U 23 bb'cc' cos a) Table Anisotropic temperature factors (A2) for C 4 H 8 BiCIS 3 with e.s.d.s in parentheses. U U 22 U 33 U 2 U 3 U 23 Bi() 0.07(4) 0.36(0) 0.02(4) (3) Cl() 0.036(3) 0.94(8) 0.025(2) (2) S() 0.045(3) 0.83(8) 0.02(2) (2) (6) 0.065(3) 0.038(2) 0.008(4) 0.005(3) 0.002(2) C() 0.7(2) 0.05() 0.05() -0.02() -0.02() 0.008(9) 0.2(2) 0.8(2) 0.05() 0.06(2) 0.03() 0.04() The general temperature factor expression: exp(-2r'(a" Uith + b' U 2 2 k 2 + c" 2 U 3? + 2a'b'U, 2 hk + 2a'c"U 3 hi + 2b'c'U 2 3 ki))

5 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 4 Table :Interic distances (A) for C 4 H 8 BiCIS Bi() Bi() S() Cl() C() distance 2.682(5) 2.54(6).75(2).78(2) Bi() Bi() S() C() S() C() distance 2.849(5) 2.54(6).75(2).42(2) Table :Interic distances (A) for C4H 8 BiCIS 3. distance distance C() H().08 C() H(2).08 H(3).08 H(4).08 Table :Intramolecular bond angles (degrees) involving non-hydrogen s for C 4 H 8 BiCIS 3. angle angle Cl() Bi() S() 55.3(2) Cl() Bi() 85.2() Cl() Bi() 85.2() s() Bi() 79.0() S() Bi() 79.0() Bi() 99.4(3) Bi() S() C() 0.T(6) Bi() S() C() 0.7(6) C() S() C() 05() Bi() 07.5(8) S() C() 2() C() 23() 0

6 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 5 Table :Intramolecular bond angles (degrees) involving non-hydrogen s for C4H 8 BiCIS 3. S() H() C() C() C() C() H() H() H(2) H(4) H(4) angle S( ) C() H(3) C() C() H(2) H(2) H(3) H(3) H(4) angle Table :Special contacts (A) involving non-hydrogen s for C4H 8 BiCIS 3. distance ADC distance ADC Bi() Cl( ) 3.288(5) Bi() 3.5(6) Bi() 3.5(6) Cl() S() 3.430(7) CI() 3.83(2) Cl() 3.83(2) Cl() C() 3.87(2) 5540 Cl() C() 3.87(2) S() C() 3.96(2) S() C() 3.96(2) C() 3.52(2) (2) Bi() 2.54(6) Bi() 2.54(6) Bi() Cl() 2.682(5) Bi() S( ) 2.849(5) Bi() Cl() 3.286(5) Bi() 3.5(2) Bi() 3.5(2) Bi() 3.5(6) Bi() 3.5(6) Bi() C() 3.63(2) Bi() C() 3.63(2)

7 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 6 J& - 3 :L -4-v, 2-bis (2- (, 3-dithia-2-bismolane) thio) ethane 6 C3 C4 SIO* S3 / / C2 S2 SIO* CI Si i /' S5 S6 C5 C6 S7*

8 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 7 Table :Fractional ic positional parameters and equivalent isotropic temperature factors (A2) for C 6 H 2 Bi 2 S 6 with e.s.d.s in parentheses. Bi() Bi(3) Bi(4) S() S(0) S() C() x 0.668() 0.989() 0.453() () (7) (7) 0.455(7) (8) (7) 0.46(8) 0.04(7) 0.350(7) (7) -0.20(8) (7) (8) 0.750(3) 0.782(3) 0.483(3) 0.39(4) 0.357(3) 0.207(3) 0.223(2) 0.257(3) y (6) (5) (6) (5) (4) 0.045(4) (4) 0.3(4) (4) 0.202(4) (4) 0.067(4) (4) (3) (4) (4) -0.02() () 0.57(2) 0.223(2) 0.095() 0.28(2) () -0.02(2) z (6) (6) (6) (6) -0.98(4) (4) (4) (4) (3) (4) (4) (4) (4) (4) (4) (4) -0.7() -0.06() () (2) () (2) () (l) e,3.79(3).70(3).62(3).89(3).8(2) 2.3(2) 2.0(2) 2.7(2).8(2) 2.9(2) 2.0(2) 2.5(2) 2.2(2) 2.(2).8(2) 3.2(2) 2.2(5) 2.9(6) 3.0(6) 4.4(7) 2.7(6) 3.3(6).(5) 3.(6) 8

