J. Med. Chem., 1997, 40(7), , DOI: /jm960723m

Transcription

1 J. Med. Chem., 1997, 40(7), , DOI: /jm960723m 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 1997 American Chemical Society

2 '' YIvIu1aRd1 I %'I11VI111Rd 1 3UUdVL JULUIldI Jil IVIuldImdI %_1aliil V -tv rage, Iu'-t:; iiiuyu 0UPPRI111l~d1 rage I 1 Experimental Data Collection An unknown unknown crystal of C 2 oh 26 NClO 2 having approximate dimensions of 0.00 x 0.00 x 0.00 mm was mounted on a glass fiber. All measurements were made on a Rigaku AFC5R diffractometer with graphite monochromated Cu-Ka radiation and a 12kW rotating anode generator. Cell constants and an orientation matrix for data collection, obtained from a least-squares refinement using the setting angles of 0 carefully centered reflections in the range 0.00 < 20 < corresponded to a primitive monoclinic cell with dimensions: a = 8.197(2) A b = (3) A c = 8.335(3) A V = (8) A 3 = 95.64(3)o For Z = 4 and F.W. = , the calculated density is 1.27 g/cm 3. Based on the systematic absences of: OkO: k 0 2n packing considerations, a statistical analysis of intensity distribution, and the successful solution and refinement of the structure, the space group was determined to be: P2 1 (#4) The data were collected at a temperature of 21 - lpc using the w scan technique to a maximum 20 value of Omega scans of several intense reflections, made prior to data collection, had an average width at half-height of 0.00* with a take-off angle of Scans of ( tan 6)0 were made at a speed of /min (in omega). Stationary background counts were recorded on each side of the reflection. The ratio of peak counting time to background counting time was 2:1. The diameter of the incident beam collimator was 1.0 mm, the crystal to detector distance was 285 mm, and the detector aperture was 6.0 x 6.0 mm (horizontal x vertical). Data Reduction Of the 2531 reflections which were collected, 2346 were unique (ra applied ). No decay correction was The linear absorption coefficient, p, for Cu-Ka radiation is 19.6 cm-. An empirical absorption correction based on azimuthal scans of several reflections was applied which resulted in transmission factors ranging from 0.51 to The data were corrected for Lorentz and polarization effects. Structure Solution and Refinement

3 I:,; /Y '"ir-u111 %R11 '11111RUd1 13UULdY JULU IIa di 'Iviuua IVRI Ilr 1 V -tku ragr I k'-t:; ivir~ra 0UPPR11111Ld1 rage z 2 The structure was solved by direct methods' and expanded using Fourier techniques'. The non-hydrogen s were refined anisotropically. Hydrogen s were included but not refined. The final cycle of fullmatrix least-squares refinement' was based on 2189 observed reflections (I > 3.00o(I)) and 432 variable parameters and converged (largest parameter shift was 3.92 times its esd) with unweighted and weighted agreement factors of: R = E FoJ - IFcJJ/EFol = R,,, = N/(Ew( Fo - IFcJ) 2 /1wFo 2 )] = The standard deviation of an observation of unit weight' was The weighting scheme was based on counting statistics and included a factor (p = 0.003) to downweight the intense reflections. Plots of Ew(jFol - IFC)2 versus IFol, reflection order in data collection, sin 9/A and various classes of indices showed no unusual trends. The maximum and minimum peaks on the final difference Fourier map corresponded to 0.37 and e- /A', respectively. Neutral scattering factors were taken from Cromer and Wabers. Anomalous dispersion effects were included in Fcalc 6 ; the values for Af' and Af' were those of Creagh and McAuley 7. The values for the mass attenuation coefficients are those of Creagh and Hubbel'. All calculations were performed using the texsan 9 crystallographic software package of Molecular Structure Corporation. References (1) SHELXS86: Sheldrick, G.M. (1985). In: "Crystallographic Computing 3" (Eds G.M. Sheldrick, C. Kruger and R. Goddard) Oxford University Press, pp (2) DIRDIF94: Beurskens, P.T., Admiraal, G., Beurskens, G., Bosman, W.P., de Gelder, R., Israel, R. and Smits, J.M.M. (1994). The DIRDIF-94 program system, Technical Report of the Crystallography Laboratory, University of Nijmegen, The Netherlands. (3) Least-Squares: Function minimized: Ew(IFo - JFc) 2 where w = )= [o(fo) + 4Fo' or,(fo) = e.s.d. based on counting statistics p = p-factor (4) Standard deviation of an observation of unit weight:,/ew(ifo - FcJ) 2 /(No - where: No = number of observations Nv = number of variables Nv) (5) Cromer, D. T. & Waber, J. T.; "International Tables for X-ray Crystallography", Vol. IV, The Kynoch Press, Birmingham, England, Table 2.2 A (1974).

