Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103000751/sq1005sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103000751/sq1005Isup2.hkl |
CCDC reference: 205300
All experiments were conducted under an argon atmosphere. The solvents were dried and distilled prior to use. (3,5-Dimethylphenylamino)(dimethyl)(isodicyclopentadienyl)silane was prepared according to published methods, using chlorodimethyl(isodicyclopentadienyl)silane (Gentil et al., 2000) and solid lithium (3,5-dimethyl)phenylamine in diethyl ether. To a solution of (3,5-dimethylphenylamino)(dimethyl)(isodicyclopentadienyl)silane (3.04 mmol, 897 mg) in diethyl ether (15 ml) at 195 K was slowly added n-butyllithium (6.1 mmol, 3.8 ml of a 1.6 M solution in hexane). The mixture was allowed to warm to room temperature, refluxed overnight, and filtered. The pale-yellow precipitate was washed three times with diethyl ether and dried in vacuo (628 mg, 69%). The pale-yellow powder was then placed in diethyl ether (15 ml) and the suspension treated gradually with solid zirconium tetrachloride (1.05 mmol, 244 mg, 0.5 equivalents). The mixture was warmed to room temperature and stirred for 48 h, and the resulting suspension was filtered off. Concentration of the filtrate and cooling to 253 K over a period of 2 d afforded colourless crystals of (I) (164 mg, 20% yield).
Besides the Zr complex, the asymmetric unit of (I) contains a diethyl ether solvent molecule. The methyl group H atoms were added at calculated positions using a riding model with Uiso(H) = 1.5Ueq(C). For each methyl group, the torsion angle which defines the orientation about the Si—C or the C—C bond was refined. The remaining H atoms were included in the model at calculated positions using a riding model with Uiso(H) = 1.2Ueq(C). Data integration was done with DENZO (Otwinowski & Minor, 1997). Scaling and merging of the data were done with SCALEPACK (Otwinowski & Minor, 1997); application of an absorption correction is inherent in this treatment and is reflected in the scale factor range of 9.93 to 11.54 for the frames. PLATON (Spek, 1990) was used to calculate some metric parameters.
Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: ORTEPII (Johnson, 1976).
Fig. 1. A view of the molecule of complex (I), with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity. |
[Zr(C20H25NSi)2]·C4H10O | Z = 2 |
Mr = 780.34 | F(000) = 828 |
Triclinic, P1 | Dx = 1.289 Mg m−3 |
a = 10.7036 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.6479 (2) Å | Cell parameters from 9071 reflections |
c = 17.4618 (3) Å | θ = 2.0–27.5° |
α = 70.848 (1)° | µ = 0.37 mm−1 |
β = 78.069 (1)° | T = 150 K |
γ = 84.194 (1)° | Square plate, colourless |
V = 2010.81 (6) Å3 | 0.35 × 0.35 × 0.04 mm |
Nonius Kappa CCD area-detector diffractometer | 7028 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.051 |
Graphite monochromator | θmax = 27.5°, θmin = 2.0° |
ϕ and ω scans | h = 0→13 |
50007 measured reflections | k = −14→15 |
9121 independent reflections | l = −21→22 |
Refinement on F2 | 0 constraints |
Least-squares matrix: full | Primary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.038 | Secondary atom site location: difference Fourier map |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0319P)2 + 1.2411P] where P = (Fo2 + 2Fc2)/3 |
9118 reflections | (Δ/σ)max = 0.037 |
461 parameters | Δρmax = 0.51 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
[Zr(C20H25NSi)2]·C4H10O | γ = 84.194 (1)° |
Mr = 780.34 | V = 2010.81 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.7036 (2) Å | Mo Kα radiation |
b = 11.6479 (2) Å | µ = 0.37 mm−1 |
c = 17.4618 (3) Å | T = 150 K |
α = 70.848 (1)° | 0.35 × 0.35 × 0.04 mm |
β = 78.069 (1)° |
Nonius Kappa CCD area-detector diffractometer | 7028 reflections with I > 2σ(I) |
50007 measured reflections | Rint = 0.051 |
9121 independent reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.51 e Å−3 |