9 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 8 x y z B, -0.07(4) 0.87(2) (2) 5.9(8) C(0) (5) 0.25(2) (2) 7.8(8) C() (3) 0.3(2) (2) 3.8(6) -0.2(3) 0.96() () 3.0(6) H() H (2) H (3) H(4) H(5) H(6) H(7) H(8) H(9) H(0) H() H(2) H(3) H(4) H(5) H(6) H(7) H(8) H(9) H(20)

10 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 9 x y z Beq H(2) H(22) H(23) H() Beq = x--(uit(aa') 2 + U 22 (bb*) 2 + U 33 (bb*) 2 + 2Ul 2 aa'bb' cos y + 2Ut 3 aa'cc' cosl3 + 2U 23 bbcc* cos a) 0

11 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 0 I Table :Interic distances (A) for C 6 Hl 2 Bi 2 S / 4 distance distance Bi() S() 2.59(6) Bi() 2.565(6) Bi() 2.634(7) 2.635(7) 2.552(6) 2.553(7) Bi(3) 2.580(7) Bi(3) 2.540(6) Bi(3) Bi(4) S() 2.665(7) 2.554(7) Bi(4) Bi(4) S(0) 2.643(6) 2.550(7) S() C().82(2).8(3) C (3).79(3).83(3).75(3).85(3).8(2).87(3).8(4) S(0) C(0).78(4) S() C().83(3).8(3) C().42(3).46(4).48(3).50(3) C(0).34(5) C().47(3) 2

12 (0996 American Chemical Society J. Am. Chem. Soc. VI 8 Page3225 Agocs Supplemental Page distance distance C() H() C( ) H(2) H(3) H(4) H(S) H(6) H(7) H(8) H(9) H(0) H() H(2) H(3) H(4) C(S) H(5) C(s) H(6) H(7) 0.94 H(8) C(0) H(9) 0.9 C(0) H(20) 0.98 C() H(2) C() H(22) H(23) H() 3

13 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 2 3 B 8 a 3t Bi BI 52 B2 B2 82 B2 B2 Bn2 Table :Special contacts (A) S2 SI S3 S7 S5 S0 s5 S6 S3 S7 50 $ distance 2.565(7) 2.59(7) 2.633(7) 3.34(7) 3.70(6) 3.39(l) (" 2.552(7) 2.553(7) 2.637(7) 3.(7) 3.257(6) 3.52(9) 3.590(9) i3 involving non-hydrogen s for Q I 2 Bi 2 S 6. ADC(*) B3 B3 g B B4 B4 B4 B4 so S7 S9 SI S SO S2 Sl S0 S9 S S5 distance 2.539(7) 2 58(7) 2 664() 3.099(7) 3.28(9) 3.389(7) (9) 2.549() 2.553() (9) 3.77(9) 3.292(6) 3.453(7) 3.628(7) ADC(*) Contacts out to 4.9 angstroms. Estimated standard deviations in the least significant figure are given in parentheses.

14 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 3 Table :Intramolecular bond angles (degrees) involving non-hydrogen s for C 6 H 2 Bi 2-2S 6. S() S(0) Bi() Bi() Bi(3) Bi(3) Bi(4) S() Bi() Bi() Bi(3) Bi(3) Bi(4) S() S() C() C() C() C(0) angle 83.7(2) 9.2(2) 86.4(2) 83.5(2) 94.2(2) 87.(2) 00.4(8) 99.6(9) 0.6(9) 02.2(7) 04() 0.(9) 6() 20(2) 5() 5() 9(3) S() C() 3() S() S(0) S() Bi() Bi(3) Bi(4) Bi(4) S(0) Bi() Bi(3) Bi(4) Bi(4) S(0) C(0) S() C (4) C(0) C() C() angle 84.7(2) 04.0(2) 84.3(2) 82.6(2) 00.3(2) 85.0(2) 95.2(8) 99() 97.6(9) 96.9(8) 03() 97.5(9) 7() 4(2) 3() () 30(3) 6() 4