4 I:,; /Y '"ir-u111 %R11 '11111RUd1 13UUdrL JULU IIa di 'Iviuua IVRI Ilr 1 V -tv ragr I k'-t:; ivir~ra OUPPR11111Ld1 rager z' 3 (6) Ibers, J. A. & Hamilton, W. C.; Acta Crystallogr., 17, 781 (1964). (7) Creagh, D. C. & McAuley, W.J.; "International Tables for Crystallography", Vol C, (A.J.C. Wilson, ed.), Kluwer Academic Publishers, Boston, Table , pages (1992). (8) Creagh, D. C. & Hubbell, J.H..; "International Tables for Crystallography", Vol C, (A.J.C. Wilson, ed.), Kluwer Academic Publishers, Boston, Table , pages (1992). (9) kxsa.: Crystal Structure Analysis Package, Molecular Structure Corporation (1985 & 1992).

5 I> - I IVA~~hU ~ llh.,i 1~h1~1 U1.1hh~uy J1t fjiiu - J Vu T'J x U,. x - xvjt> 1VI.i 31 JJI.,hl.,ILUI x U,. - 1 ~ 4 EXPERIMENTAL DETAILS A. Crystal Data Empirical Formula Formula Weight Crystal Color, Habit Crystal Dimensions Crystal System Lattice Type C 20 H 26 NCIO unknown, unknown 0.00 X 0.00 X 0.00 mm monoclinic Primitive No. of Reflections Used for Unit Cell Determination (20 range) 0 ( ) Omega Scan Peak Width at Half-height Lattice Parameters a = 8.197(2)A b = (3) A c = 8.335(3) A # = 95.64(3). V = (8) A 3 Space Group Z value Dcalc Fooo p(cuka) P2 1 (#4) g/cm' cm- 1 B. Intensity Measurements Diffractometer Rigaku AFC5R

6 I I;/ '"irv11lua11 %'.11r1111d 13UUdrLY J UU Iaidil 11 1VJU1d1d1 ulma L1y V'-luJ ragr, IU9 k 1t;VIr r1 01tPJIU1iiiiiLai radgr - 5 Radiation Attenuator Take-off Angle Detector Aperture Crystal to Detector Distance Temperature Scan Type Scan Rate Scan Width 20mar No. of Reflections Measured Corrections CuKa (A = A) graphite monochromated Ni foil (factors = 1.00, 3.59, 12.23, 44.03) mm horizontal 6.0 mm vertical 285 mm 21.00C w 16.0*/min (in w) (up to 0 scans) ( tan 0) Total: 2531 Unique: 2346 (Rim = 0.031) Lorentz-polarization Absorption (trans. factors: ) C. Structure Solution and Refinement Structure Solution Refinement Function Minimized Direct Methods (SHELXS86) Full-matrix least-squares Ew(IFo - IFc) 2 Least Squares Weights p-factor w = (Fo)= [a(fo) + F Anomalous Dispersion No. Observations (I>3.00ot(I)) No. Variables All non-hydrogen s Reflection/Parameter Ratio Residuals: R; Rw * ; 0.063

7 I I:,; 7 / U11i1JtcI11 % RcId1 13UULdY JUU IIC i 'Iviuua IVRUIrdIdI y V -tv ragr, I k'-t:; 1I~ryr OUPP111111Ld1 radgr U 6 Goodness of Fit Indicator Max Shift/Error in Final Cycle Maximum peak in Final Diff. Map Minimum peak in Final Diff. Map e-/a e-/a 3

8 7 Table 1. Atomic coordinates and Bio/Beq x y z Beq Cl(1) (1) (1) 4.49(2) CI(2) (1) (5) (1) 4.33(2) 0(1) (4) (1) (3) 5.12(7) 0(3) (4) (1) (4) 5.90(8) 0(4) (3) (1) (3) 5.47(8) 0(5) (3) (1) (3) 5.39(8) N(1) (3) (1) (3) 3.05(6) N(2) (3) (1) (3) 3.19(6) C(1) (5) (1) (4) 3.25(7) C(2) (5) (2) (5) 4.08(9) C(6) (5) (1) (4) 3.42(8) C(7) (5) (2) (5) 4.28(10) C(8) (6) (2) (6) 6.3(1) C(9) (6) (2) (7) 7.1(1) C(10) (5) (2) (5) 4.05(9) C( 11) (5) (2) (5) 4.24(10) C(12) (5) (1) (4) 3.31(8) C(13) (4) (1) (4) 3.33(8) C(14) (4) (2) (4) 3.74(9) C(18) (5) (2) (5) 4.33(10) C(19) (7) (2) (6) 6.7(1) C(20) (5) (2) (5) 3.89(8) C(21) (5) (2) (5) 4.95(10) C(22) (5) (2) (5) 4.92(10)

9 I:,; /Y I I-i111Jtd1 '%111rIId 13UUdrL JULU IIa di 'Iviuua IVRI Ilr 1 V -tku ragr, I k'-t:; ii~ryr OUPPRI11U11Ld1 ragr 0 8 Table 1. Atomic coordinates and Biso/Beq (continued) x y z Beq C(23) (5) (2) (5) 4.70(10) C(24) (4) (1) (4) 3.09(7) C(25) (4) (1) (4) 3.46(8) C(26) (5) (2) (5) 4.53(10) C(27) (6) (2) (7) 7.5(2) C(28) (6) (2) (5) 4.59(10) C(29) (6) (2) (5) 4.7(1) C(30) (4) (1) (4) 3.52(8) C(31) (4) (2) (5) 3.40(7) C(32) (5) (1) (5) 3.84(8) C(33) (5) (2) (5) 4.9(1) C(34) (6) (2) (6) 5.4(1) C(35) (6) (2) (6) 5.9(1) C(36) (6) (2) (10) 9.1(2) C(37) (5) (2) (5) 4.33(9) C(38) (5) (2) (4) 4.11(9) C(39) (8) (2) (7) 7.7(2) C(40) (5) (2) (5) 4.9(1) C(41) (5) (2) (5) 4.14(9) C(42) (5) (2) (5) 4.7(1) C(43) (6) (2) (6) 5.5(1) C(44) (5) (1) (4) 3.85(8) C(45) (6) (2) (5) 4.92(9) C(46) (5) (2) (5) 4.8(1)