9118 reflections | Δρmin = −0.33 e Å−3 |
461 parameters |
Experimental. All work was done at 150 K using an Oxford Cryosystems Cryostream Cooler. A hemisphere of data was measured with a redundancy factor of 2.8, which means that 90% of the data was measured at least 2.8 times. A combination of ϕ and ω scans with a frame width of 1.0° was used for data collection. 1H and 13C NMR spectra were recorded with a Bruker DRX500 spectrometer. 1H NMR (C6D6, δ, p.p.m.): 6.92 (s, 1H, Ar), 6.65 (s, 2H, Ar), 5.60 (s, 2H, peripheral), 3.09 (br s, 2H, bridgehead), 2.39 (s, 6H, CH3), 1.81 (dm, 1H, syn-methano bridge), 1.67 (dm, 2H, exo-ethano bridge), 1.39 (dm, 1H, anti-methano bridge), 1.03 (dm, 2H, endo-ethano bridge), 0.85 (s, 3H, SiCH3), 0.70 (s, 3H, SiCH3); 13C NMR (C6D6, δ, p.p.m.): 148.3 (quaternary), 137.7 (Ar ipso), 123.0 (Ar para), 121.6 (Ar ortho), 110.5 (Ar meta), 103.8 (peripheral), 50.1 (methano bridge), 40.5 (bridgehead), 29.8 (ethano bridge), 21.9 (CH3), 3.0 (SiCH3), −1.3 (SiCH3). |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement on F2 for ALL reflections except for 3 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(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. |
x | y | z | Uiso*/Ueq | ||
Zr | 0.39150 (2) | 0.04658 (2) | 0.256091 (13) | 0.01798 (7) | |
Si1 | 0.60202 (5) | −0.04139 (6) | 0.13603 (4) | 0.02049 (14) | |
Si2 | 0.32191 (6) | 0.21426 (6) | 0.36521 (4) | 0.02163 (14) | |
O | 0.8742 (2) | 0.6112 (2) | 0.21117 (11) | 0.0403 (4) | |
N1 | 0.4006 (2) | 0.2236 (2) | 0.26655 (11) | 0.0212 (4) | |
N2 | 0.5841 (2) | −0.0194 (2) | 0.23123 (11) | 0.0204 (4) | |
C1 | 0.3787 (2) | −0.1409 (2) | 0.39085 (13) | 0.0224 (5) | |
C2 | 0.4030 (2) | −0.0373 (2) | 0.40897 (13) | 0.0228 (5) | |
H2 | 0.4777 | −0.0254 | 0.42642 | 0.027* | |
C3 | 0.2965 (2) | 0.0477 (2) | 0.39682 (13) | 0.0216 (5) | |
C4 | 0.2052 (2) | −0.0089 (2) | 0.37240 (13) | 0.0227 (5) | |
H4 | 0.1235 | 0.0245 | 0.36163 | 0.027* | |
C5 | 0.2579 (2) | −0.1233 (2) | 0.36712 (13) | 0.0234 (5) | |
C6 | 0.2240 (2) | −0.2443 (2) | 0.36336 (15) | 0.0287 (5) | |
H6 | 0.1588 | −0.2417 | 0.32920 | 0.034* | |
C7 | 0.1964 (2) | −0.3274 (2) | 0.4548 (2) | 0.0341 (6) | |
H7A | 0.1342 | −0.2873 | 0.4892 | 0.041* | |
H7B | 0.1627 | −0.4059 | 0.4592 | 0.041* | |
C8 | 0.3288 (2) | −0.3465 (2) | 0.48108 (15) | 0.0324 (6) | |
H8A | 0.3555 | −0.4337 | 0.49763 | 0.039* | |
H8B | 0.3270 | −0.3151 | 0.52755 | 0.039* | |
C9 | 0.4197 (2) | −0.2726 (2) | 0.40241 (14) | 0.0274 (5) | |
H9 | 0.5131 | −0.2931 | 0.40017 | 0.033* | |
C10 | 0.3599 (2) | −0.2951 (2) | 0.33567 (15) | 0.0321 (6) | |
H10A | 0.3608 | −0.3824 | 0.34078 | 0.038* | |
H10B | 0.3999 | −0.2477 | 0.27906 | 0.038* | |
C11 | 0.2254 (2) | 0.0547 (2) | 0.16633 (13) | 0.0210 (5) | |
C12 | 0.3199 (2) | −0.0363 (2) | 0.15759 (13) | 0.0216 (5) | |
H12 | 0.3070 | −0.1212 | 0.17473 | 0.026* | |
C13 | 0.4393 (2) | 0.0221 (2) | 0.11817 (13) | 0.0212 (5) | |
C14 | 0.4125 (2) | 0.1500 (2) | 0.10134 (13) | 0.0206 (5) | |
H14 | 0.4728 | 0.2118 | 0.07452 | 0.025* | |
C15 | 0.2826 (2) | 0.1689 (2) | 0.13095 (13) | 0.0202 (5) | |
C16 | 0.1762 (2) | 0.2654 (2) | 0.12446 (13) | 0.0239 (5) | |
H16 | 0.1998 | 0.3487 | 0.11980 | 0.029* | |
C17 | 0.1116 (2) | 0.2553 (2) | 0.05503 (15) | 0.0291 (5) | |
H17A | 0.1758 | 0.2568 | 0.00496 | 0.035* | |
H17B | 0.0474 | 0.3223 | 0.04046 | 0.035* | |
C18 | 0.0472 (2) | 0.1302 (2) | 0.09400 (15) | 0.0306 (6) | |
H18A | 0.0811 | 0.0750 | 0.06126 | 0.037* | |
H18B | −0.0466 | 0.1402 | 0.09763 | 0.037* | |
C19 | 0.0824 (2) | 0.0802 (2) | 0.18159 (14) | 0.0252 (5) | |
H19 | 0.0293 | 0.0136 | 0.22306 | 0.030* | |
C20 | 0.0770 (2) | 0.2014 (2) | 0.20089 (14) | 0.0275 (5) | |
H20A | −0.0085 | 0.2428 | 0.20083 | 0.033* | |
H20B | 0.1052 | 0.1912 | 0.25336 | 0.033* | |
C21 | 0.1678 (2) | 0.3047 (2) | 0.37536 (15) | 0.0308 (6) | |
H21A | 0.1858 | 0.3908 | 0.3611 | 0.046* | |
H21B | 0.1213 | 0.2756 | 0.4323 | 0.046* | |