15 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 4 Table :Special angles (degrees) involving non-hydrogen s for CHI 2 Bi 2 S 6. S2 B S Bril S2 B S2 8l S2 8 S 8l SI. l SI BI Si li Si a S3 all S3 all S3 a S3 Bil 87 Bl S7 al S7 all $5 SI i S5 B S0 ar 55 B2 85 B2 S5 2 S5 B2 85 s2 angle angle Sl S3 S7 S5 S0 S3 S7 S5 SO S7 S5 50 S5 S0 $0 84 S6 S3 S (2) 9.2(2) 87.9(2) 55.9(2) 79.3(2) 22.8(2) 84.7(2) 82.0(2) 73.9(2) 5.6() 32.7(2) 66.6(2) 78.0(2) 8.(2) 59.2(2) 97.7(2) 74.9() 3.5(2).8() 69.8(2) 75.6() 84.3(2) 04.(2) 78.3(2) 90.0(2) 57.3() S5 S6 S6 S6 S6 S6 54 S3 S3 S3 S7 S7 50 S8 S8 s$ s5 S8 Se $ B2 82 B2 B2 B2 B2 B2 B B2 B2 B2 33 B3 53 BI3 B3 B3 33 B3 B3 3 5 S3 87 S0 sli S3 S7 50 S $ S0 Sl Si S7 89 S Sl 80 S9 S Si 66.3(2) 86.4(2) 46.3(2) 78.7(2) 79.(2) 28.2(2) 70.5(2) 58.5(2) 90.4(2) 40.0(2) 29.3(2) 23.7() 69.5() 7.7() 60.7() 3.03(3) 83.6(2) 94.4(2) 88.3(2) 54.2(2) 77.5(2) 27.9(2) 83.2(2) 82.8(2) 7.4() 5.3(2) Angles are in degrees. Estimated standard deviations in the least significant figure are given in parentheses.

16 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 5 J3)?2, -)- /65 $7 S9 S9 S9 S9 S S Sl S Si S2 S2 82 S2 S2 S2 Si Si Si 5 80 S angle B3 3 B3 B3 B3 B33 B3 B3 83 S3 33 BI B4 84 B4 Bi4 84 B4 BI4 BI4 B4 B4 B4 84 S0 S Si S0 Si S0 SIO SIO Si 50 S9 S S3 S0 89 S S5 59 Si S5 3.9() 65.4() (2) 9.3() 6.77(2) 94.6() 75.4(2) 26.6() 28.0() 69.39(2) 76.6() 84.95(3) 87.5(3) 50.34(4) 77.5() 82.4() 26.57(9) 00.33(3) 80.34(2) 90.7() 60.5() 65.6() 70.52(2) 60.3() 93.9() 39.2() S9 S9 S9 S 84 B4 a B4 84 Sl 28.0() angle 7.4(l) S (9) 72.(2) S5 60.4(2) SS.0(2) Angles are in degrees. Estimated standard deviations in the least significant figure are given in parentheses.

17 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 6 3) 3w /b Table :Anisotropic temperature factors (A2) for C 6 H 2 Bi 2 S 6 with e.s.d.s in parentheses. Bi() Bi(3) Bi(4) S() S(0) S() U 0.023(6) 0.069(6) 0.099(6) 0.074(6) 0.022(4) 0.0(4) 0.030(4) 0.022(4) 0.026(4) 0.04(4) 0.020(4) 0.027(4) 0.026(4) 0.026(4) 0.02(4) 0.04(5) U (7) 0.092(7) 0.094(7) (7) 0.02(4) 0.032(5) 0.025(4) 0.025(5) 0.023(4) 0.030(5) 0.025(5) 0.035(5) 0.025(4) 0.02(4) 0.0(5) 0.028(5) U (7) 0.028(7) (7) (7) 0.026(4) 0.029(4) 0.022(4) 0.055(6) 0.09(4) 0.037(5) 0.032(4) 0.029(5) 0.036(5) 0.040(5) 0.023(4) 0.053(5) Ut (5) (5) 0.00(5) (5) (3) (3) 0.003(3) (3) 0.002(3) 0.008(4) (3) 0.005(3) 0.00(3) (3) 0.002(3) 0.005(4) U (5) 0.006(5) (5) (5) -0.00(3) (3) 0.005(3) (4) 0.002(3) (4) (3) (3) 0.03(3) (3) (3) -0.00(4) U (5) (5) 0.00(5) (5) 0.00(3) (3) 0.004(3) -0.0(4) (3) 0.02(4) 0.00(3) 0.005(3) 0.008(3) (3) 0.006(3) 0.022(4) The general temperature factor expression: exp(-27r2(a' 2 Ujh 2 + b 2 U 22 k 2 + c' 2 U 3 3l 2 + 2a*b*U 2 hk + 2a'c'Ul 3 hl + 2b'c'U 2 3kI))

18 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 7 bis(2-(, 3, 6-trithia-2-bismocane)thio)ethyl sulfide 9. S8* S5 C7 S9* * C8 Bi2* S6* C6 S5* C5 vi- S9 S 4 Bi2 C 2 SB CiI - Ci0C S3* S3*x C9 S2 Bi SI* S2x BiS7 Si S7sI* S7x ( S7* C4 Bi IM S7* C2 S3 C3