10 v i/ american onemicai zociety Joumai ui ivieaicinai knemistry v4u rage i u4ay ivieyer 3uppiemental rage ' 9 Table 1. Atomic coordinates and Biso/Beq (continued) x y z Beq H(1) H(2) H(3) H(4) H(5) H(6) H(7) H(8) H(9) H(10) H(11) H(12) H(13) H(14) H(15) H(16) H(17) H(18) H(19) H(20) H(21) H(22) H(23) H(24)

11 I:,; /Y '"ir-u111 %R11 '11111Ud 13UUdrL JULU Id il 'Iviuua IVRI Ilr 1 V -tv ragr, I k'-t:; ivir ra OUPPR111r1L1 rage IV 10 Table 1. Atomic coordinates and Bio/Beq (continued) x y z Beq H(25) H(26) H(27) H(28) H(29) H(30) H(31) H(32) H(33) H(34) H(35) H(36) H(37) H(38) H(39) H(40) H(41) H(42) H(43) H(44) H(45) H(46) H(47) H(48)

12 I I:,;/ 7 I-Mir1luRd1 %'I11rI11Rd 13UUdrL JULU IIadil 'Iviuua IVRUIrdIdI y V -tku ragr, I k'-t:; ii~ryr OUPPRI11U11Ld1 rdgr Table 1. Atomic coordinates and Bio/Beq (continued) x y z Beq H(49) H(50) * Beq = 3*(Un(aa*) 2 + U 22 (bb*) 2 + U33(cc*) 2 + 2Ul 2 aa*bb* cos-y + 2U 13 aa*cc* cos/3 + 2U 23 bb*cc* cos a)

13 I:,; /Y I I-ir1luRd1 '%111R13-dL UIIIrII~dI 1lklIviuua 'JuryJUL IVRI Ilr 1 V -tku ragr I k'-t:; ii~ryr OUPPRI11U11Ld1 rage I/- 12 Table 3. Bond Lengths(A) distance distance 0(1) C(19) 1.40(1) 0(1) C(44) 1.35(1) 0(3) C(20) 1.38(1) 0(3) C(39) 1.41(1) 0(4) C(37) 1.43(1) 0(5) C(38) 1.42(1) N(1) ((11) 1.50(1) N(1) C(12) 1.521(10) N(1) H(1) 0.97 N(1) H(2) 0.96 N(2) C(29) 1.49(1) N(2) C(30) 1.50(1) N(2) 11(3) 0.96 N(2) 11(4) 0.97 C(1) C(2) 1.41(1) ((1) C(6) 1.38(1) C(1) C(10) 1.49(1) C(2) C(46) 1.36(1) C(2) 11(5) 0.99 C(6) C(7) 1.51(1) C(6) C(44) 1.40(1) C(7) C(8) 1.48(1) C(7) H(6) 0.96 C(7) II(7) 0.98 C(8) C(9) 1.42(2) C(8) 11(8) 0.97 C(8) 11(9) 1.01 C(9) ((10) 1.56(1) C(9) 11(10) 0.98 C(9) IH(11) 0.95 ((10) 0((11) 1.52(1) C(10) H(12) 0.97 C(11) H(13) 0.94 C(11) H(14) 0.97 C(12) 0(13) 1.51(1) C(12) C(38) 1.52(1) C(12) H(15) 0.97 C(13) C(14) 1.36(1) C(13) C(18) 1.39(1) C(14) C(41) 1.40(1) C(14) H(16) 0.96 C(18) C(43) 1.39(1) ((18) H(17) 0.96 ((19) H(18) 0.98 C(19) H(19) (19) H(20) 0.94 C(20) C(21) 1.39(1) C(20) C(25) 1.39(1)