H21C | 0.1158 | 0.2949 | 0.3380 | 0.046* | |
C22 | 0.4251 (2) | 0.2503 (2) | 0.42732 (15) | 0.0327 (6) | |
H22A | 0.3795 | 0.2341 | 0.4844 | 0.049* | |
H22B | 0.4465 | 0.3362 | 0.4039 | 0.049* | |
H22C | 0.5038 | 0.1994 | 0.4264 | 0.049* | |
C23 | 0.6299 (2) | −0.1999 (2) | 0.13303 (15) | 0.0286 (5) | |
H23A | 0.6295 | −0.2011 | 0.0772 | 0.043* | |
H23B | 0.5621 | −0.2508 | 0.1721 | 0.043* | |
H23C | 0.7128 | −0.2315 | 0.1482 | 0.043* | |
C24 | 0.7281 (2) | 0.0518 (2) | 0.05696 (14) | 0.0295 (5) | |
H24A | 0.7217 | 0.0492 | 0.0024 | 0.044* | |
H24B | 0.8123 | 0.0194 | 0.0693 | 0.044* | |
H24C | 0.7167 | 0.1362 | 0.0575 | 0.044* | |
C25 | 0.6768 (2) | −0.0481 (2) | 0.28281 (13) | 0.0204 (5) | |
C26 | 0.7339 (2) | −0.1643 (2) | 0.30747 (13) | 0.0222 (5) | |
H26 | 0.7133 | −0.2248 | 0.28703 | 0.027* | |
C27 | 0.8202 (2) | −0.1937 (2) | 0.36114 (13) | 0.0234 (5) | |
C28 | 0.8531 (2) | −0.1037 (2) | 0.38912 (13) | 0.0239 (5) | |
H28 | 0.9130 | −0.1227 | 0.42515 | 0.029* | |
C29 | 0.7995 (2) | 0.0137 (2) | 0.36504 (13) | 0.0216 (5) | |
C30 | 0.7113 (2) | 0.0394 (2) | 0.31281 (13) | 0.0212 (5) | |
H30 | 0.6733 | 0.1189 | 0.29699 | 0.025* | |
C31 | 0.8726 (2) | −0.3230 (2) | 0.3913 (2) | 0.0339 (6) | |
H31A | 0.9376 | −0.3263 | 0.4241 | 0.051* | |
H31B | 0.9110 | −0.3502 | 0.3438 | 0.051* | |
H31C | 0.8031 | −0.3762 | 0.4253 | 0.051* | |
C32 | 0.8339 (2) | 0.1110 (2) | 0.39588 (14) | 0.0279 (5) | |
H32A | 0.7585 | 0.1347 | 0.4307 | 0.042* | |
H32B | 0.8637 | 0.1820 | 0.34880 | 0.042* | |
H32C | 0.9018 | 0.0795 | 0.4281 | 0.042* | |
C33 | 0.4538 (2) | 0.3289 (2) | 0.20567 (13) | 0.0202 (5) | |
C34 | 0.5777 (2) | 0.3239 (2) | 0.16038 (13) | 0.0210 (5) | |
H34 | 0.6256 | 0.2490 | 0.17154 | 0.025* | |
C35 | 0.6323 (2) | 0.4257 (2) | 0.09968 (13) | 0.0231 (5) | |
C36 | 0.5613 (2) | 0.5351 (2) | 0.08268 (14) | 0.0242 (5) | |
H36 | 0.5974 | 0.6048 | 0.04060 | 0.029* | |
C37 | 0.4388 (2) | 0.5437 (2) | 0.12632 (14) | 0.0242 (5) | |
C38 | 0.3867 (2) | 0.4408 (2) | 0.18761 (14) | 0.0240 (5) | |
H38 | 0.3032 | 0.4470 | 0.21803 | 0.029* | |
C39 | 0.7680 (2) | 0.4189 (2) | 0.0547 (2) | 0.0354 (6) | |
H39A | 0.8234 | 0.4612 | 0.0741 | 0.053* | |
H39B | 0.7715 | 0.4576 | −0.0047 | 0.053* | |
H39C | 0.7972 | 0.3336 | 0.0655 | 0.053* | |
C40 | 0.3608 (2) | 0.6615 (2) | 0.1076 (2) | 0.0331 (6) | |
H40A | 0.3143 | 0.6729 | 0.1594 | 0.050* | |
H40B | 0.2997 | 0.6588 | 0.0735 | 0.050* | |
H40C | 0.4176 | 0.7292 | 0.0779 | 0.050* | |
C41 | 0.8483 (3) | 0.4862 (3) | 0.2493 (2) | 0.0562 (8) | |
H41A | 0.8967 | 0.4510 | 0.2948 | 0.067* | |
H41B | 0.8756 | 0.4420 | 0.2086 | 0.067* | |
C42 | 0.7091 (3) | 0.4729 (3) | 0.2823 (2) | 0.0526 (8) | |
H42A | 0.6911 | 0.3866 | 0.3092 | 0.079* | |
H42B | 0.6617 | 0.5064 | 0.2369 | 0.079* | |
H42C | 0.6825 | 0.5170 | 0.3224 | 0.079* | |
C43 | 1.0030 (3) | 0.6371 (3) | 0.1759 (2) | 0.0565 (8) | |
H43A | 1.0321 | 0.5997 | 0.1316 | 0.068* | |
H43B | 1.0570 | 0.6028 | 0.2184 | 0.068* | |
C44 | 1.0153 (3) | 0.7716 (3) | 0.1413 (2) | 0.0583 (9) | |
H44A | 1.1055 | 0.7905 | 0.1195 | 0.087* | |
H44B | 0.9826 | 0.8085 | 0.1850 | 0.087* | |
H44C | 0.9661 | 0.8044 | 0.0969 | 0.087* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zr | 0.01738 (11) | 0.01934 (12) | 0.01615 (11) | −0.00010 (8) | −0.00245 (8) | −0.00473 (8) |
Si1 | 0.0174 (3) | 0.0255 (3) | 0.0198 (3) | 0.0025 (2) | −0.0041 (2) | −0.0093 (3) |
Si2 | 0.0228 (3) | 0.0229 (3) | 0.0184 (3) | −0.0004 (3) | −0.0013 (2) | −0.0071 (3) |
O | 0.0403 (10) | 0.0329 (11) | 0.0435 (11) | 0.0075 (8) | −0.0060 (9) | −0.0102 (9) |
N1 | 0.0222 (9) | 0.0196 (10) | 0.0192 (9) | 0.0002 (8) | −0.0011 (8) | −0.0048 (8) |
N2 | 0.0195 (9) | 0.0227 (10) | 0.0195 (9) | 0.0016 (7) | −0.0052 (8) | −0.0072 (8) |
C1 | 0.0241 (11) | 0.0231 (12) | 0.0165 (11) | −0.0040 (9) | −0.0026 (9) | −0.0013 (9) |
C2 | 0.0221 (11) | 0.0281 (13) | 0.0151 (11) | −0.0034 (9) | −0.0030 (9) | −0.0022 (9) |
C3 | 0.0233 (11) | 0.0236 (12) | 0.0142 (11) | −0.0014 (9) | 0.0006 (9) | −0.0035 (9) |
