3 CHAPTER THREE
B. Appendix B
Table B.1. Crystal data and structure refinement for (S)-4: (CCDC_213422)
Empirical formula C32H50Cl2Si2Zr · 1½(CH2Cl2)
Formula weight 776.90
Crystallization Solvent Dichloromethane
Crystal Habit Plate
Crystal size 0.26 x 0.20 x 0.09 mm3
Crystal color Colorless
Data Collection
Preliminary Photos Rotation
Type of diffractometer Bruker SMART 1000
Wavelength 0.71073 Å MoKα
Data Collection Temperature 100(2) K θ range for 20,102 reflections used
in lattice determination 2.54 to 28.33°
Unit cell dimensions a = 13.2833(7) Å
b = 19.3805(10) Å β= 107.1950(10)°
c = 14.7651(8) Å
Volume 3631.2(3) Å3
Z 4
Crystal system Monoclinic
Space group P21
Density (calculated) 1.428 Mg/m3
F(000) 1628
Data collection program Bruker SMART v5.054 θ range for data collection 1.44 to 28.37°
Completeness to θ = 28.37° 94.5%
Index ranges –17 ≤ h ≤ 16, –25 ≤ k ≤ 25, –19 ≤ l ≤ 19 Data collection scan type ω scans at 5 φ settings
Data reduction program Bruker SAINT v6.022
Reflections collected 54,234
Independent reflections 16,726 [Rint = 0.0645]
Absorption coefficient 0.760 mm-1
Absorption correction None
Max. and min. transmission (predicted) 0.9348 and 0.8269
Structure Solution and Refinement
Structure solution program SHELXS-97 (Sheldrick, 1990) Primary solution method Direct methods
Secondary solution method Difference Fourier map
Hydrogen placement Geometric positions
Structure refinement program SHELXL-97 (Sheldrick, 1997) Refinement method Full matrix least-squares on F2 Data/restraints/parameters 16,726/1/765
Treatment of hydrogen atoms Riding
Goodness-of-fit on F2 1.130
Final R indices [I > 2s(I), 12,842 reflections] R1 = 0.0374, wR2 = 0.0604 R indices (all data) R1 = 0.0589, wR2 = 0.0643 Type of weighting scheme used Sigma
Weighting scheme used w = 1 / σ2(Fo2)
Max shift/error 0.002
Average shift/error 0.000
Absolute structure parameter –0.08(3)
Largest diff. peak and hole 1.171 and –0.758 e.Å-3
Special Refinement Details
The crystals contain dichloromethane as a solvent of crystallization. There are three molecules of solvent per asymmetric unit with one site being disordered over at least two orientations. The carbon and hydrogen atoms of the alternate orientation(s) were not included in least squares refinement because they were not discernable in the electron density map.
Refinement of F2 against all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2, conventional R-factors (R) are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for
refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on all data will be even larger.
All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Figure B.1. ORTEP view of (S)-4.
Figure B.2. ORTEP view for (S)-4.
Figure B.3. Unit cell of X-ray structure of (S)-4.
Table B.2. Atomic coordinates and Ueq for (S)-4
Atomic coordinates (x 104) and equivalent isotropic displacement parameters, Ueq (Å2x 103):
(CCDC_213422).