14 I:,; /Y I I-i111Jtd1 '%111rIId 13UUdrL JULU IIa di 'Iviuua IVRI Ilr 1 V -tku ragr, I k'-t:; ii~ryr OUPPRI11U11Ld1 rage I J 13 Table 3. Bond Lengths(A) (continued) distance distance C(21) C(22) 1.36(1) C(21) H(21) 0.99 C(22) C(23) 1.37(1) C(22) H(22) 0.95 C(23) C(24) 1.41(1) C(23) H(23) 1.00 C(24) C(25) 1.38(1) C(24) C(28) 1.50(1) C(25) C(26) 1.51(1) C(26) C(27) 1.49(1) C(26) H(24) 0.96 C(26) H(25) 0.96 C(27) C(36) 1.38(2) C(27) H(26) 1.01 C(27) H(27) 0.97 C(28) C(29) 1.55(1) C(28) C(36) 1.49(2) C(28) H(28) 0.99 C(29) H(29) 0.94 C(29) H(30) 0.98 C(30) C(31) 1.50(1) C(30) C(37) 1.51(1) C(30) H(31) 0.98 C(31) C(32) 1.37(1) C(31) C(40) 1.40(1) C(32) C(33) 1.40(1) C(32) H(32) 0.97 C(33) C(34) 1.37(1) C(33) H(33) 0.99 C(34) C(35) 1.38(1) C(34) H(34) 0.98 C(35) C(40) 1.35(1) C(35) H(35) 0.97 C(36) H(36) 0.97 C(36) H(37) 1.02 C(37) H(38) 0.94 C(37) H(39) 0.97 C(38) H(40) 0.99 C(38) H(41) 0.94 C(39) H(42) 0.98 C(39) H(43) 0.98 C(39) H(44) 0.96 C(40) H(45) 1.00 C(41) C(42) 1.35(1) C(41) H(46) 0.99 C(42) C(43) 1.36(1) C(42) H(47) (43) H(48) 0.96

15 SI I ~ ll.li.ui 1~h1U I~~t.flJLXIIU JUM- [ 1V.A11hU x1.1h~1 V ' EIU,.. x - xvxt> ~ 1VI.F.. 3L 1 JJI.,l ILUI x U,. I 14 Table 3. Bond Lengths(A) (continued) distance distance C(44) C(45) 1.40(1) C(45) C(46) 1.38(1) C(45) H(49) 0.98 C(46) H(50) 0.99

16 I:,; /Y I I-ir1luRd1 % a 13uulrL JULU IIa di 'Iviuua IVRI Ilr 1 V -tku ragr, I k'-t:; ii~ryr OUPPRI11U11Ld1 rager I 15 Table 4. Bond Angles(*) angle angle C(19) 0(1) C(44) 119.0(8) C(20) 0(3) C(39) 117.1(9) C(11) N(1) C(12) 115.7(6) C(11) N(1) H(1) C(11) N(1) H(2) C(12) N(1) H(1) C(12) N(1) H(2) H(1) N(1) H(2) C(29) N(2) C(30) 114.8(6) C(29) N(2) H(3) C(29) N(2) H(4) C(30) N(2) H(3) C(30) N(2) H(4) H(3) N(2) H(4) C(2) C(1) C(6) 118.6(8) C(2) C(1) C(10) 119.2(8) C(6) C(1) C(10) 122.2(8) C(1) C(2) C(46) 120.9(9) C(1) C(2) H(5) C(46) C(2) H(5) C(1) C(6) C(7) 121.5(8) C(1) C(6) C(44) 120.3(8) C(7) C(6) C(44) 118.1(8) C(6) C(7) C(8) 113.3(8) C(6) C(7) H(6) C(6) C(7) H(7) C(8) C(7) H(6) C(8) C(7) H(7) H(6) C(7) H(7) C(7) C(8) C(9) 115.5(10) C(7) C(8) H(8) C(7) C(8) H(9) C(9) C(8) H(8) C(9) C(8) H(9) H(8) C(8) H(9) C(8) C(9) C(10) 114.0(9) C(8) C(9) H(10) C(8) C(9) H(11) C(10) C(9) H(10) C(10) C(9) H(11) H(10) C(9) H(11) C(1) C(10) C(9) 113.6(8) C(1) C(10) C(11) 111.1(7) C(1) C(10) H(12) C(9) C(10) C(11) 108.4(8) C(9) C(10) H(12) C(11) C(10) H(12) N(1) C(11) C(10) 113.1(7)

17 16 Table 4. Bond Angles(*) (continued) angle angle 0(4) C(37) H(38) (4) C(37) H(39) C(30) C(37) H(38) C(30) C(37) H(39) H(38) C(37) H(39) (5) C(38)* C(12) 110.9(7) 0(5) C(38) H(40) (5) C(38) H(41) C(12) C(38) H(40) C(12) C(38) H(41) H(40) C(38) H(41) (3) C(39) H(42) (3) C(39) H(43) (3) C(39) H(44) H(42) C(39) H(43) H(42) C(39) H(44) H(43) C(39) H(44) C(31) C(40) C(35) 120.9(10) C(31) C(40) H(45) C(35) C(40) H(45) C(14) C(41) C(42) 120.8(8) C(14) C(41) H(46) C(42) C(41) H(46) C(41) C(42) C(43) 119.4(9) C(41) C(42) H(47) C(43) C(42) H(47) C(18) C(43) C(42) 121.6(9) C(18) C(43) H(48) C(42) C(43) H(48) (1) C(44) C(6) 116.8(8) 0(1) C(44) C(45) 123.3(8) C(6) C(44) C(45) 120.0(9) C(44) C(45) C(46) 119.3(9) C(44) C(45) H(49) C(46) C(45) H(49) C(2) C(46) C(45) 120.8(9) C(2) C(46) H(50) C(45) C(46) H(50) 119.3