C4 | 0.0194 (11) | 0.0254 (13) | 0.0180 (11) | −0.0018 (9) | −0.0004 (9) | −0.0015 (9) |
C5 | 0.0231 (11) | 0.0236 (13) | 0.0202 (11) | −0.0052 (9) | −0.0026 (9) | −0.0022 (10) |
C6 | 0.0310 (13) | 0.0243 (13) | 0.0301 (13) | −0.0045 (10) | −0.0096 (11) | −0.0044 (11) |
C7 | 0.0367 (14) | 0.0267 (14) | 0.0343 (14) | −0.0092 (11) | −0.0056 (11) | −0.0015 (11) |
C8 | 0.0384 (14) | 0.0245 (13) | 0.0290 (13) | −0.0047 (11) | −0.0062 (11) | −0.0004 (11) |
C9 | 0.0284 (12) | 0.0227 (13) | 0.0283 (13) | −0.0007 (10) | −0.0065 (10) | −0.0036 (10) |
C10 | 0.0420 (14) | 0.0255 (14) | 0.0272 (13) | −0.0028 (11) | −0.0052 (11) | −0.0066 (11) |
C11 | 0.0201 (11) | 0.0258 (13) | 0.0181 (11) | −0.0002 (9) | −0.0049 (9) | −0.0075 (10) |
C12 | 0.0228 (11) | 0.0239 (12) | 0.0212 (11) | −0.0014 (9) | −0.0065 (9) | −0.0095 (10) |
C13 | 0.0216 (11) | 0.0269 (13) | 0.0165 (11) | 0.0032 (9) | −0.0054 (9) | −0.0088 (9) |
C14 | 0.0200 (11) | 0.0261 (13) | 0.0144 (10) | −0.0021 (9) | −0.0024 (9) | −0.0048 (9) |
C15 | 0.0208 (11) | 0.0217 (12) | 0.0171 (11) | 0.0018 (9) | −0.0058 (9) | −0.0040 (9) |
C16 | 0.0231 (11) | 0.0224 (12) | 0.0244 (12) | 0.0028 (9) | −0.0050 (9) | −0.0055 (10) |
C17 | 0.0223 (12) | 0.0374 (15) | 0.0269 (13) | 0.0062 (10) | −0.0086 (10) | −0.0087 (11) |
C18 | 0.0223 (12) | 0.039 (2) | 0.0343 (14) | 0.0049 (10) | −0.0113 (11) | −0.0141 (12) |
C19 | 0.0189 (11) | 0.0287 (13) | 0.0261 (12) | −0.0016 (9) | −0.0013 (9) | −0.0077 (10) |
C20 | 0.0228 (12) | 0.0332 (14) | 0.0254 (12) | 0.0058 (10) | −0.0037 (10) | −0.0101 (11) |
C21 | 0.0320 (13) | 0.0331 (15) | 0.0248 (13) | 0.0032 (11) | 0.0019 (10) | −0.0114 (11) |
C22 | 0.0376 (14) | 0.0339 (15) | 0.0284 (13) | −0.0049 (11) | −0.0056 (11) | −0.0114 (11) |
C23 | 0.0256 (12) | 0.0317 (14) | 0.0324 (13) | 0.0047 (10) | −0.0063 (10) | −0.0165 (11) |
C24 | 0.0243 (12) | 0.0365 (15) | 0.0268 (13) | 0.0009 (10) | −0.0032 (10) | −0.0105 (11) |
C25 | 0.0163 (10) | 0.0271 (13) | 0.0156 (11) | −0.0022 (9) | 0.0007 (8) | −0.0057 (9) |
C26 | 0.0211 (11) | 0.0249 (13) | 0.0220 (11) | −0.0005 (9) | −0.0057 (9) | −0.0084 (10) |
C27 | 0.0187 (11) | 0.0259 (13) | 0.0224 (12) | 0.0004 (9) | −0.0029 (9) | −0.0042 (10) |
C28 | 0.0193 (11) | 0.0321 (14) | 0.0187 (11) | −0.0028 (10) | −0.0049 (9) | −0.0048 (10) |
C29 | 0.0185 (11) | 0.0278 (13) | 0.0175 (11) | −0.0042 (9) | 0.0009 (9) | −0.0072 (10) |
C30 | 0.0201 (11) | 0.0226 (12) | 0.0199 (11) | 0.0017 (9) | −0.0032 (9) | −0.0064 (10) |
C31 | 0.0314 (13) | 0.0317 (15) | 0.0388 (15) | 0.0044 (11) | −0.0172 (12) | −0.0065 (12) |
C32 | 0.0269 (12) | 0.0347 (14) | 0.0234 (12) | −0.0061 (10) | −0.0026 (10) | −0.0108 (11) |
C33 | 0.0241 (11) | 0.0197 (12) | 0.0175 (11) | −0.0029 (9) | −0.0042 (9) | −0.0060 (9) |
C34 | 0.0239 (11) | 0.0173 (12) | 0.0217 (11) | 0.0010 (9) | −0.0049 (9) | −0.0061 (9) |
C35 | 0.0250 (11) | 0.0241 (13) | 0.0211 (12) | −0.0039 (10) | −0.0018 (9) | −0.0090 (10) |
C36 | 0.0301 (12) | 0.0184 (12) | 0.0221 (12) | −0.0065 (10) | −0.0052 (10) | −0.0017 (9) |
C37 | 0.0272 (12) | 0.0199 (12) | 0.0287 (13) | −0.0012 (9) | −0.0104 (10) | −0.0086 (10) |
C38 | 0.0218 (11) | 0.0251 (13) | 0.0256 (12) | −0.0003 (9) | −0.0040 (10) | −0.0088 (10) |
C39 | 0.0320 (13) | 0.0284 (14) | 0.040 (2) | −0.0052 (11) | 0.0026 (12) | −0.0071 (12) |
C40 | 0.0303 (13) | 0.0220 (13) | 0.043 (2) | 0.0017 (10) | −0.0096 (12) | −0.0047 (11) |
C41 | 0.073 (2) | 0.035 (2) | 0.065 (2) | 0.010 (2) | −0.022 (2) | −0.018 (2) |
C42 | 0.076 (2) | 0.039 (2) | 0.044 (2) | −0.018 (2) | −0.020 (2) | −0.0046 (14) |
C43 | 0.039 (2) | 0.062 (2) | 0.062 (2) | 0.0126 (15) | −0.0011 (15) | −0.018 (2) |
C44 | 0.033 (2) | 0.063 (2) | 0.061 (2) | 0.0000 (15) | 0.0011 (15) | −0.003 (2) |
Zr—N2 | 2.135 (2) | C18—H18B | 0.99 |
Zr—N1 | 2.143 (2) | C19—C20 | 1.549 (3) |
Zr—C13 | 2.461 (2) | C19—H19 | 1.00 |
Zr—C3 | 2.461 (2) | C20—H20A | 0.99 |
Zr—C4 | 2.499 (2) | C20—H20B | 0.99 |