U(eq) the trace of the orthogonalized Uij tensor.
_______________________________________________________________________
x y z Ueq
_______________________________________________________________________
Zr(1) 4648(1) 9913(1) 3917(1) 11(1) Cl(1A) 5002(1) 11108(1) 3624(1) 17(1) Cl(2A) 3090(1) 9994(1) 4456(1) 17(1) Si(1A) 6558(1) 9243(1) 3288(1) 13(1) Si(2A) 4824(1) 8270(1) 4134(1) 14(1) C(1A) 6376(3) 9368(2) 4492(3) 13(1) C(2A) 5647(4) 8978(3) 4850(3) 16(1) C(3A) 5406(3) 9398(2) 5554(3) 14(1) C(4A) 5956(3) 10036(3) 5651(3) 13(1) C(5A) 6534(3) 10001(3) 4981(3) 14(1) C(6A) 5090(3) 9254(2) 2698(3) 14(1) C(7A) 4356(4) 8834(2) 3050(3) 14(1) C(8A) 3322(3) 9139(3) 2670(3) 14(1) C(9A) 3447(4) 9729(2) 2153(3) 13(1) C(10A) 4485(3) 9788(2) 2118(3) 13(1) C(11A) 7265(4) 10012(3) 3038(3) 21(1) C(12A) 7277(4) 8472(3) 3097(3) 20(1) C(13A) 5582(4) 7484(3) 4006(3) 22(1) C(14A) 3759(3) 8005(2) 4648(3) 18(1)
C(15A) 5947(3) 10615(3) 6308(3) 17(1) C(16A) 4927(3) 10636(2) 6583(3) 22(1) C(17A) 6957(3) 10624(2) 7201(3) 19(1) C(18A) 7953(3) 10687(2) 6899(3) 35(1) C(19A) 6898(3) 11263(2) 7824(3) 28(1) C(20A) 7021(3) 9989(2) 7805(3) 33(1) C(21A) 2283(4) 8847(2) 2690(3) 14(1) C(22A) 2090(3) 8162(2) 2139(3) 18(1) C(23A) 1050(3) 7833(2) 2125(3) 22(1) C(24A) 141(3) 8327(2) 1699(3) 24(1) C(25A) 300(3) 8993(2) 2262(3) 19(1) C(26A) 1362(3) 9336(2) 2282(3) 17(1) C(27A) 4860(4) 10281(3) 1492(3) 17(1) C(28A) 5258(4) 9870(3) 787(3) 24(1) C(29A) 5685(4) 10353(3) 159(3) 26(1) C(30A) 4855(4) 10864(3) –360(3) 24(1) C(31A) 4440(4) 11269(3) 335(3) 22(1) C(32A) 4026(4) 10794(2) 982(3) 18(1)
Zr(2) 9687(1) 1753(1) 3963(1) 11(1) Cl(1B) 8186(1) 1615(1) 4572(1) 18(1) Cl(2B) 9994(1) 579(1) 3541(1) 17(1) Si(1B) 9910(1) 3393(1) 4259(1) 13(1)
Si(2B) 11576(1) 2417(1) 3330(1) 15(1) C(1B) 10711(3) 2661(2) 4928(3) 9(1) C(2B) 11429(3) 2267(2) 4538(3) 13(1) C(3B) 11595(3) 1627(2) 5033(3) 11(1) C(4B) 11032(3) 1607(3) 5692(3) 14(1) C(5B) 10488(3) 2244(2) 5622(3) 13(1) C(6B) 9398(3) 2850(2) 3149(3) 12(1) C(7B) 10102(3) 2441(2) 2757(3) 13(1) C(8B) 9468(4) 1929(2) 2160(3) 13(1) C(9B) 8427(4) 1996(3) 2208(3) 13(1) C(10B) 8370(4) 2562(2) 2773(3) 13(1) C(11B) 8912(3) 3627(2) 4861(3) 17(1) C(12B) 10698(3) 4175(3) 4162(3) 20(1) C(13B) 12311(4) 3206(3) 3137(3) 22(1) C(14B) 12262(3) 1655(3) 3019(3) 20(1) C(15B) 11048(4) 1030(2) 6407(3) 13(1) C(16B) 11396(3) 350(2) 6063(2) 23(1) C(17B) 11739(3) 1228(2) 7423(3) 15(1) C(18B) 11292(3) 1865(2) 7783(2) 24(1) C(19B) 11735(3) 632(2) 8098(3) 25(1) C(20B) 12866(3) 1392(2) 7437(3) 23(1) C(21B) 9819(4) 1432(2) 1518(3) 14(1) C(22B) 10225(4) 1842(3) 799(3) 19(1)
C(23B) 10653(4) 1371(3) 199(3) 27(1) C(24B) 9819(4) 853(3) –317(3) 27(1) C(25B) 9371(4) 459(3) 360(3) 21(1) C(26B) 8962(4) 929(3) 984(3) 18(1) C(27B) 7349(3) 2875(2) 2874(3) 13(1) C(28B) 7185(4) 3589(2) 2390(3) 19(1) C(29B) 6186(3) 3936(2) 2487(3) 27(1) C(30B) 5219(3) 3476(2) 2067(3) 25(1) C(31B) 5384(4) 2755(3) 2512(3) 24(1) C(32B) 6376(4) 2426(2) 2435(3) 17(1) C(51) 4060(5) 7942(4) 937(4) 52(2) Cl(5) 5289(1) 7888(1) 781(1) 48(1) Cl(6) 3092(1) 7442(1) 149(1) 29(1) C(52) 7669(6) 8551(4) –427(5) 57(2) Cl(7) 7516(2) 8942(1) 560(2) 59(1) Cl(8) 7307(2) 7688(1) –545(2) 45(1) C(53) 1013(4) 8648(3) 9161(4) 35(1) Cl(9) 2000(1) 9239(1) 9758(1) 28(1) Cl(10) –203(1) 9047(1) 8703(1) 44(1)