18 I:,; /Y I I-i111Jtd1 '%111rIId 13UUdrL JULU IIa di 'Iviuua IVRI Ilr 1 V -tku ragr, I k'-t:; ii~ryr OUPPRI11U11Ld1 rage I / 17 Table 4. Bond Angles(o) (continued) angle angle C(27) C(26) H(25) H(24) C(26) H(25) C(26) C(27) C(36) 118(1) C(26) C(27) H(26) C(26) C(27) H(27) C(36) C(27) H(26) C(36) C(27) H(27) H(26) C(27) H(27) C(24) C(28) C(29) 110.5(8) C(24) C(28) C(36) 112.7(8) C(24) C(28) H(28) C(29) C(28) C(36) 112.6(10) C(29) C(28) H(28) C(36) C(28) H(28) N(2) C(29) C(28) 111.4(7) N(2) C(29) H(29) N(2) C(29) H(30) C(28) C(29) H(29) C(28) C(29) H(30) H(29) C(29) H(30) N(2) C(30) C(31) 112.6(7) N(2) C(30) C(37) 109.5(7) N(2) C(30) H(31) C(31) C(30) C(37) 110.7(7) C(31) C(30) H(31) C(37) C(30) H(31) C(30) C(31) C(32) 123.1(8) C(30) C(31) C(40) 118.8(8) C(32) C(31) C(40) 118.1(9) C(31) C(32) C(33) 120.3(8) C(31) C(32) H(32) C(33) C(32) H(32) C(32) C(33) C(34) 121.0(9) C(32) C(33) H(33) C(34) C(33) H(33) C(33) C(34) C(35) 118.3(10) C(33) C(34) H(34) C(35) C(34) H(34) C(34) C(35) C(40) 121.3(10) C(34) C(35) H(35) C(40) C(35) H(35) C(27) C(36) C(28) 117(1) C(27) C(36) H(36) C(27) C(36) H(37) C(28) C(36) H(36) C(28) C(36) H(37) H(36) C(36) H(37) (4) C(37) C(30) 109.4(7)

19 18 Table 4. Bond Angles(*) (continued) angle angle N(1) C(11) H(13) N(1) C(11) H(14) C(10) C(11) H(13) C(10) C(11) H(14) H(13) C(11) H(14) N(1) 0(12) C(13) 109.7(6) N(1) C(12) C(38) 111.5(7) N(1) C(12) H(15) C(13) C(12) C(38) 114.9(7) C(13) C(12) H(15) C(38) C(12) BH(15) C(12) C(13) C(14) 121.4(8) C(12) C(13) C(18) 119.0(8) C(14) C(13) C(18) 119.6(8) C(13) C(14) C(41) 119.8(8) C(13) C(14) H(16) C(41) C(14) BH(16) C(13) C(18) C(43) 118.7(9) C(13) C(18) H(17) (43) C(18) H(17) (1) C(19) H(18) (1) C(19) H(19) (1) C(19) H(20) H(18) C(19) H(19) BH(18) C(19) B(20) B1(19) C(19) BH(20) (3) C(20) C(21) 123.6(8) 0(3) C(20) C(25) 115.7(8) C(21) C(20) C(25) 120.7(9) C(20) C(21) C(22) 119.6(9) C(20) C(21) BH(21) C(22) C(21) 11(21) C(21) C(22) C(23) 120.8(9) C(21) C(22) BH(22) C(23) C(22) H(22) C(22) C(23) C(24) 120.6(9) C(22) C(23) H(23) C(24) C(23) H(23) C(23) C(24) C(25) 118.8(8) C(23) C(24) C(28) 118.2(8) C(25) C(24) C(28) 122.9(8) C(20) C(25) C(24) 119.5(8) C(20) C(25) C(26) 118.7(8) C(24) C(25) C(26) 121.8(8) C(25) C(26) C(27) 111.5(8) C(25) C(26) BH(24) C(25) C(26) H(25) C(27) C(26) H(24) 111.9

20 10b 19

21 I:,; YY -U11l1Jtd11 i 1r1111RUd1 13UULd Y JULU IIa di 'Iviuu IVRI a Ilr 1 V -tku ragr I k'-t:; ivir~ra 0UPPR11111Ld1 rager /zv 20 EXPERIMENTAL DATA COLLECTION A clear rod crystal of C2 4 H 3 1 NSO6 having approximate dimensions of X X mm was mounted on a glass fiber. All measurements were made on a Rigaku AFC5R diffractometer with graphite monochromated Cu Ka radiation and a 12KW rotating anode generator. Cell constants and an orientation matrix for data collection, obtained from a least-squares refinement using the setting angles of 25 carefully centered reflections in the range < 20 < corresponded to an orthorhombic cell with dimensions: a = (1)A b = (2)A c = )A V = 4585 (2)A For = 8 a:d F.W. = , the calculated density is g/cm. Based on the systematic absences of: 0<.l: k? 2n hol: 1 7 2n hko: h L 2n and the successful solution and refinement of the structure, the space group was determined to be: Pbca (#61) The data were collected at a temperature of C using the w scan technique to a maximum 20 value of Omega scans of several intense reflections, made prior to data collection, had an average width at half-height of with a take-off angle of Scans of ( tan 0)o were made at a speed of /min (in omega). The weak reflections (I < 10.0a(I)) were rescanned (maximum of 2 rescans) and the counts were accumulated to assure good counting statistics. Stationary background counts were recorded on each side of the reflection. The ratio of peak counting time to background counting time was 2:1. The diameter of the incident beam collimator was 0.5 mm and the crystal to detector distance was mm.