Zr—C12 | 2.502 (2) | C21—H21A | 0.98 |
Zr—C14 | 2.544 (2) | C21—H21B | 0.98 |
Zr—C2 | 2.549 (2) | C21—H21C | 0.98 |
Zr—C5 | 2.575 (2) | C22—H22A | 0.98 |
Zr—C11 | 2.579 (2) | C22—H22B | 0.98 |
Zr—C15 | 2.615 (2) | C22—H22C | 0.98 |
Zr—C1 | 2.623 (2) | C23—H23A | 0.98 |
Si1—N2 | 1.733 (2) | C23—H23B | 0.98 |
Si1—C23 | 1.856 (2) | C23—H23C | 0.98 |
Si1—C24 | 1.857 (2) | C24—H24A | 0.98 |
Si1—C13 | 1.869 (2) | C24—H24B | 0.98 |
Si2—N1 | 1.728 (2) | C24—H24C | 0.98 |
Si2—C22 | 1.860 (2) | C25—C26 | 1.396 (3) |
Si2—C3 | 1.867 (2) | C25—C30 | 1.399 (3) |
Si2—C21 | 1.874 (2) | C26—C27 | 1.390 (3) |
O—C43 | 1.408 (3) | C26—H26 | 0.95 |
O—C41 | 1.416 (3) | C27—C28 | 1.394 (3) |
N1—C33 | 1.412 (3) | C27—C31 | 1.514 (3) |
N2—C25 | 1.418 (3) | C28—C29 | 1.393 (3) |
C1—C2 | 1.404 (3) | C28—H28 | 0.95 |
C1—C5 | 1.414 (3) | C29—C30 | 1.390 (3) |
C1—C9 | 1.512 (3) | C29—C32 | 1.509 (3) |
C2—C3 | 1.435 (3) | C30—H30 | 0.95 |
C2—H2 | 0.95 | C31—H31A | 0.98 |
C3—C4 | 1.435 (3) | C31—H31B | 0.98 |
C4—C5 | 1.417 (3) | C31—H31C | 0.98 |
C4—H4 | 0.95 | C32—H32A | 0.98 |
C5—C6 | 1.515 (3) | C32—H32B | 0.98 |
C6—C7 | 1.556 (3) | C32—H32C | 0.98 |
C6—C10 | 1.557 (3) | C33—C38 | 1.396 (3) |
C6—H6 | 1.00 | C33—C34 | 1.403 (3) |
C7—C8 | 1.551 (3) | C34—C35 | 1.389 (3) |
C7—H7A | 0.99 | C34—H34 | 0.95 |
C7—H7B | 0.99 | C35—C36 | 1.392 (3) |
C8—C9 | 1.554 (3) | C35—C39 | 1.510 (3) |
C8—H8A | 0.99 | C36—C37 | 1.386 (3) |
C8—H8B | 0.99 | C36—H36 | 0.95 |
C9—C10 | 1.542 (3) | C37—C38 | 1.392 (3) |
C9—H9 | 1.00 | C37—C40 | 1.507 (3) |
C10—H10A | 0.99 | C38—H38 | 0.95 |
C10—H10B | 0.99 | C39—H39A | 0.98 |
C11—C12 | 1.413 (3) | C39—H39B | 0.98 |
C11—C15 | 1.413 (3) | C39—H39C | 0.98 |
C11—C19 | 1.514 (3) | C40—H40A | 0.98 |
C12—C13 | 1.440 (3) | C40—H40B | 0.98 |
C12—H12 | 0.95 | C40—H40C | 0.98 |
C13—C14 | 1.431 (3) | C41—C42 | 1.487 (4) |
C14—C15 | 1.401 (3) | C41—H41A | 0.99 |
C14—H14 | 0.95 | C41—H41B | 0.99 |
C15—C16 | 1.511 (3) | C42—H42A | 0.98 |
C16—C20 | 1.545 (3) | C42—H42B | 0.98 |
C16—C17 | 1.555 (3) | C42—H42C | 0.98 |
C16—H16 | 1.00 | C43—C44 | 1.492 (4) |
C17—C18 | 1.556 (3) | C43—H43A | 0.99 |
C17—H17A | 0.99 | C43—H43B | 0.99 |
C17—H17B | 0.99 | C44—H44A | 0.98 |
C18—C19 | 1.559 (3) | C44—H44B | 0.98 |
C18—H18A | 0.99 | C44—H44C | 0.98 |
N2—Zr—N1 | 106.64 (7) | C11—C12—H12 | 126.0 |
N2—Zr—C13 | 70.03 (7) | C13—C12—H12 | 126.0 |
N1—Zr—C13 | 118.92 (7) | Zr—C12—H12 | 117.6 |
N2—Zr—C3 | 119.32 (7) | C14—C13—C12 | 106.4 (2) |
N1—Zr—C3 | 69.59 (7) | C14—C13—Si1 | 119.3 (2) |
C13—Zr—C3 | 166.38 (7) | C12—C13—Si1 | 126.6 (2) |
N2—Zr—C4 | 136.22 (7) | C14—C13—Zr | 76.61 (12) |
N1—Zr—C4 | 92.99 (7) | C12—C13—Zr | 74.73 (12) |
C13—Zr—C4 | 132.75 (7) | Si1—C13—Zr | 89.79 (8) |
C3—Zr—C4 | 33.63 (7) | C15—C14—C13 | 108.7 (2) |
N2—Zr—C12 | 93.51 (7) | C15—C14—Zr | 77.05 (12) |
N1—Zr—C12 | 135.66 (7) | C13—C14—Zr | 70.21 (12) |
C13—Zr—C12 | 33.72 (7) | C15—C14—H14 | 125.6 |
C3—Zr—C12 | 132.69 (7) | C13—C14—H14 | 125.6 |
C4—Zr—C12 | 99.09 (7) | Zr—C14—H14 | 118.9 |
N2—Zr—C14 | 87.02 (7) | C14—C15—C11 | 108.5 (2) |
N1—Zr—C14 | 87.17 (7) | C14—C15—C16 | 142.6 (2) |
C13—Zr—C14 | 33.18 (7) | C11—C15—C16 | 107.4 (2) |
C3—Zr—C14 | 148.44 (7) | C14—C15—Zr | 71.47 (12) |
C4—Zr—C14 | 133.66 (7) | C11—C15—Zr | 72.80 (12) |
C12—Zr—C14 | 54.22 (7) | C16—C15—Zr | 130.43 (14) |
N2—Zr—C2 | 87.62 (7) | C15—C16—C20 | 100.3 (2) |
N1—Zr—C2 | 86.78 (7) | C15—C16—C17 | 104.4 (2) |
C13—Zr—C2 | 149.41 (7) | C20—C16—C17 | 99.8 (2) |
C3—Zr—C2 | 33.22 (7) | C15—C16—H16 | 116.6 |
C4—Zr—C2 | 54.14 (7) | C20—C16—H16 | 116.6 |
C12—Zr—C2 | 134.12 (7) | C17—C16—H16 | 116.6 |
C14—Zr—C2 | 170.44 (7) | C16—C17—C18 | 103.5 (2) |
N2—Zr—C5 | 109.38 (7) | C16—C17—H17A | 111.1 |
N1—Zr—C5 | 123.02 (7) | C18—C17—H17A | 111.1 |
C13—Zr—C5 | 114.21 (7) | C16—C17—H17B | 111.1 |
C3—Zr—C5 | 54.58 (7) | C18—C17—H17B | 111.1 |
C4—Zr—C5 | 32.40 (7) | H17A—C17—H17B | 109.0 |
C12—Zr—C5 | 84.04 (7) | C17—C18—C19 | 104.1 (2) |
C14—Zr—C5 | 136.53 (7) | C17—C18—H18A | 110.9 |