Table B.3. Selected bond lengths [Å] and angles [°] for (S)-4: (CCDC_213422)
_______________________________________________________________________
Zr(1)-Cl(1A) 2.4267(12) Zr(1)-Cl(2A) 2.4322(12) Zr(1)-C(1A) 2.439(4)
Zr(1)-C(2A) 2.420(5) Zr(1)-C(3A) 2.532(4) Zr(1)-C(4A) 2.646(4) Zr(1)-C(5A) 2.539(4)
Zr(1)-C(6A) 2.417(4) Zr(1)-C(7A) 2.423(4) Zr(1)-C(8A) 2.612(4) Zr(1)-C(9A) 2.645(4) Zr(1)-C(10A) 2.612(4) Zr(2)-Cl(1B) 2.4321(12) Zr(2)-Cl(2B) 2.4253(12) Zr(2)-C(1B) 2.414(4)
Zr(2)-C(2B) 2.430(4) Zr(2)-C(3B) 2.571(4) Zr(2)-C(4B) 2.663(4) Zr(2)-C(5B) 2.549(4)
Zr(2)-C(6B) 2.417(4) Zr(2)-C(7B) 2.415(4) Zr(2)-C(8B) 2.613(4) Zr(2)-C(9B) 2.678(4) Zr(2)-C(10B) 2.605(4)
Cl(1A)-Zr(1)-Cl(2A) 103.01(4)
Cl(2B)-Zr(2)-Cl(1B) 102.09(4)
Table B.4. Bond lengths [Å] and angles [°] for (S)-4: (CCDC_213422)
_______________________________________________________________________
Zr(1)-C(6A) 2.417(4) Zr(1)-C(2A) 2.420(5) Zr(1)-C(7A) 2.423(4) Zr(1)-Cl(1A) 2.4267(12) Zr(1)-Cl(2A) 2.4322(12) Zr(1)-C(1A) 2.439(4) Zr(1)-C(3A) 2.532(4) Zr(1)-C(5A) 2.539(4) Zr(1)-C(10A) 2.612(4) Zr(1)-C(8A) 2.612(4) Zr(1)-C(9A) 2.645(4) Zr(1)-C(4A) 2.646(4) Si(1A)-C(12A) 1.840(5) Si(1A)-C(11A) 1.855(5) Si(1A)-C(1A) 1.880(5) Si(1A)-C(6A) 1.885(4) Si(2A)-C(14A) 1.865(5) Si(2A)-C(13A) 1.866(5) Si(2A)-C(2A) 1.875(5) Si(2A)-C(7A) 1.885(4) C(1A)-C(5A) 1.408(6) C(1A)-C(2A) 1.445(6)
C(2A)-C(3A) 1.429(6) C(3A)-C(4A) 1.422(6) C(4A)-C(5A) 1.422(6) C(4A)-C(15A) 1.485(6) C(6A)-C(10A) 1.429(6) C(6A)-C(7A) 1.479(6) C(7A)-C(8A) 1.448(6) C(8A)-C(9A) 1.410(6) C(8A)-C(21A) 1.500(6) C(9A)-C(10A) 1.400(6) C(10A)-C(27A) 1.512(6) C(15A)-C(16A) 1.527(5) C(15A)-C(17A) 1.579(5) C(17A)-C(20A) 1.508(5) C(17A)-C(18A) 1.522(5) C(17A)-C(19A) 1.558(5) C(21A)-C(26A) 1.523(6) C(21A)-C(22A) 1.538(6) C(22A)-C(23A) 1.515(6) C(23A)-C(24A) 1.524(6) C(24A)-C(25A) 1.516(6) C(25A)-C(26A) 1.552(6)
C(27A)-C(32A) 1.513(6) C(27A)-C(28A) 1.524(6) C(28A)-C(29A) 1.538(6) C(29A)-C(30A) 1.512(7) C(30A)-C(31A) 1.518(6) C(31A)-C(32A) 1.540(6) Zr(2)-C(1B) 2.414(4) Zr(2)-C(7B) 2.415(4) Zr(2)-C(6B) 2.417(4) Zr(2)-Cl(2B) 2.4253(12) Zr(2)-C(2B) 2.430(4) Zr(2)-Cl(1B) 2.4321(12) Zr(2)-C(5B) 2.549(4) Zr(2)-C(3B) 2.571(4) Zr(2)-C(10B) 2.605(4) Zr(2)-C(8B) 2.613(4) Zr(2)-C(4B) 2.663(4) Zr(2)-C(9B) 2.678(4) Si(1B)-C(11B) 1.858(5) Si(1B)-C(12B) 1.870(5) Si(1B)-C(1B) 1.872(5) Si(1B)-C(6B) 1.897(5) Si(2B)-C(14B) 1.864(5)
Si(2B)-C(2B) 1.874(4) Si(2B)-C(13B) 1.880(5) Si(2B)-C(7B) 1.891(5) C(1B)-C(5B) 1.404(6) C(1B)-C(2B) 1.466(6) C(2B)-C(3B) 1.422(6) C(3B)-C(4B) 1.392(6) C(4B)-C(5B) 1.418(6) C(4B)-C(15B) 1.534(6) C(6B)-C(10B) 1.427(6) C(6B)-C(7B) 1.469(6) C(7B)-C(8B) 1.424(6) C(8B)-C(9B) 1.412(6) C(8B)-C(21B) 1.519(6) C(9B)-C(10B) 1.392(6) C(10B)-C(27B) 1.533(6) C(15B)-C(16B) 1.532(5) C(15B)-C(17B) 1.557(5) C(17B)-C(20B) 1.524(5) C(17B)-C(19B) 1.526(5) C(17B)-C(18B) 1.532(5) C(21B)-C(26B) 1.529(6) C(21B)-C(22B) 1.545(6)