22 v i american onemicai zociety Joumai ui ivieaicinai knemistry v 4u rage i u4a' ivieyer 3uppiemental rage L i 21 DATA REDUCTION A total of 3834 reflections was collected. The intensities of three representative reflections which were measured after every 150 reflections remained constant throughout data collection indicating crystal and electronic stability (no decay correction was applied). - The linear absorption coefficient for Cu Ka is 15.5 cm. An empirical absorption correction, based on azimuthal scans of several reflections, was applied which resulted in transmission factors ranging from 0.89 to The data were corrected for Lorentz and polarization effects. STRUCTURF SOLUTION AND REFINEMENT The structure was solved by direct methods 3. The non-hydrogen s were refined anisotropicilly. The final cycle of full-matrix least-squares refinement was based on 2180 observed reflections (I > 3.00o(I)) and 289 variable parameters and converged (largest parameter shift was 0.05 times its esd) with unweighted and weighted agreement factors of: R = I Fol - IFcIl / Z IFol = / Rw =[( I w (Fol --IFcl) / Z w Fo )]/2 = The standard deviation of an observation of unit weight was The weighting scheme was based on counting statistics and included a factor (p = 0.03) to d~wnweight the intense reflections. Plots of I w (IFol - lfe) versus IFol, reflection order in data collection, sin O/X, and various classes of indices showed no unusual trends. The maximum and minimum peaks on the final difference Fourier map corresponded to 0.14 and e /A, respectively. Neutrgl scattering factors were taken from Cromer and Vaber. Anomalous dispersion effects were include in Fcalc ; the values for Af' and Af" were those of Cromer All calculations were performed using the TEXSAN 9 crystallographic software package of Molecular Structure Corporation.

23 I:,; YY -U11l1Jtd11 i 11111RUd1 13UULd Y JULU IIa di 'Iviuu IVRI a Ilr 1 V -tku ragr I k'-t:; ivir~ra 0UPPR11111Ld1 rage zz References (1) PLUTO: Motherwell,S. & Clegg,W.; PLUTO. Program for plotting molecular and crystal structures. Univ. of Cambridge, England (1978). (2) ORTEP: Johnson,C.K.; ORTEPII. Report ORNL Oak Ridge National Laboratory, Oak Ridge, Tennessee (1976). (3) Structure Solution Methods: MITHRIL Gilmore,C.J.; MITHRIL - an integrated direct methods computer program. J. Appl. Cryst. 17, 42-46, Univ. of Glasgow, Scotland, (1984). DIRDIF Beurskens,P.T.; DIRDIF: Direct Methods for Difference Structures - an automatic procedure for phase extension and refinement of difference structure factors. Technical Report 1984/1 Crystallography Laboratory, Toernooiveld, 6525 Ed Nijmegen, Netherlands. (4) Least-Squares: Function minimized: I w (IF I - IF51)2 whe e: 2w = 4F /a Fo ) a (Fo ) = [S (C+R B) + (pfo 21/Lp S = Scan rate C = Total Integrated Peak Count R = Ratio of Scan Time to background counting time. B = Total Background Count Lp = Lorentz-polarization factor p = p-factor (5) Standard deviation of an observation of unit weight: [I w(ifol - 2FcJ)2/(No - Nv)] 1 / 2 22 where: No = number of observations Nv = number of variables (6) Cromer,D.T. & Waber,J.T.; "International Tables for X-ray Crystallography", Vol. IV, The Kynoch Press, Birmingham, England, Table 2.2 A (1974). (7) Ibers,J.A. & Hamilton,W.C.; Acta Crystallogr., 17, 781 (1964). (8) D.T. Cromer, "International Tables for X-ray Crystallography", Vol/ IV, The Kynoch Press, Birmingham, England, Table (1974).

24 I:;,:;, / 'M111JtcI1 '%1111rcIIId 1 3UU~r'L JUU IIC i 'Iviuua IVRUIr'dIdI y V -tv ragr, I k-ty 1v IV~ar OUPP1IU11~1Ld1 radgr IU 23 (9) TEXSAN - TEXRAY Structure Analysis Package, Molecular Structure Corporation (1985).