C2—Zr—C5 | 52.94 (7) | C19—C18—H18A | 110.9 |
N2—Zr—C11 | 123.37 (7) | C17—C18—H18B | 110.9 |
N1—Zr—C11 | 108.88 (7) | C19—C18—H18B | 110.9 |
C13—Zr—C11 | 54.48 (7) | H18A—C18—H18B | 109.0 |
C3—Zr—C11 | 113.78 (7) | C11—C19—C20 | 100.4 (2) |
C4—Zr—C11 | 83.82 (7) | C11—C19—C18 | 104.9 (2) |
C12—Zr—C11 | 32.25 (7) | C20—C19—C18 | 99.1 (2) |
C14—Zr—C11 | 52.94 (7) | C11—C19—H19 | 116.6 |
C2—Zr—C11 | 136.34 (7) | C20—C19—H19 | 116.6 |
C5—Zr—C11 | 85.78 (7) | C18—C19—H19 | 116.6 |
N2—Zr—C15 | 118.22 (7) | C16—C20—C19 | 95.8 (2) |
N1—Zr—C15 | 82.66 (7) | C16—C20—H20A | 112.6 |
C13—Zr—C15 | 53.85 (7) | C19—C20—H20A | 112.6 |
C3—Zr—C15 | 120.93 (7) | C16—C20—H20B | 112.6 |
C4—Zr—C15 | 102.58 (7) | C19—C20—H20B | 112.6 |
C12—Zr—C15 | 53.12 (7) | H20A—C20—H20B | 110.1 |
C14—Zr—C15 | 31.48 (6) | Si2—C21—H21A | 109.5 |
C2—Zr—C15 | 153.93 (7) | Si2—C21—H21B | 109.5 |
C5—Zr—C15 | 115.13 (7) | H21A—C21—H21B | 109.5 |
C11—Zr—C15 | 31.57 (7) | Si2—C21—H21C | 109.5 |
N2—Zr—C1 | 83.20 (7) | H21A—C21—H21C | 109.5 |
N1—Zr—C1 | 117.94 (7) | H21B—C21—H21C | 109.5 |
C13—Zr—C1 | 121.81 (7) | Si2—C22—H22A | 109.5 |
C3—Zr—C1 | 53.91 (7) | Si2—C22—H22B | 109.5 |
C4—Zr—C1 | 53.14 (7) | H22A—C22—H22B | 109.5 |
C12—Zr—C1 | 103.11 (7) | Si2—C22—H22C | 109.5 |
C14—Zr—C1 | 154.74 (7) | H22A—C22—H22C | 109.5 |
C2—Zr—C1 | 31.46 (7) | H22B—C22—H22C | 109.5 |
C5—Zr—C1 | 31.56 (7) | Si1—C23—H23A | 109.5 |
C11—Zr—C1 | 115.25 (7) | Si1—C23—H23B | 109.5 |
C15—Zr—C1 | 146.16 (7) | H23A—C23—H23B | 109.5 |
N2—Si1—C23 | 117.41 (10) | Si1—C23—H23C | 109.5 |
N2—Si1—C24 | 113.17 (10) | H23A—C23—H23C | 109.5 |
C23—Si1—C24 | 107.41 (11) | H23B—C23—H23C | 109.5 |
N2—Si1—C13 | 94.67 (9) | Si1—C24—H24A | 109.5 |
C23—Si1—C13 | 112.83 (10) | Si1—C24—H24B | 109.5 |
C24—Si1—C13 | 110.99 (10) | H24A—C24—H24B | 109.5 |
C23—Si1—Zr | 125.89 (8) | Si1—C24—H24C | 109.5 |
C24—Si1—Zr | 126.65 (8) | H24A—C24—H24C | 109.5 |
C13—Si1—Zr | 52.92 (6) | H24B—C24—H24C | 109.5 |
N1—Si2—C22 | 112.82 (10) | C26—C25—C30 | 117.6 (2) |
N1—Si2—C3 | 94.46 (9) | C26—C25—N2 | 121.9 (2) |
C22—Si2—C3 | 111.85 (11) | C30—C25—N2 | 120.5 (2) |
N1—Si2—C21 | 117.18 (10) | C27—C26—C25 | 121.7 (2) |
C22—Si2—C21 | 107.90 (11) | C27—C26—H26 | 119.1 |
C3—Si2—C21 | 112.22 (11) | C25—C26—H26 | 119.1 |
C22—Si2—Zr | 127.16 (8) | C26—C27—C28 | 119.0 (2) |
C3—Si2—Zr | 52.75 (7) | C26—C27—C31 | 120.0 (2) |
C21—Si2—Zr | 124.87 (8) | C28—C27—C31 | 120.9 (2) |
C43—O—C41 | 115.5 (2) | C29—C28—C27 | 121.0 (2) |
C33—N1—Si2 | 126.07 (15) | C29—C28—H28 | 119.5 |
C33—N1—Zr | 128.32 (14) | C27—C28—H28 | 119.5 |
Si2—N1—Zr | 105.55 (9) | C30—C29—C28 | 118.6 (2) |
C25—N2—Si1 | 126.21 (14) | C30—C29—C32 | 120.3 (2) |
C25—N2—Zr | 128.38 (14) | C28—C29—C32 | 121.1 (2) |
Si1—N2—Zr | 105.27 (8) | C29—C30—C25 | 122.1 (2) |
C2—C1—C5 | 108.3 (2) | C29—C30—H30 | 118.9 |
C2—C1—C9 | 143.2 (2) | C25—C30—H30 | 118.9 |
C5—C1—C9 | 107.0 (2) | C27—C31—H31A | 109.5 |
C2—C1—Zr | 71.35 (12) | C27—C31—H31B | 109.5 |
C5—C1—Zr | 72.34 (12) | H31A—C31—H31B | 109.5 |
C9—C1—Zr | 130.39 (15) | C27—C31—H31C | 109.5 |
C1—C2—C3 | 108.9 (2) | H31A—C31—H31C | 109.5 |
C1—C2—Zr | 77.18 (12) | H31B—C31—H31C | 109.5 |
C3—C2—Zr | 70.04 (12) | C29—C32—H32A | 109.5 |
C1—C2—H2 | 125.6 | C29—C32—H32B | 109.5 |
C3—C2—H2 | 125.6 | H32A—C32—H32B | 109.5 |
Zr—C2—H2 | 118.9 | C29—C32—H32C | 109.5 |
C2—C3—C4 | 106.4 (2) | H32A—C32—H32C | 109.5 |
C2—C3—Si2 | 119.9 (2) | H32B—C32—H32C | 109.5 |
C4—C3—Si2 | 126.3 (2) | C38—C33—C34 | 117.4 (2) |
C2—C3—Zr | 76.74 (12) | C38—C33—N1 | 122.2 (2) |
C4—C3—Zr | 74.62 (12) | C34—C33—N1 | 120.4 (2) |
Si2—C3—Zr | 90.11 (8) | C35—C34—C33 | 121.7 (2) |
C5—C4—C3 | 108.2 (2) | C35—C34—H34 | 119.1 |
C5—C4—Zr | 76.76 (12) | C33—C34—H34 | 119.1 |
C3—C4—Zr | 71.75 (12) | C34—C35—C36 | 119.0 (2) |
C5—C4—H4 | 125.9 | C34—C35—C39 | 120.5 (2) |
C3—C4—H4 | 125.9 | C36—C35—C39 | 120.4 (2) |
Zr—C4—H4 | 117.5 | C37—C36—C35 | 120.9 (2) |
C1—C5—C4 | 108.2 (2) | C37—C36—H36 | 119.5 |