C(22B)-C(23B) 1.496(6) C(23B)-C(24B) 1.522(7) C(24B)-C(25B) 1.513(6) C(25B)-C(26B) 1.507(6) C(27B)-C(32B) 1.534(6) C(27B)-C(28B) 1.544(6) C(28B)-C(29B) 1.532(6) C(29B)-C(30B) 1.535(6) C(30B)-C(31B) 1.533(6) C(31B)-C(32B) 1.498(6) C(51)-Cl(5) 1.718(6) C(51)-Cl(6) 1.750(6) C(52)-Cl(7) 1.708(8) C(52)-Cl(8) 1.734(7) C(53)-Cl(10) 1.737(5) C(53)-Cl(9) 1.768(5) C(6A)-Zr(1)-C(2A) 79.39(15) C(6A)-Zr(1)-C(7A) 35.58(14) C(2A)-Zr(1)-C(7A) 68.29(15) C(6A)-Zr(1)-Cl(1A) 105.59(11) C(2A)-Zr(1)-Cl(1A) 135.48(12) C(7A)-Zr(1)-Cl(1A) 137.62(11) C(6A)-Zr(1)-Cl(2A) 134.05(11)
C(2A)-Zr(1)-Cl(2A) 103.79(11) C(7A)-Zr(1)-Cl(2A) 102.09(11) Cl(1A)-Zr(1)-Cl(2A) 103.01(4) C(6A)-Zr(1)-C(1A) 67.66(14) C(2A)-Zr(1)-C(1A) 34.59(15) C(7A)-Zr(1)-C(1A) 78.31(15) Cl(1A)-Zr(1)-C(1A) 105.28(11) Cl(2A)-Zr(1)-C(1A) 135.89(11) C(6A)-Zr(1)-C(3A) 112.81(15) C(2A)-Zr(1)-C(3A) 33.45(13) C(7A)-Zr(1)-C(3A) 96.94(14) Cl(1A)-Zr(1)-C(3A) 120.18(11) Cl(2A)-Zr(1)-C(3A) 81.35(11) C(1A)-Zr(1)-C(3A) 55.23(14) C(6A)-Zr(1)-C(5A) 94.81(14) C(2A)-Zr(1)-C(5A) 54.80(16) C(7A)-Zr(1)-C(5A) 111.09(16) Cl(1A)-Zr(1)-C(5A) 80.70(12) Cl(2A)-Zr(1)-C(5A) 124.96(10) C(1A)-Zr(1)-C(5A) 32.78(14) C(3A)-Zr(1)-C(5A) 52.77(14) C(6A)-Zr(1)-C(10A) 32.73(14) C(2A)-Zr(1)-C(10A) 112.11(15)
C(7A)-Zr(1)-C(10A) 55.28(14) Cl(1A)-Zr(1)-C(10A) 82.49(11) Cl(2A)-Zr(1)-C(10A) 121.05(10) C(1A)-Zr(1)-C(10A) 95.78(14) C(3A)-Zr(1)-C(10A) 145.54(15) C(5A)-Zr(1)-C(10A) 113.92(14) C(6A)-Zr(1)-C(8A) 55.49(14) C(2A)-Zr(1)-C(8A) 96.54(15) C(7A)-Zr(1)-C(8A) 33.15(14) Cl(1A)-Zr(1)-C(8A) 123.20(11) Cl(2A)-Zr(1)-C(8A) 78.79(10) C(1A)-Zr(1)-C(8A) 111.46(15) C(3A)-Zr(1)-C(8A) 116.21(15) C(5A)-Zr(1)-C(8A) 144.22(15) C(10A)-Zr(1)-C(8A) 52.70(14) C(6A)-Zr(1)-C(9A) 53.41(14) C(2A)-Zr(1)-C(9A) 121.93(15) C(7A)-Zr(1)-C(9A) 53.66(14) Cl(1A)-Zr(1)-C(9A) 92.62(10) Cl(2A)-Zr(1)-C(9A) 90.38(11) C(1A)-Zr(1)-C(9A) 121.04(15) C(3A)-Zr(1)-C(9A) 147.17(14) C(5A)-Zr(1)-C(9A) 144.66(14)
C(10A)-Zr(1)-C(9A) 30.88(13) C(8A)-Zr(1)-C(9A) 31.10(14) C(6A)-Zr(1)-C(4A) 122.26(14) C(2A)-Zr(1)-C(4A) 54.83(15) C(7A)-Zr(1)-C(4A) 123.09(15) Cl(1A)-Zr(1)-C(4A) 88.86(11) Cl(2A)-Zr(1)-C(4A) 93.25(10) C(1A)-Zr(1)-C(4A) 54.63(14) C(3A)-Zr(1)-C(4A) 31.77(14) C(5A)-Zr(1)-C(4A) 31.75(13) C(10A)-Zr(1)-C(4A) 145.67(14) C(8A)-Zr(1)-C(4A) 147.88(15) C(9A)-Zr(1)-C(4A) 175.67(14) C(12A)-Si(1A)-C(11A) 107.8(2) C(12A)-Si(1A)-C(1A) 117.8(2) C(11A)-Si(1A)-C(1A) 107.4(2) C(12A)-Si(1A)-C(6A) 116.8(2) C(11A)-Si(1A)-C(6A) 114.5(2) C(1A)-Si(1A)-C(6A) 91.79(19) C(12A)-Si(1A)-Zr(1) 149.35(17) C(11A)-Si(1A)-Zr(1) 102.85(17) C(1A)-Si(1A)-Zr(1) 48.91(13) C(6A)-Si(1A)-Zr(1) 48.24(13)