19 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 8 Table : Fractional ic positional parameters and equivalent isotropic temperature factors ( ) for CI 2 H B 2 S 9 with e.s.d.s in parentheses. x Y z Bq Bi() (7) (4) (9) 2.3(2) (6) (4) (9).93() s() (5) (3) (6) 2.92(0) (5) (3) (7) 3.3() (5) (3) (7) 3.3() 0.665(4) (3) (6) 2.70(9) (5).0732(3) (7) 3.() (5).09(3) 0.936(6) 2.7(9) 0.965(5) 0.600(3) (6) 2.8(9) (5) (3) 0.685(6) 2.86(0) (5) (3) (7) 3.() C() 0.635(2) 0.393() -0.78(3) 3.8(5) 0.683(2) 0.36() (3) 3.4(4) 0.643(2) 0.237() 0.05(3) 3.9(5) 0.673(2) 0.277() 0.283(3) 3.9(5) 0.682(2) 0.935() 0.327(3) 3.4(5) 0.7(2).030() 0.36(2) 3.(4) 0.823(2).29() 0.684(3) 3.(4) ((8) 0.78(2).074() 0.770(2) 2.4(4) 0(9) 0.778(2) 0.6() 0.327(3) 2.7(4) C(0) 0.790(2) 0.70() 0.386(2) 2.6(4) (() 0.728(3) 0.674() 0.698(3) 4.0(5) ((2) 0.767(3) 0.700() 0.895(3) 4.(5) ()

20 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 9 J) 3o -/ x y z B, H(2) H(3) H(4) H(5) H(6) H(7) H(8) H(9) H(0) H() H(2) H(3) H(4) H(5) H(6) H(7) H(8) H(9) H(20) H(2) H(22) H(23) H() B,.q = r (U (aa') + U2 bbo ) + U.;a(cc') + 2Ut 2 aa'bb cos- + 2U 3 aa'cc" cos3 + 2U 2.3bb'cc' cosa) 0

21 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 20 Table : Anisotropic temperature factors (A' ) for C, 2 H, 4 Bi 2 S 9 with e.s.d.s in parentheses. U U054 U.3 Bi() 0.0(3) (4) (4) (2) (3) (3) (3) (4) (4) (2) (3) (3) S() 0.026(2) 0.03(2) 0.046(3) 0.003(2) 0.005(2) 0.002(2) 0.09(2) 0.044(3) 0.063(3) 0.003(2) 0.08(2) 0.00(2) 0.029(2) 0.027(2) 0.06(3) 0.003(2) 0.008(2) -0.02(2) 0.02(2) 0.035(2) 0.040(3) 0.00(2) (2) (2) 0.025(2) 0.033(2) 0.058(3) 0.00(2) 0.09(2) 0.003(2) 0.028(2) 0.035(2) 0.035(2) 0.00(2) 0.002(2) (2) 0.08(2) 0.029(2) 0.05(3) 0.003(2) 0.003(2) (2) 0.029(2) 0.029(2) 0.047(3) 0.02(2) 0.004(2) (2) 0.034(2) 0.036(2) 0.048(3) 0.008(2) 0.07(2) 0.004(2) C() 0.005(8) 0.05() 0.06() -0.02(8) -0.0(8) 0.0() 0.03() 0.04() 0.05() -0.06(8) 0.00(9) -0.05(9) 0.04() 0.04() 0.07(2) (9) 0.02() 0.0() 0.03() 0.05() 0.06() (9) 0.020(0) 0.0() 0.04() 0.05() 0.04() 0.05(9) 0.007(9) -0.00(9) 0.04() 0.06() 0.03() 0.020(0) 0.02(9) 0.00(9) 0.04() 0.028(0) 0.05() 0.0(8) 0.009(9) (8) 0.020(9) 0.04() 0.03() 0.04(8) 0.006(7) (8) 0.02(8) 0.04() 0.05() 0.00(7) 0.003(8) (8) C(0) 0.0(9) 0.034(0) 0.04() 0.03(8) 0.005(8) 0.006(8) C() 0.06() 0.0(0) 0.06() 0.00(0) 0.02() 0.000(9) 0.06() 0.04() 0.05() 0.0() 0.0() 0.0() The general temperature factor expression: exp(-2r 2 (a'"ul Ikh + b 2 U 22 k 2 + c 2 U a'b'Ul 2 hk + 2a'c'U] 3 hi + 2b'c'U 23 kl))

22 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 2 Table Intic distances (A) for C 2 IL 4 Bi 2 S 9. distance distance Bi() S() 2.597(5) Bi() 2.659(4) Bi() 2.65(4) 2.567(4) 2.599(4) 2.566(5) S() C().8(2).83(2).79(2).82(2).84(2).82(2).80(2) C(s).8(2).8(2) C(0).79(2) C().83(2).8(2) C().5(3).48(3).52(3).5(3) C(0).53(2) C().53(3) 4