C1—C5—C6 | 106.8 (2) | C35—C36—H36 | 119.5 |
C4—C5—C6 | 143.1 (2) | C36—C37—C38 | 119.0 (2) |
C1—C5—Zr | 76.10 (12) | C36—C37—C40 | 121.2 (2) |
C4—C5—Zr | 70.85 (12) | C38—C37—C40 | 119.8 (2) |
C6—C5—Zr | 129.4 (2) | C37—C38—C33 | 121.9 (2) |
C5—C6—C7 | 105.0 (2) | C37—C38—H38 | 119.0 |
C5—C6—C10 | 99.9 (2) | C33—C38—H38 | 119.0 |
C7—C6—C10 | 99.5 (2) | C35—C39—H39A | 109.5 |
C5—C6—H6 | 116.6 | C35—C39—H39B | 109.5 |
C7—C6—H6 | 116.6 | H39A—C39—H39B | 109.5 |
C10—C6—H6 | 116.6 | C35—C39—H39C | 109.5 |
C8—C7—C6 | 103.8 (2) | H39A—C39—H39C | 109.5 |
C8—C7—H7A | 111.0 | H39B—C39—H39C | 109.5 |
C6—C7—H7A | 111.0 | C37—C40—H40A | 109.5 |
C8—C7—H7B | 111.0 | C37—C40—H40B | 109.5 |
C6—C7—H7B | 111.0 | H40A—C40—H40B | 109.5 |
H7A—C7—H7B | 109.0 | C37—C40—H40C | 109.5 |
C7—C8—C9 | 103.9 (2) | H40A—C40—H40C | 109.5 |
C7—C8—H8A | 111.0 | H40B—C40—H40C | 109.5 |
C9—C8—H8A | 111.0 | O—C41—C42 | 109.4 (2) |
C7—C8—H8B | 111.0 | O—C41—H41A | 109.8 |
C9—C8—H8B | 111.0 | C42—C41—H41A | 109.8 |
H8A—C8—H8B | 109.0 | O—C41—H41B | 109.8 |
C1—C9—C10 | 100.1 (2) | C42—C41—H41B | 109.8 |
C1—C9—C8 | 105.3 (2) | H41A—C41—H41B | 108.3 |
C10—C9—C8 | 99.8 (2) | C41—C42—H42A | 109.5 |
C1—C9—H9 | 116.4 | C41—C42—H42B | 109.5 |
C10—C9—H9 | 116.4 | H42A—C42—H42B | 109.5 |
C8—C9—H9 | 116.4 | C41—C42—H42C | 109.5 |
C9—C10—C6 | 95.5 (2) | H42A—C42—H42C | 109.5 |
C9—C10—H10A | 112.6 | H42B—C42—H42C | 109.5 |
C6—C10—H10A | 112.6 | O—C43—C44 | 109.0 (2) |
C9—C10—H10B | 112.6 | O—C43—H43A | 109.9 |
C6—C10—H10B | 112.6 | C44—C43—H43A | 109.9 |
H10A—C10—H10B | 110.1 | O—C43—H43B | 109.9 |
C12—C11—C15 | 108.3 (2) | C44—C43—H43B | 109.9 |
C12—C11—C19 | 143.2 (2) | H43A—C43—H43B | 108.3 |
C15—C11—C19 | 106.6 (2) | C43—C44—H44A | 109.5 |
C12—C11—Zr | 70.90 (11) | C43—C44—H44B | 109.5 |
C15—C11—Zr | 75.64 (12) | H44A—C44—H44B | 109.5 |
C19—C11—Zr | 130.16 (14) | C43—C44—H44C | 109.5 |
C11—C12—C13 | 108.0 (2) | H44A—C44—H44C | 109.5 |
C11—C12—Zr | 76.85 (12) | H44B—C44—H44C | 109.5 |
C13—C12—Zr | 71.55 (11) | ||
C22—Si2—N1—C33 | −61.7 (2) | C23—Si1—C13—C12 | 47.9 (2) |
C3—Si2—N1—C33 | −177.7 (2) | C24—Si1—C13—C12 | 168.5 (2) |
C21—Si2—N1—C33 | 64.5 (2) | C12—C13—C14—C15 | 1.3 (2) |
Zr—Si2—N1—C33 | 177.4 (2) | Si1—C13—C14—C15 | −150.1 (2) |
C22—Si2—N1—Zr | 120.82 (11) | C13—C14—C15—C11 | −0.3 (2) |
C3—Si2—N1—Zr | 4.85 (10) | C13—C14—C15—C16 | −163.0 (3) |
C21—Si2—N1—Zr | −112.96 (11) | C12—C11—C15—C14 | −0.9 (2) |
Zr—Si2—N1—Zr | 0.0 | C19—C11—C15—C14 | −168.8 (2) |
N2—Zr—N1—C33 | 63.0 (2) | C12—C11—C15—C16 | 168.2 (2) |
N2—Zr—N1—Si2 | −119.64 (8) | C19—C11—C15—C16 | 0.3 (2) |
C23—Si1—N2—C25 | 61.7 (2) | C14—C15—C16—C20 | −165.0 (3) |
C24—Si1—N2—C25 | −64.3 (2) | C11—C15—C16—C20 | 32.2 (2) |
C13—Si1—N2—C25 | −179.5 (2) | C14—C15—C16—C17 | 92.0 (3) |
C23—Si1—N2—Zr | −114.26 (10) | C11—C15—C16—C17 | −70.9 (2) |
C24—Si1—N2—Zr | 119.70 (10) | C15—C16—C17—C18 | 68.4 (2) |
C13—Si1—N2—Zr | 4.49 (10) | C20—C16—C17—C18 | −35.0 (2) |
N1—Zr—N2—C25 | 65.1 (2) | C16—C17—C18—C19 | −0.6 (2) |
N1—Zr—N2—Si1 | −118.98 (9) | C12—C11—C19—C20 | 166.8 (3) |
C5—C1—C2—C3 | 0.1 (2) | C15—C11—C19—C20 | −32.6 (2) |
C9—C1—C2—C3 | −162.9 (3) | C12—C11—C19—C18 | −90.8 (3) |
C1—C2—C3—C4 | 1.2 (2) | C15—C11—C19—C18 | 69.8 (2) |
C1—C2—C3—Si2 | −150.4 (2) | C17—C18—C19—C11 | −67.6 (2) |
N1—Si2—C3—C2 | 70.7 (2) | C17—C18—C19—C20 | 35.8 (2) |
C22—Si2—C3—C2 | −46.1 (2) | C15—C16—C20—C19 | −49.7 (2) |
C21—Si2—C3—C2 | −167.5 (2) | C17—C16—C20—C19 | 57.1 (2) |
N1—Si2—C3—C4 | −74.9 (2) | C11—C19—C20—C16 | 50.0 (2) |
C22—Si2—C3—C4 | 168.3 (2) | C18—C19—C20—C16 | −57.0 (2) |
C21—Si2—C3—C4 | 46.8 (2) | Si1—N2—C25—C26 | −54.2 (3) |
C2—C3—C4—C5 | −2.1 (2) | Zr—N2—C25—C26 | 120.9 (2) |
Si2—C3—C4—C5 | 147.2 (2) | Si1—N2—C25—C30 | 127.7 (2) |
C2—C1—C5—C4 | −1.4 (2) | Zr—N2—C25—C30 | −57.2 (3) |
C9—C1—C5—C4 | 168.1 (2) | C30—C25—C26—C27 | 1.2 (3) |
C2—C1—C5—C6 | −169.8 (2) | N2—C25—C26—C27 | −176.9 (2) |
C9—C1—C5—C6 | −0.4 (2) | C25—C26—C27—C28 | −1.9 (3) |