C(14A)-Si(2A)-C(13A) 108.3(2) C(14A)-Si(2A)-C(2A) 111.0(2) C(13A)-Si(2A)-C(2A) 114.3(2) C(14A)-Si(2A)-C(7A) 114.0(2) C(13A)-Si(2A)-C(7A) 116.1(2) C(2A)-Si(2A)-C(7A) 92.6(2) C(14A)-Si(2A)-Zr(1) 105.86(15) C(13A)-Si(2A)-Zr(1) 145.81(17) C(2A)-Si(2A)-Zr(1) 48.80(14) C(7A)-Si(2A)-Zr(1) 48.89(14) C(5A)-C(1A)-C(2A) 106.4(4) C(5A)-C(1A)-Si(1A) 123.8(4) C(2A)-C(1A)-Si(1A) 124.5(3) C(5A)-C(1A)-Zr(1) 77.5(3) C(2A)-C(1A)-Zr(1) 72.0(3) Si(1A)-C(1A)-Zr(1) 95.58(17) C(3A)-C(2A)-C(1A) 106.7(4) C(3A)-C(2A)-Si(2A) 127.5(4) C(1A)-C(2A)-Si(2A) 121.2(3) C(3A)-C(2A)-Zr(1) 77.6(3) C(1A)-C(2A)-Zr(1) 73.4(2) Si(2A)-C(2A)-Zr(1) 95.54(18) C(4A)-C(3A)-C(2A) 110.4(4)
C(4A)-C(3A)-Zr(1) 78.5(3) C(2A)-C(3A)-Zr(1) 69.0(2) C(3A)-C(4A)-C(5A) 104.8(4) C(3A)-C(4A)-C(15A) 128.3(4) C(5A)-C(4A)-C(15A) 126.9(4) C(3A)-C(4A)-Zr(1) 69.7(2) C(5A)-C(4A)-Zr(1) 70.0(2) C(15A)-C(4A)-Zr(1) 124.8(3) C(1A)-C(5A)-C(4A) 111.6(4) C(1A)-C(5A)-Zr(1) 69.7(2) C(4A)-C(5A)-Zr(1) 78.3(2) C(10A)-C(6A)-C(7A) 107.3(4) C(10A)-C(6A)-Si(1A) 127.4(3) C(7A)-C(6A)-Si(1A) 122.0(3) C(10A)-C(6A)-Zr(1) 81.2(3) C(7A)-C(6A)-Zr(1) 72.4(2) Si(1A)-C(6A)-Zr(1) 96.17(17) C(8A)-C(7A)-C(6A) 106.7(4) C(8A)-C(7A)-Si(2A) 127.1(3) C(6A)-C(7A)-Si(2A) 122.1(3) C(8A)-C(7A)-Zr(1) 80.6(3) C(6A)-C(7A)-Zr(1) 72.0(2) Si(2A)-C(7A)-Zr(1) 95.21(17)
C(9A)-C(8A)-C(7A) 106.9(4) C(9A)-C(8A)-C(21A) 124.9(4) C(7A)-C(8A)-C(21A) 127.7(4) C(9A)-C(8A)-Zr(1) 75.7(3) C(7A)-C(8A)-Zr(1) 66.2(2) C(21A)-C(8A)-Zr(1) 129.5(3) C(10A)-C(9A)-C(8A) 111.2(4) C(10A)-C(9A)-Zr(1) 73.3(2) C(8A)-C(9A)-Zr(1) 73.2(2) C(9A)-C(10A)-C(6A) 107.7(4) C(9A)-C(10A)-C(27A) 125.5(4) C(6A)-C(10A)-C(27A) 126.5(4) C(9A)-C(10A)-Zr(1) 75.9(2) C(6A)-C(10A)-Zr(1) 66.1(2) C(27A)-C(10A)-Zr(1) 128.3(3) C(4A)-C(15A)-C(16A) 111.9(4) C(4A)-C(15A)-C(17A) 112.7(4) C(16A)-C(15A)-C(17A) 112.2(3) C(20A)-C(17A)-C(18A) 109.6(4) C(20A)-C(17A)-C(19A) 107.8(3) C(18A)-C(17A)-C(19A) 108.0(3) C(20A)-C(17A)-C(15A) 111.7(3) C(18A)-C(17A)-C(15A) 110.7(3)
C(19A)-C(17A)-C(15A) 108.9(3) C(8A)-C(21A)-C(26A) 113.2(4) C(8A)-C(21A)-C(22A) 109.1(4) C(26A)-C(21A)-C(22A) 109.8(4) C(23A)-C(22A)-C(21A) 112.4(4) C(22A)-C(23A)-C(24A) 110.4(3) C(25A)-C(24A)-C(23A) 110.1(3) C(24A)-C(25A)-C(26A) 110.7(4) C(21A)-C(26A)-C(25A) 111.2(4) C(10A)-C(27A)-C(32A) 113.2(4) C(10A)-C(27A)-C(28A) 109.3(4) C(32A)-C(27A)-C(28A) 110.7(4) C(27A)-C(28A)-C(29A) 111.0(4) C(30A)-C(29A)-C(28A) 111.1(4) C(29A)-C(30A)-C(31A) 110.5(4) C(30A)-C(31A)-C(32A) 112.2(4) C(27A)-C(32A)-C(31A) 111.0(4) C(1B)-Zr(2)-C(7B) 79.73(14) C(1B)-Zr(2)-C(6B) 68.39(14) C(7B)-Zr(2)-C(6B) 35.40(14) C(1B)-Zr(2)-Cl(2B) 136.64(11) C(7B)-Zr(2)-Cl(2B) 103.68(12) C(6B)-Zr(2)-Cl(2B) 135.39(11)
C(1B)-Zr(2)-C(2B) 35.24(14) C(7B)-Zr(2)-C(2B) 68.32(15) C(6B)-Zr(2)-C(2B) 78.97(15) Cl(2B)-Zr(2)-C(2B) 105.01(12) C(1B)-Zr(2)-Cl(1B) 104.03(11) C(7B)-Zr(2)-Cl(1B) 136.39(11) C(6B)-Zr(2)-Cl(1B) 104.70(11) Cl(2B)-Zr(2)-Cl(1B) 102.09(4) C(2B)-Zr(2)-Cl(1B) 135.73(11) C(1B)-Zr(2)-C(5B) 32.72(13) C(7B)-Zr(2)-C(5B) 112.43(15) C(6B)-Zr(2)-C(5B) 96.30(14) Cl(2B)-Zr(2)-C(5B) 122.88(11) C(2B)-Zr(2)-C(5B) 55.09(14) Cl(1B)-Zr(2)-C(5B) 80.81(11) C(1B)-Zr(2)-C(3B) 54.93(15) C(7B)-Zr(2)-C(3B) 96.17(14) C(6B)-Zr(2)-C(3B) 111.85(15) Cl(2B)-Zr(2)-C(3B) 81.88(11) C(2B)-Zr(2)-C(3B) 32.89(14) Cl(1B)-Zr(2)-C(3B) 121.95(10) C(5B)-Zr(2)-C(3B) 52.38(14) C(1B)-Zr(2)-C(10B) 96.24(15)