23 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 22 distance distance C() H() C() H(2) 0.97 H(3) 0.96 H(4) 0.93 H(5) 0.96 H(6) 0.96 H(7) 0.96 H(8) 0.98 H(9) H(0) 0.96 H() 0.99 H(2) H(3) 0.97 H(4) 0.96 H(5) H(6) H(7) 0.96 H(8) 0.96 C(0) H(9) C(0) H(20) 0.97 C() H(2) 0.97 C() H(22) 0.96 H(23) H()

24 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 23 Table : Intramolecular bond angles (degrees) involving non-hydrogen s for C 2H., 4 Bi 2 S 9. angle angle S() Bi() 92.4(2) S() Bi( ) S( 7) 88.8(2) Bi() 95.6(2) 93.9() 93.5(2) 8.7(2) Bi() S() C() 04.0(7) Bi() 96.6(6) 03.7(0) 00.(6) 0.4(9) 03.3(6) Bi() 04.8(6) C(0) C() 98.3(9) 08.8(8) S() C() 4() C() 6() 5() 5() 3() 3() 4() 5() C(0) 09() C(0) 3() C() 09() C() 5() 6

25 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 3)?~ S() H() C() H(5) H(9) H(3) c(0) H(7) C() C() C() H() H() H(2) H(4) H(4) H(5) H(3) H(6) H(8) H(8) H(9) (9) H(0) H(2) H(2) H(3) H(3) H(4) H(6) H(6) H(7) H(7) H(8) angle C(0) H(20) 08.0 S( ) C() H(3) H(7) H() H(5) c(0) C() C() c(9) C(0) H(2) H(2) H(3) H(3) H(4) H(6) H(6) H(7) H(7) H(8) H(0) H(0) H() H() H(2) H(4) H(4) H(5) H(5) H(6) H(8) H(8) H(9) C(0) H(9) angle

26 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 25 angle angle C(0) H(20) 07. H(9) C(0) H(20) 07.9 C() H(2) 09.5 C() H(22) 09.9 C() H(2) 09.8 C() H(22).0 H(2) C() H(22) 06.9 H(23) 09.6 H() 07.9 C() H(23) 08.2 C() H() 07.6 H(23) H()

27 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 26 Table : Special contacts (A) involving non-hydrogen s for C 2 H Bi 2 S,. distance ADC(*) distance ADC (*) Bi () S() 2.597(5) 2.82(2) Bi () S() 3.346(5) (2) Bi() 2.559(4).82 (2) Bi() 3.07(5).80(2) Bi() 2.65(4) 2.80(2) Bi () 3.26(5) (6) Bi() C() 3.5(2) 2.8t2) Bi () 3.3(2).8(2) Bi (2) 2.567(4) 3.369(6) Bi (2) 3.97(5).8(2) 2.599(4) C(0) 2.73 (2) 3.342(4) (2) S() S() S() C() C (3) C() C (2) 3.92(4) 2.566(5) 3.4(2) 3.49(2) 3.490(7).8(2) 2.80(2) 2.79(2).83(2) 2.8(2).79(2).82(2) 2.78(2).84(2) C() C() C(0) C() C() C(0).79(2).83(2) 2.75(2) 2.83(2).8(2).5(3) 3.44(3) 2.84(3).46(3).52(3) 2.80(3) 3.36(3).5(3).53(2) Distances are in angstroms. Estimated standard deviations in the least significant figure are given in parentheses.

28 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 27 atcm distance C() 3.34(3) C(0) C() 2.74(3) C().53(3) ADC%*) distance J ADC (*) Distances are in angstroms. Estimated standard deviations in the least significant figure are given in parentheses.

29 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 28. Table : Special angles (degrees) involving non-hydrogen s for C, H 2 4 Bi 2 S,. S() S( ) S() S() S( ) S( ) S() S() S() S() S() S() S() angle angle Bi() S() 79.8() Bi() 70.9(4) Bi() (2) C () Bi(l) 74.(5) Bi() 75.5() 74.9() Bi() 88.8(2) 93.9() Bi() 69.7() 67.4() Bi() C() 30.0(3) 86.() Bi() 03.(4) 93.5(2) Bi() 70.0() 32.(4) Bi() 94.9() 7.9(3) Bi() 90.6() 74.2() Bi() 0.2() 92.9() Bi() C() 98.(4) 27.0( Bi() 42.5(4) 52.3( Bi() 76.9() 50.0(4) Bi() 95.6(2) 49.2(3) Bi() 78.0() 79.4() Bi() C() 72.3(4) 57.6( Bi() 33.3 (4) 8.7(2) Bi() 62.() 02.3(] Bi() 05.6() 30.3(3) Bi() C() 50.(4) 04.(' Bi() 5.5(4) 96.0(: Bi() 88.3() 38.8(, Bi() C() 2.2(4) 97.8(3 Bi() 26.6(4) 75.9( Bi() C() 45.0(3) 89.6(3 Angles are in degrees. Estimated standard deviations in the least significant figure are given in parentheses. J 3=2 3j