25 SI I IVA~~hU ~ llh.,i,1.1hi.u U1.1hh~uy ~ ~ 111~J Vu - T'J x U,. x - xvjt> 1VI ~ 3Lu.'I 1 JJI.,lx.,ILUI x U, EXPERIMENTAL DETAILS A. Crystal Data Empirical Formula Formula Weight Crystal Color, Habit C 2 4 H 3 1 NSO clear, rod Crystal Dimensions (mm) Crystal System No. Reflections Used for Unit Cell Determination (20 range) Omega Scan Peak Width at Half-height X X orthorhombic 25 ( ) 0.22 Lattice Parameters: a = b = c = (1)A (2)A (4)A V = 4585 (2)A 3 Space Group Z value Dcalc F (CuKa) Pbca (#61) g/cm cm- 1 B. Intensity Measurements Diffractometer Radiation Temperature Attenuators Take-off Angle Rigaku AFC5R CuKa (X = A) 20 0 C Zr foil (factors: 3.6, 12.2, 44.0) 6.00

26 I I; / "iru11ujtd1 %_11111R1d113UUdrL JULU II id 'Iviuua IVRUIrdIdI y V -tku ragr, I k'-t:; ii~ryr 0UPPR11111Ld1 rager /-- Detector Aperture 6.0 mm horizontal 6.0 mm vertical 25 Crystal to Detector Distance 40 cm Scan Type Scan Rate Scan Width 20max No. of Reflections Meas.red Corrections 0) /min (in omega) (2 rescans) ( tano)o Total Lorentz-polarizatic~n Absorption (trans. factors: ) C. Structure Solution anci Refinement Structure Solution Refinement Direct Methods Full-matrix least-squares Function Minimized Least-squares Weights p-factor Z w (lfol - 4Fo2 / 2(Fo IFcl)2 Anomalous Dispersion No. Observations (I>3.00o(I)) No. Variables Reflection/Parameter Ratio All non-hydrogen s Residuals: R; R 0.041; Goodness of Fit Indicator Max Shift/Error in Final Cycle Maximum Peak in Final Diff. Map Minimum Peak in Final Diff. Map e /A e /A 3

27 I:,; / I Mir~1llud11 '..I11r1111ud 13uulrLy J ULUtldil 11 1VJU1d1d1 ulma L1y V'-luJ ragr, k1u9y; IVIryr Oa 31PIUM11~Ld1 ragr /zu 26 Positional parameters for xray (inst=xraya) x y z S(1) 0(1) 0(2) 0(3) 0(4) 0(5) 0(6) N( 1) C( 1) C(2) C(3) C(4) C(5) C(6) C(7) C(8) C(9) C(10) C(11) C(12) C(13) C(14) C(15) C(16) C(17) C(18) C(19) C(20) C(21) C(22) C(23) C(24) H(1) H(2) H(3) H(4) H(5) H(6) 11(7) H(8) H(9) H(10) H(11) H(12) H(13) H(14) H(15) H(16) H(17) H(18) (6) (2) (2) (2) (2) (2) (2) (2) (3) (2) (2) (2) (2) (3) (3) (2) (2) (2) (2% (2) (2) (2) (2) (2) (2) (2) (3) (3) (3) (3) (3) (3) (8) (2) (3) (3) (2) (2) (2) (2) (4) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (4) (5) (4) (4) (3) (3) (3) (4) (1) (1) (1) (1) (1) (1) (1) (2) (2) (1) (1) (1) (2) (2) (1) (1) (1) (1) (1) (2) (2) (1) (1) (1) (2) (2) (2) (2) (2) (2) (2)

28 vi i american onemicai zociety Journal ui ivieaicinai knemistry v 4u rage i u4a' ivieyer 3uppiemental rage L i 27 Positional parameters for xray (inst=xraya) x y z H(19) H(20) H(21) H(22) H(23) H(24) H(25) H(26) H(27) H(28) H(29) H(30) H(31)

29 SI I ~ llla 1 I.1.lhl.* Jt.,f..,t ju m-ml~ S..J IvxI xxx~ vsi.,h~ -.,1.,h1t x TO, xw xvx 5... lot>xx -~ xv.....l J-JJI.ll.11t1I0 28 Positional parameters and B(eq) for xray (inst~xraya) x S(1) 0(1) 0(2) 0(3) 0(4) 0(5) 0(6) N(1) C( 1) C(2) C(3) C(4) C(5) C(6) C(7) C(8) C(9) C(10) C(11) C(12) C(13) C(14) C(15) C(16) C(17) C(18) C(19) C(20) C(21) C(22) C(23) C(24) H(1) H(2) H(3) H(4) H(5) H(6) H(7) H(8) H(9) H(10) H(11) H(12) H(13) H(14) H(15) H(16) H(17) H(18) y (6) (2) (2) (2) (2) (2) (2) (2) (3) (2) (2) (2) (2) (3) (3) (2) (2) (2) (2) (2) (2) (2) (2) (2) (2) (2) (3) (3) (3) (3) (3) (3) z (8) (2) (3) (3) (2) (2) (2) (2) (4) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (4) (5) (4) (4) (3) (3) (3) B(eq) (4) (1) (1) (1) (1) (1) (1) (1) (2) (2) (1) (1) (1) (2) (2) (1) (1) (1) (1) (1) (2) (2) (1) (1) (i) (2) (2) (2) (2) (2) (2) (2) (4) 6.1(1) 6.4(2) 7.4(2) 6.2(2) 5.1(1) 5.6(1) 3.4(1) 7.2(3) 4.5(2) 4.3(2) 4.2(2) 3.9(2) 4.8(2) 5.1(2) 4.5(2) 3.6(2) 4.9(2) 4.0(2) 3.9(2) 4.8(2) 5.3(2) 4.4(2) 4.1(2) 4.0(2) 5.7(2) 6.8(3) 5.4(2) 6.4(3) 5.3(2) 6.4(3) 5.6(2)