C(7B)-Zr(2)-C(10B) 54.87(15) C(6B)-Zr(2)-C(10B) 32.74(14) Cl(2B)-Zr(2)-C(10B) 121.44(10) C(2B)-Zr(2)-C(10B) 111.70(15) Cl(1B)-Zr(2)-C(10B) 81.68(10) C(5B)-Zr(2)-C(10B) 115.46(14) C(3B)-Zr(2)-C(10B) 144.59(15) C(1B)-Zr(2)-C(8B) 112.32(14) C(7B)-Zr(2)-C(8B) 32.61(14) C(6B)-Zr(2)-C(8B) 54.90(14) Cl(2B)-Zr(2)-C(8B) 80.66(11) C(2B)-Zr(2)-C(8B) 96.33(14) Cl(1B)-Zr(2)-C(8B) 122.31(10) C(5B)-Zr(2)-C(8B) 145.04(15) C(3B)-Zr(2)-C(8B) 115.52(14) C(10B)-Zr(2)-C(8B) 51.99(14) C(1B)-Zr(2)-C(4B) 53.87(14) C(7B)-Zr(2)-C(4B) 122.09(15) C(6B)-Zr(2)-C(4B) 122.23(15) Cl(2B)-Zr(2)-C(4B) 91.74(11) C(2B)-Zr(2)-C(4B) 53.77(14) Cl(1B)-Zr(2)-C(4B) 91.41(10) C(5B)-Zr(2)-C(4B) 31.49(14)
C(3B)-Zr(2)-C(4B) 30.79(13) C(10B)-Zr(2)-C(4B) 146.81(14) C(8B)-Zr(2)-C(4B) 146.25(14) C(1B)-Zr(2)-C(9B) 121.65(15) C(7B)-Zr(2)-C(9B) 53.33(14) C(6B)-Zr(2)-C(9B) 53.26(14) Cl(2B)-Zr(2)-C(9B) 91.22(11) C(2B)-Zr(2)-C(9B) 121.62(15) Cl(1B)-Zr(2)-C(9B) 91.78(10) C(5B)-Zr(2)-C(9B) 145.89(15) C(3B)-Zr(2)-C(9B) 146.28(14) C(10B)-Zr(2)-C(9B) 30.52(13) C(8B)-Zr(2)-C(9B) 30.92(13) C(4B)-Zr(2)-C(9B) 175.11(14) C(11B)-Si(1B)-C(12B) 109.5(2) C(11B)-Si(1B)-C(1B) 107.9(2) C(12B)-Si(1B)-C(1B) 114.3(2) C(11B)-Si(1B)-C(6B) 115.1(2) C(12B)-Si(1B)-C(6B) 116.7(2) C(1B)-Si(1B)-C(6B) 92.18(19) C(11B)-Si(1B)-Zr(2) 104.84(15) C(12B)-Si(1B)-Zr(2) 145.33(16) C(1B)-Si(1B)-Zr(2) 48.38(13)
C(6B)-Si(1B)-Zr(2) 48.54(13) C(14B)-Si(2B)-C(2B) 107.9(2) C(14B)-Si(2B)-C(13B) 107.1(2) C(2B)-Si(2B)-C(13B) 118.4(2) C(14B)-Si(2B)-C(7B) 115.2(2) C(2B)-Si(2B)-C(7B) 92.54(19) C(13B)-Si(2B)-C(7B) 115.3(2) C(14B)-Si(2B)-Zr(2) 103.65(16) C(2B)-Si(2B)-Zr(2) 49.24(13) C(13B)-Si(2B)-Zr(2) 149.26(17) C(7B)-Si(2B)-Zr(2) 48.83(13) C(5B)-C(1B)-C(2B) 106.8(4) C(5B)-C(1B)-Si(1B) 127.7(3) C(2B)-C(1B)-Si(1B) 121.5(3) C(5B)-C(1B)-Zr(2) 78.9(3) C(2B)-C(1B)-Zr(2) 73.0(2) Si(1B)-C(1B)-Zr(2) 96.18(17) C(3B)-C(2B)-C(1B) 105.8(4) C(3B)-C(2B)-Si(2B) 125.5(4) C(1B)-C(2B)-Si(2B) 123.7(3) C(3B)-C(2B)-Zr(2) 79.0(3) C(1B)-C(2B)-Zr(2) 71.8(2) Si(2B)-C(2B)-Zr(2) 95.01(17)
C(4B)-C(3B)-C(2B) 110.5(4) C(4B)-C(3B)-Zr(2) 78.3(3) C(2B)-C(3B)-Zr(2) 68.1(2) C(3B)-C(4B)-C(5B) 107.0(4) C(3B)-C(4B)-C(15B) 126.9(4) C(5B)-C(4B)-C(15B) 126.0(4) C(3B)-C(4B)-Zr(2) 70.9(2) C(5B)-C(4B)-Zr(2) 69.8(2) C(15B)-C(4B)-Zr(2) 127.3(3) C(1B)-C(5B)-C(4B) 109.9(4) C(1B)-C(5B)-Zr(2) 68.4(2) C(4B)-C(5B)-Zr(2) 78.7(3) C(10B)-C(6B)-C(7B) 106.4(4) C(10B)-C(6B)-Si(1B) 127.7(3) C(7B)-C(6B)-Si(1B) 122.2(3) C(10B)-C(6B)-Zr(2) 80.9(3) C(7B)-C(6B)-Zr(2) 72.2(2) Si(1B)-C(6B)-Zr(2) 95.44(16) C(8B)-C(7B)-C(6B) 106.9(4) C(8B)-C(7B)-Si(2B) 127.2(4) C(6B)-C(7B)-Si(2B) 122.2(3) C(8B)-C(7B)-Zr(2) 81.4(3) C(6B)-C(7B)-Zr(2) 72.4(2)