30 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 29 Bi () Bi () Bi () Bi () Bi () Bi() Bi () C() Bi() Bi () Bi() Bi() Bi() Bi() Bi() S() S() S() S() Bi (2) S() S() S() S() S() S( ) S() S() S() S() Bi() C() C() C() S() C() C() angle 58.0(3) 25.(4) 03.5(3) 72.6(4) 00.2() 58.4() 04.0(7) 89.0(5) 02.0() 2.8(8) 0.2(4) 53.3(7) 30.7(4) 29.4(8) 87.8(4) 96.6(6) 28.2(8) 46.() 73.0(4) 98.8(6) 95.3(7) 68.7(4) 3.0(4) 52.9(6) 08.0(7) 95.0(5) C() C () C() Bi (2) angle 28.8(8) 93.2(8) 94.5(7) 04() 6.4(8) 28.4(8) 00.(6) 90.7(4) 29.6(7) 68.9(4) 95.9(6) 97.(6) 70.9(4) 30.0(7) 6.5(8) 93.8(5) 0.4(9) 90.7(7) 29.4(7) 00.6() 48.7() 90.9(4) 03.3(6) 02.8() 99.6(4) 2.7(6) Anales are in degrees. Estimated standard deviations in the least significant figure are given in parentheses. 3c 3,)'0

31 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 30 angle 36.5(4) C(0) 32.6(6) C() 29.0(7) Bi (2) S(6 Bi() Bi () 9.7() Bi (2) C() Bi () 48.0(2) a3ng3- le angle 29.3 (8) 3.6 8) 49.6() 86.8(4) 08.8(8) Bi() 04.8(6) C() 33.8(5) Bi() C(0) 36.7(4) 58.3 (8) Bi() 72.7() C() 29.0(6) Bi () 05.6(6) Bi () C() S() 46.0(5) Bi() C(0) 02.0(4) Bi () C() 56.9 (3 S{7) 55.7(6) Bi () C() 89() C(0) 3.9(4) Bi() C() 64.7(5) C(0) 32.0(7) S() C() 95.7(7) Bi (2) 54.5(2) S() C() 5() Bi (2) 43.7(4) S() C() 0.6(9) C(0) 4.(6) C() 34.8(9) Bi (2) C() 9.4(7) C() 32.0(4) Bi (2) 73.8(5) C() 55() 32.5(3) S() 96.4(7) C(0) 53.9(6) S() C() 35.9(7) C().8(7) S() 02.8(8) 3.7(5) C() 6() C(0) 30.2(7) 38.5(6) C() 90.4(8) C() 00() 20.(6) 97.3(8) C(0) C() 98.3(9) C() 7.0(6) Angles are in degrees. Estimated standard deviations in the least significant figure are given in parentheses.

32 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 3 angle angle C (3) 94.4(7) 56.4(6) 36() 29() C (3) C() 54.8(7) 08() 37.8(6) 6.5 (5, 5() 97.3(7) C() 25.7(6) C( 7 ) 39.5(6) C() C (3) 07().5() 28() 03.8(7) Bi () 50.(5) C (7) 35.5(8) Bi() 59.8(4) 98() Bi() 94() Bi (2) 59.9(3) 97.5(8) 46.4(4) 6(2) 68.2(4) 36.3(9) 92() Bi (2) 47.9(5) 97.7(7) 6.(4) 32.9(4) 94() 35.8(8) 97.5(8) 4.4(8) 4() 6() 36.7(9) 56() 97.(8) 9.8(7) 36.6(9) C(0) 09() 95.4(7) C() 3.4(9) 7.6(5) C(0) 35.9(8) 3() C() 33.2(4) 39.0(6) C(0) C() 54() Angles are in degrees. Estimated standard deviations in the least significant figure are given in parentheses.

33 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 32 angle angle C(0) 94.2(7) C(0) C (0) C() 38.8(7) 06.8(8) j,32 C (0) 4() C(0) C() 4.4(6) C (0) C() 99() C () 97.8(8) C() 56.4(7) C() C(0) 40.3 (6) C () C (2) 0() C() 50.7(8) C() C(0).(8) C() 35.(9) C() C (0) 26.9(5) C() C (2) 58(2) C(0) C() 49() 0.2(9) C() 39() C() 6() Angles are in degrees. Estimated standard deviations in the least significant figure are given in parentheses.