30 I:,; YY IMir~1llud1 '..I11r1111ud 13uulrLy J ULUtl il i 1J,1L11 ruu a %1.. r 11111ML1 V'-luJ ragr, k1u9y; iviryr Oa 31 PIUM11~ Ld1 fr 29 Positional parameters and B(eq) for xray (inst=xraya) x y z B(eq) H(19) H(20) H(21) H(22) H(23) H(24) H(25) H(26) H(27) H(28) H(29) H(30) H(31)

31 Intramolecular Distances 30 distance distance Si (3) C8 C (5) Si (3) C8 H Si (3) C8 H S1 C (4) C9 H C (5) C9 H C (4) C10 H C (5) 010 H C (4) 010 H C (6) C (4) 03 C (5) N1 C (4) C NI C (4) C (5) N1 C (4) (5) N1 H C12 H Cl H (5) C1 H C C2 C (5) C2 C (5) C (5) C3 C (5) 014 H C4 C (5) C4 H C15 C (5) C5 C (5) (5) C5 C (5) C15 H C6 C (5) 016 C (5) C6 H C16 C (5) C7 H C17 C (5) Distances are in angstroms. Estimated standard deviations in the least significant figure are given in parentheses.

32 I I;/ 'Mir~1llud11 '..I11r1111~d 13UUdrLy J ULUtldil 11 1V-ULd1d ulma 'r,1~1111m V'-luJ ragr, k1u9y; IVIryr Oa 31PIUM11~Ld1 rdgr J I Intramolecular Distances (cont) 31 distance distance C18 C (6) C18 H C C19 H C19 H C20 C (6) C21 C (6) C21 H C22 C (6) C22 H C23 H24 J.95"' C24 H C24 H C24 H Distances are in angstroms. Estimated standard deviations in the least significant figure are given in parentheses.

33 I I;/ 'Mir~1llud11 % LUd113UUdrLy J ULUtldil 11 1VJU1d1d1 ulma L1y V'-luJ ragr, k1u9y; IVIryr 0a 31PIUM11~Ld1 rager J1 Intramolecular Bond Angles 32 angle angle 04 Sl (2) C2 C3 C (4) 04 Sl (2) C3 C4 C (3) 04 Sl C (2) C3 04 H Sl (2) C5 C4 H Si C (2) C4 C5 C (3) 06 Si C (2) C4 C5 C (3) C1 01 C (3) C6 C5 C C3) Cl 02 C (3) C5 C6 C (4) C (3) C5 C6 H C9 NI C (2) C7 C6 H Ni (3) C2 C7 C (4) C9 N! H C2 C7 H C10 N (3) C6 C7 H C30 N1 H C5 C8 C (3) 011 NI H C5 C8 H Cl (3) C5 C8 H H C8 H C1 H C9 C8 H C1 H H3 C8 H C1 H N1 C9 C (3) H28 C1 H NI C9 H C2 C (4) Ni C9 H C2 C (4) C8 C9 H C3 C2 C (4) C8 C9 H C3 C (3) H5 C9 H C3 C (4) Ni C10 H Angles are in degrees. Estimated standard deviations in the least significant figure are given in parentheses.

34 vi/ american onemicai zociety Journal ui ivieacicnai knemistry vu rage iu4a' ivieyer 3uppiemental rage ii Intramolecular Bond Angles (cont) 33 angle angle NI C10 H C15 C14 H Ni C10 H9, C15 C14 H H7 C10 H8, H15 C14 H H7 C10 H C14 C15 C (3) H8 C10 H C (3) N1 C11 C (3) 014 C Ni C (3) Ni C11 ill C H C12 C C15 H H C15 C16 C (3) 110 c1l H C15 C16 C (4) C (3) C I' 016 C (4) (3) C (3) C11 C12 H C (3) (3) C16 C17 C (4) 013 C12 H C15 C (3) H C15 C18 H C13 C (3) H C12 C13 H H C12 C13 H C18 H C14 C13 H C18 H C14 C13 H C19 C (4) H13 C13 H H C13 C14 C (3) 03 C19 H C13 C14 H C18 C19 H C13 C14 H C18 C19 H Angles are in degrees. Estimated standard deviations significant figure are given in parentheses. in the least

35 vi/ american onemicai zociety Journal ui ivieacicnai knemistry vu rage iu4a' ivieyer 3uppiemental rage.i, Intramolecular Bond Angles (cont) 34 angle angle H H C20 C (4) 03 C20 C (4) 016 C20 C (4) C20 C21 C (4) C20 C21 H C23 C21 H C22 C (4) 017 C22 H C23 C22 H C21 C23 C (4) C21 C23 H C22 C23 H Sl C24 H Si C24 H Si C24 H H25 C24 H H25 C24 H H26 C24 H Angles are in degrees. Estimated standard deviations in the least significant figure are given in parentheses.

36 - If I IlAWA~S UAAAAA~I4 jukmaai4 %Sx xy~&~aa4 "VAWAAAhA x - 7VxY~ u~~xx-~ x41 "VT. "J.41A U~~JWAAAI C(!! 32