Si(2B)-C(7B)-Zr(2) 95.07(17) C(9B)-C(8B)-C(7B) 108.2(4) C(9B)-C(8B)-C(21B) 125.2(4) C(7B)-C(8B)-C(21B) 126.4(4) C(9B)-C(8B)-Zr(2) 77.1(2) C(7B)-C(8B)-Zr(2) 66.0(2) C(21B)-C(8B)-Zr(2) 126.2(3) C(10B)-C(9B)-C(8B) 109.3(4) C(10B)-C(9B)-Zr(2) 71.8(2) C(8B)-C(9B)-Zr(2) 72.0(2) C(9B)-C(10B)-C(6B) 109.0(4) C(9B)-C(10B)-C(27B) 125.2(4) C(6B)-C(10B)-C(27B) 125.4(4) C(9B)-C(10B)-Zr(2) 77.7(3) C(6B)-C(10B)-Zr(2) 66.4(2) C(27B)-C(10B)-Zr(2) 127.6(3) C(16B)-C(15B)-C(4B) 110.0(3) C(16B)-C(15B)-C(17B) 112.4(3) C(4B)-C(15B)-C(17B) 111.6(3) C(20B)-C(17B)-C(19B) 110.0(3) C(20B)-C(17B)-C(18B) 107.9(3) C(19B)-C(17B)-C(18B) 107.8(3) C(20B)-C(17B)-C(15B) 111.2(3)
C(19B)-C(17B)-C(15B) 109.1(3) C(18B)-C(17B)-C(15B) 110.7(3) C(8B)-C(21B)-C(26B) 114.0(4) C(8B)-C(21B)-C(22B) 109.7(4) C(26B)-C(21B)-C(22B) 109.4(4) C(23B)-C(22B)-C(21B) 111.3(4) C(22B)-C(23B)-C(24B) 110.5(4) C(25B)-C(24B)-C(23B) 111.9(4) C(26B)-C(25B)-C(24B) 112.4(4) C(25B)-C(26B)-C(21B) 110.7(4) C(10B)-C(27B)-C(32B) 113.2(4)
C(10B)-C(27B)-C(28B) 108.5(4) C(32B)-C(27B)-C(28B) 109.1(3) C(29B)-C(28B)-C(27B) 111.0(4) C(28B)-C(29B)-C(30B) 110.6(4) C(31B)-C(30B)-C(29B) 111.1(4) C(32B)-C(31B)-C(30B) 111.9(4) C(31B)-C(32B)-C(27B) 112.1(4) Cl(5)-C(51)-Cl(6) 114.7(3) Cl(7)-C(52)-Cl(8) 114.5(4) Cl(10)-C(53)-Cl(9) 111.9(3)
_______________________________________________________________________
Table B.5. Anisotropic displacement parameters (Å2x 104) for (S)-4
The anisotropic displacement factor exponent takes the form: -2π2 [ h2 a*2U 11 + ... + 2 h k a* b* U12 ]
_______________________________________________________________________
U11 U22 U33 U23 U13 U12
_______________________________________________________________________
Zr(1) 106(2) 102(2) 132(2) 3(2) 30(2) 10(2) Cl(1A) 156(6) 119(6) 241(6) 10(5) 47(5) –24(5) Cl(2A) 129(5) 199(6) 200(5) –14(5) 64(4) 21(5) Si(1A) 120(7) 156(8) 124(6) 0(6) 37(5) 13(6) Si(2A) 150(7) 103(6) 150(6) –10(5) 43(5) 5(5) C(1A) 110(20) 90(20) 170(20) –12(19) –3(19) 35(19) C(2A) 190(30) 130(30) 140(20) 20(20) 18(19) 80(20) C(3A) 70(20) 130(30) 170(20) 40(20) –4(18) 8(19) C(4A) 100(20) 170(30) 90(20) 30(20) –17(17) 20(20) C(5A) 90(20) 200(30) 120(20) 80(20) 21(17) 30(20) C(6A) 100(20) 150(30) 150(20) 0(20) 14(19) –40(20) C(7A) 190(30) 120(20) 110(20) 4(18) 41(19) 10(20) C(8A) 100(20) 180(30) 110(20) –73(19) –17(18) 10(20) C(9A) 150(20) 70(20) 120(20) 15(17) –28(18) 4(18) C(10A) 110(20) 120(20) 100(20) –29(18) –38(17) –18(19) C(11A) 200(30) 260(30) 200(30) –20(20) 90(20) –60(30) C(12A) 190(30) 230(30) 180(30) –30(20) 50(20) 80(20) C(13A) 240(30) 160(30) 240(20) 10(20) 30(20) 30(20) C(14A) 210(20) 180(20) 140(20) 2(17) 45(18) 33(19) C(15A) 120(20) 180(30) 180(20) 30(20) 11(18) –40(20)