34 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 33 'I bis (pyridyl) -2-chloro-, 3-dithia-2-bismolane C0 C4 C5 X C>9 C3C Ca C2 NI X C7X N2 N2~ C I x SIXx Cx C SIX SI B xx S2 CI N2X C7 C8 C2X C3 C4 C5 C6 CIOx Clix

35 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 34 Table :Fractional ic positional parameters and equivalent isotropic temperature factors (A2) for C 2 H 4 BiClN 2 S 2 with e.s.d.s in parentheses. x y z U(eq) Bi() cl() S() N() N(2) C() H(A) H(B) H(2A) H(2B) H(3A) C (4) H(4A) H(5A) H (6A) H (7A) H(8A) H(9A) C(0) H(0A) C() H(A) H(2A) 03() 788(6) 547(6) 345(3) 272(9) -535() 3542(4) 4337(4) 3836(4) 3738(6) 29(6) 4904(6) 4098(3) 4468(3) 5060(3) 685(3) 4574(9) 5284(9) 366(22) 2782(22) 26(6) 2(6) -230(3) 576(3) -94(6) -703(6) -20(9) -267(9) -2327(6) -337(6) -603(4) -853(4) (4) 3845(4) 679(8) 6566(2) 6288(3) 3857(5) 464(5) 2767(5) 4895(5) 466(5) 4775(5) 7235(4) 7936(4) 7054(8) 7589(8) 6200(6) 6080(6) 5473(23) 4750(23) 5677(8) 546(8) 744(4) 804(4) 6988(9) 765(9) 5858(20) 5653(20) 4957(8) 406(8) 599(6) 4539(6) 23() 569(6) 587(6) 380(3) -38(8) 2808() 34(4) 2686(4) 359(4) 4430(5) 4854(5) 5367(5) 409(3) 400(3) -309(6) 42(6) -583(9) -274(9) -29(20) -3096(20) -369(5) -793(5) 407(4) 4274(4) 495(4) 5946(4) 466(7) 5308(7) 3386(8) 306(8) 70(5) 469(5) 34() 52() 46() 49() 50(2) 52(4) 58(3) (4) (4) 86 85(6) 02 90(6) 09 22(7) 46 86(5) 03 7(4) 85 85(7) 02 0(8) 32 94(6) 3 73(4) 88

36 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 35 Table :Interic distances (A) for C 2 H 4 BiClN 2 S 2. j3d, D 3'S-- Bi() -N() Bi() - Bi() -S() Bi() -N(2) Bi()-C() S() -C() - N() - N() - N(2)- N(2)- C()- C() -H(IA) C() -H(B) -H(2A) -H(2B) - -H(3A) - -H(4A) - -H(5A) c(6)- -H(6A) -H(7A) - -H(8A) c(9) -C(0) -H(9A) C(0)-C() C(0)-H(0A) c()- C()-H(A) -H(2A) 2.534(8) 2.542(6) 2.545(4) 2.592(9) 3.(4).822(3).83(2).336(2).35(4).336(2).362(3).52(2) (2) (4).08.38(2) (4) (3).08.40(2) (4) (3).08.08

37 (0996 American Chemical Society J Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 36 Table :Intramolecular bond angles (degrees) involving non-hydrogen s for C 2 H 4 BCIN 2 S 2. N()-Bi()- N()-Bi(-S() -Bi()-S() N()-Bi()-N(2) -Bi()-N(2) S()-Bi()-N(2) N(2)-Bi()-C() s(2)-st()-cl() S()-Bi()-C() N(2)-Bi()-C() C()-S()-Bi() --Bi() -N()- -N()-Bi() c(7)-n()-bi() -N(2)-0(2) -N(2)-Bi() 0(2)-N(2)-Bi() -C()-S() c(2)-c()-h(a) S()-C()-H(A) c(2)-c()-h(b) S()-c()-H(B) H(A)-C()-H(B) C()-0(2)- C()--H(2A) --H(2A) C()--H(2B) --H(2B) H(2A)--H(2B) N()-- N()--H(3A) 0(4)--H(3A) c(5)-c(4)-c(3) --H(4A) 0(3)--H(4A) -0(5)-0(6) --H(5A) 0(6)--H(5A) c(5)-c(6)-0(7) --H(6A) --H(6A) N()--0(6) N()--H(7A) c(6)-0(7)-h(7a) N(2)-- N(2)--H(8A) c(9)-c(8)-h(8a) --C(0) c(8)-c(9)-h(9a) c(0)-c(9)-h(9a) 89.8(2) 86.3(4) 84.8(2) 73.(4) 86.6(2) 87.5(3) 82.8(4) 75.3(2) 57.26(9) 0.9(3) 00.2(5) 00.5(5) 20.0(9) 23.5(8) 5.9(8) 9.(9) 20.9(8) 9.9(8) 2.3(9) 09.3(8) 09.2(5) 09.6(7) 08.3(5) (9) 09.4(8) 09.3(5) 09.(7) 08.7(4) (0) 9.6(7) 9.8(7) 9.8() 9.9(7) 20.3(7) 9.7() 20.7(7) 9.6(7) 8.7() 2.0(7) 20.3(8) 2.2() 8.9(6) 9.9(8) 23.4() 20.(6) 6.5(8) 7.6() 25.0(8) 7.4(8)

38 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 37 _a) 3, -/3 ) C()-C(0)- C()-C(0)-H(0A) -C(0)-H(0A) C(0)-C()- C(0)-C()-H(A) -C()-H(A) N(2)--C() N(2)--H(2A) C()--H(2A) 9.4() 8.6(8) 22.0(8) 20.0() 2.5(8) 8.5(8) 20.5(0) 7.8(6) 2.7(8)

39 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 38 Table :Special contacts (A) involving non-hydrogen s for C 2 H 4 BiCIN 2 S 2 * Bi() *Bi() * Bi() *Bi() Bi() Bi(i) Bi() Bi() Bi() Bi() Bi() B() Bi() Bi() Bi() 0() 0() Cl() S() S() s() N() N() N(2) N(2) C() c(9) C(0) C() -Bi() -Bi() -cl() -C() -s() -S() - -N() -N(2) -c() S() -S() - - -c() - -c() c(0) -C() ( 0) 5.46( 0) 3.( 5) 3.23( 5) 2.545( 5) 3.443( 5) 2.542( 4) 2.53 ( ) 2.59 ( ) 3.38 ( ) 3.39 ( ) 3.46 ( ) 3.35 ( 2) 3.47 ( ) 3.48 ( ) 3.672( 7) 3.409( 7) 3.483( 7) 3.429( 7).82 ( ) 2.78 ( 2) 2.79 ( ).83 C 2).34 ( 2).35 ( 2).34 ( 2).36 ( 2).52 ( 2).40 C 2).36 ( 2).38 ( 3).39 ( 3).37 ( 2).40 ( 2).38 ( 2).38 ( 2) IDENTITY IDENTITY IDENTITY IDENTITY IDENTITY IDENTITY -x -x Y Y x Y x Y x -x Y Y Z -Z -Z -Z z -Z +,Cxuf-- < *ik:a~ f~y- 4h.ra c.ordosz9 d~*ci xcz~z~

40 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 39 < 0. Table Anisotropic displacement parameters (A 2 x 03) for C 2 Hj 4 BiCN 2 S 2 The anisotropic displacement factor exponent takes the form: -2 w ( h 2 a*2 U hk a* b* Ul2 ] Ull U22 U33 U23 U3 U2 Bi() 35() 30() 33() 2() 2() 3() CL() 54(2) 33(2) 57(3) -2(2) 6(2) -(2) S() 50(2) 28(2) 45(2) -(2) 8(2) 3(2) 44() 49(3) 40() -6(2) 7() -6(2) N(l) 5(5) 55(5) 4(4) 8() 8(4) 0() N(2) 46(5) 57(2) 56(6) -3(6) 26(5) -2(5) C() 58(7) 46(7) 55(7) -4(7) 3(6) 3(7) 68(8) 63(9) 47(7) 0(7) 8(6) 20(8) 73(8) 89() 67(8) 5(8) 44(7) -4(8) 58(7) 3(9) 97(0) 33(2) 46(8) 3(9) 3(5) 66(6) 23(4) 7(0) 00(4) 2(9) 98(22) 06(6) 9(5) -37(4) 23(7) -25(7) 07(2) 08(3) 67(0) -7(0) 6(0) -2() 57(7) 88(3) 7(8) -2(8) 32(7) -2(7) 72(9) 6(22) 72(8) -7(0) 36(8) 9() C(0) 08(4) 7(23) 78(2) 39(3) 65(2) 72(5) C() 62(9) 26(6) 09(3) 30(3) 52(0) -(0) 57(8) 93(2) 79(0) -6(9) 39(8) -7(9)

41 (0996 American Chemical Society J. Am. Chem. Soc. V8 Page3225 Agocs Supplemental Page 40,J,) 3,; -L/D OBSERVED AND CALCULATED STRUCTURE FACTORS FOR C4HgBiCIS 3. An * indicates weak relfections not used in the final refinements. k Fo Fc sigf k Fo Fc sigf k Fo Fc sigf AAAAAA^ h - 0 AAAAAAA * * AAAAAAA h ^^^^^ * * * * * * * * * * * * * * * * * * 64 * * 26 * 36 * * * 00 * 92 * * 72 * * * 57 * 75 * * * * 33 2 * 429