C(16A) 170(20) 220(20) 290(20) –102(17) 106(17) –18(16) C(17A) 230(20) 190(20) 130(20) –55(17) 43(17) –6(18) C(18A) 180(20) 610(30) 230(20) –130(20) 13(18) –50(20) C(19A) 220(20) 250(20) 330(30) –118(19) 18(19) 24(19) C(20A) 470(30) 270(20) 190(20) –46(19) 3(19) 20(20) C(21A) 180(20) 130(20) 100(20) 14(16) 46(17) –9(18) C(22A) 150(20) 150(20) 230(20) 1(18) 16(18) 26(17) C(23A) 200(20) 130(20) 310(30) –42(19) 20(19) –68(17) C(24A) 170(20) 270(20) 220(20) 27(19) 3(18) –84(18) C(25A) 130(20) 230(20) 160(20) 3(18) -3(17) 12(18) C(26A) 110(20) 190(20) 180(20) 5(18) 6(17) –16(18) C(27A) 150(30) 260(30) 90(20) 0(20) 30(20) 0(20) C(28A) 280(30) 170(30) 270(30) 10(20) 100(20) 90(30) C(29A) 270(30) 340(30) 200(30) 60(20) 140(20) –10(30) C(30A) 330(30) 260(30) 150(20) 120(20) 80(20) –40(20) C(31A) 260(30) 190(30) 190(20) 80(20) 30(20) –90(20) C(32A) 170(30) 160(30) 180(20) 30(20) –20(20) 0(20) Zr(2) 112(2) 103(2) 115(2) –6(2) 34(2) –11(2) Cl(1B) 164(6) 194(6) 192(5) –2(5) 83(4) –18(5) Cl(2B) 179(6) 130(6) 191(6) –31(5) 45(5) –16(5) Si(1B) 154(7) 100(6) 124(6) 2(5) 8(5) –4(5) Si(2B) 114(7) 164(8) 154(7) 27(6) 25(5) –16(6) C(1B) 70(20) 90(20) 80(20) –25(18) –46(17) –20(18)
C(2B) 60(20) 190(30) 100(20) –29(19) –6(18) –50(20) C(3B) 90(20) 90(20) 100(20) 21(18) –35(17) 26(19) C(4B) 140(20) 100(30) 130(20) –19(19) –10(18) –4(19) C(5B) 130(20) 170(30) 70(20) –38(19) 22(18) –20(20) C(6B) 90(20) 140(20) 130(20) 73(19) 21(18) –3(19) C(7B) 170(30) 120(20) 90(20) 60(19) 38(19) –30(20) C(8B) 170(30) 150(30) 100(20) 27(18) 70(19) 20(20) C(9B) 110(20) 190(30) 100(20) 25(18) 33(18) –19(19) C(10B) 200(30) 90(20) 90(20) 17(17) 28(19) 10(20) C(11B) 200(20) 140(20) 150(20) –26(17) 24(18) 23(18) C(12B) 200(30) 130(20) 270(20) 40(20) 50(20) 20(20) C(13B) 200(30) 260(30) 200(30) 10(20) 70(20) –70(20) C(14B) 130(30) 280(30) 180(20) 10(20) 20(20) 0(20) C(15B) 180(20) 70(20) 160(20) 55(18) 104(18) –11(19) C(16B) 320(20) 160(18) 170(20) 2(15) 31(17) –10(16) C(17B) 180(20) 150(20) 110(20) 24(16) 53(16) –1(17) C(18B) 370(20) 170(20) 164(19) –7(16) 78(18) 69(18) C(19B) 300(20) 220(20) 220(20) 95(18) 63(19) 59(19) C(20B) 200(20) 280(20) 170(20) 46(17) 10(16) –22(17) C(21B) 130(20) 120(20) 160(20) –32(19) 33(19) 10(20) C(22B) 200(30) 290(30) 110(20) –40(20) 70(20) 30(20) C(23B) 310(30) 330(30) 200(30) –30(20) 100(20) 0(30) C(24B) 280(30) 300(30) 230(30) –40(20) 90(20) 100(30)
C(25B) 220(30) 230(30) 160(20) –30(20) 10(20) 0(20) C(26B) 200(30) 190(30) 160(20) –20(20) 80(20) 50(20) C(27B) 100(20) 140(20) 120(20) –21(17) -12(16) 19(18) C(28B) 180(20) 150(20) 220(20) 24(18) 23(18) 36(18) C(29B) 240(20) 240(20) 340(30) 20(20) 100(20) 77(19) C(30B) 200(20) 300(30) 240(20) 10(20) 61(19) 109(19) C(31B) 110(20) 370(30) 220(20) 0(20) 18(18) –5(19) C(32B) 190(20) 130(20) 200(20) 14(18) 74(19) 8(18) C(51) 370(40) 610(40) 590(40) –320(40) 170(30) –80(30) Cl(5) 314(7) 378(7) 761(9) –251(7) 181(7) –42(5) Cl(6) 316(7) 266(7) 284(7) –48(6) 63(6) –34(6) C(52) 510(50) 620(50) 490(50) 210(40) 10(40) –260(40) Cl(7) 491(15) 461(16) 911(19) –13(14) 363(14) 104(11) Cl(8) 466(14) 433(14) 461(13) 113(11) 150(10) 137(11) C(53) 240(30) 260(30) 490(30) –250(30) 40(20) –20(20) Cl(9) 393(8) 207(7) 218(6) –25(5) 37(5) –72(6) Cl(10) 343(7) 344(6) 549(8) –136(6) –17(6) 80(5) _______________________________________________________________________