Zr—C1—C5—C6 | 127.5 (2) | C25—C26—C27—C31 | 175.5 (2) |
C3—C4—C5—C1 | 2.1 (2) | C26—C27—C28—C29 | 1.0 (3) |
C3—C4—C5—C6 | 163.5 (3) | C31—C27—C28—C29 | −176.4 (2) |
C1—C5—C6—C7 | 70.3 (2) | C27—C28—C29—C30 | 0.5 (3) |
C4—C5—C6—C7 | −91.2 (3) | C27—C28—C29—C32 | 179.4 (2) |
C1—C5—C6—C10 | −32.4 (2) | C28—C29—C30—C25 | −1.1 (3) |
C4—C5—C6—C10 | 166.1 (3) | C32—C29—C30—C25 | 180.0 (2) |
C5—C6—C7—C8 | −67.8 (2) | C26—C25—C30—C29 | 0.3 (3) |
C10—C6—C7—C8 | 35.2 (2) | N2—C25—C30—C29 | 178.5 (2) |
C6—C7—C8—C9 | 0.0 (2) | Si2—N1—C33—C38 | −47.2 (3) |
C2—C1—C9—C10 | −163.5 (3) | Zr—N1—C33—C38 | 129.6 (2) |
C5—C1—C9—C10 | 33.4 (2) | Si2—N1—C33—C34 | 133.1 (2) |
C2—C1—C9—C8 | 93.3 (3) | Zr—N1—C33—C34 | −50.0 (3) |
C5—C1—C9—C8 | −69.8 (2) | C38—C33—C34—C35 | −0.2 (3) |
C7—C8—C9—C1 | 67.9 (2) | N1—C33—C34—C35 | 179.5 (2) |
C7—C8—C9—C10 | −35.6 (2) | C33—C34—C35—C36 | −0.9 (3) |
C1—C9—C10—C6 | −50.8 (2) | C33—C34—C35—C39 | 177.2 (2) |
C8—C9—C10—C6 | 56.8 (2) | C34—C35—C36—C37 | 1.1 (3) |
C5—C6—C10—C9 | 50.5 (2) | C39—C35—C36—C37 | −177.0 (2) |
C7—C6—C10—C9 | −56.7 (2) | C35—C36—C37—C38 | −0.3 (3) |
C15—C11—C12—C13 | 1.7 (2) | C35—C36—C37—C40 | −179.3 (2) |
C19—C11—C12—C13 | 162.1 (3) | C36—C37—C38—C33 | −0.8 (3) |
C11—C12—C13—C14 | −1.8 (2) | C40—C37—C38—C33 | 178.2 (2) |
C11—C12—C13—Si1 | 146.9 (2) | C34—C33—C38—C37 | 1.1 (3) |
N2—Si1—C13—C14 | 70.7 (2) | N1—C33—C38—C37 | −178.6 (2) |
C23—Si1—C13—C14 | −166.9 (2) | C43—O—C41—C42 | −179.1 (3) |
C24—Si1—C13—C14 | −46.3 (2) | C41—O—C43—C44 | −177.8 (3) |
N2—Si1—C13—C12 | −74.4 (2) |
Experimental details
Crystal data | |
Chemical formula | [Zr(C20H25NSi)2]·C4H10O |
Mr | 780.34 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 10.7036 (2), 11.6479 (2), 17.4618 (3) |
α, β, γ (°) | 70.848 (1), 78.069 (1), 84.194 (1) |
V (Å3) | 2010.81 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.37 |
Crystal size (mm) | 0.35 × 0.35 × 0.04 |
Data collection | |
Diffractometer | Nonius Kappa CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 50007, 9121, 7028 |
Rint | 0.051 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.077, 1.03 |
No. of reflections | 9118 |
No. of parameters | 461 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.51, −0.33 |
Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski & Minor, 1997), SHELXS86 (Sheldrick, 1990), SHELXL93 (Sheldrick, 1993), ORTEPII (Johnson, 1976).
Zr—N2 | 2.135 (2) | C2—C3 | 1.435 (3) |
Zr—N1 | 2.143 (2) | C3—C4 | 1.435 (3) |
Zr—C13 | 2.461 (2) | C4—C5 | 1.417 (3) |
Zr—C3 | 2.461 (2) | C5—C6 | 1.515 (3) |
Zr—C4 | 2.499 (2) | C6—C7 | 1.556 (3) |
Zr—C12 | 2.502 (2) | C6—C10 | 1.557 (3) |
Zr—C14 | 2.544 (2) | C7—C8 | 1.551 (3) |
Zr—C2 | 2.549 (2) | C8—C9 | 1.554 (3) |
Zr—C5 | 2.575 (2) | C9—C10 | 1.542 (3) |
Zr—C11 | 2.579 (2) | C11—C12 | 1.413 (3) |
Zr—C15 | 2.615 (2) | C11—C15 | 1.413 (3) |
Zr—C1 | 2.623 (2) | C11—C19 | 1.514 (3) |
Si1—N2 | 1.733 (2) | C12—C13 | 1.440 (3) |
Si1—C13 | 1.869 (2) | C13—C14 | 1.431 (3) |
Si2—N1 | 1.728 (2) | C14—C15 | 1.401 (3) |
Si2—C3 | 1.867 (2) | C15—C16 | 1.511 (3) |
N1—C33 | 1.412 (3) | C16—C20 | 1.545 (3) |
N2—C25 | 1.418 (3) | C16—C17 | 1.555 (3) |
C1—C2 | 1.404 (3) | C17—C18 | 1.556 (3) |
C1—C5 | 1.414 (3) | C18—C19 | 1.559 (3) |
C1—C9 | 1.512 (3) | C19—C20 | 1.549 (3) |
N2—Zr—N1 | 106.64 (7) | C9—C10—C6 | 95.5 (2) |
N2—Si1—C13 | 94.67 (9) | C12—C11—C15 | 108.3 (2) |
N1—Si2—C3 | 94.46 (9) | C12—C11—C19 | 143.2 (2) |
C2—C1—C5 | 108.3 (2) | C15—C11—C19 | 106.6 (2) |
C2—C1—C9 | 143.2 (2) | C11—C12—C13 | 108.0 (2) |
C5—C1—C9 | 107.0 (2) | C14—C13—C12 | 106.4 (2) |
C1—C2—C3 | 108.9 (2) | C15—C14—C13 | 108.7 (2) |
C2—C3—C4 | 106.4 (2) | C14—C15—C11 | 108.5 (2) |
C5—C4—C3 | 108.2 (2) | C14—C15—C16 | 142.6 (2) |
C1—C5—C4 | 108.2 (2) | C11—C15—C16 | 107.4 (2) |
C1—C5—C6 | 106.8 (2) | C15—C16—C20 | 100.3 (2) |
C4—C5—C6 | 143.1 (2) | C15—C16—C17 | 104.4 (2) |
C5—C6—C7 | 105.0 (2) | C20—C16—C17 | 99.8 (2) |
C5—C6—C10 | 99.9 (2) | C16—C17—C18 | 103.5 (2) |
C7—C6—C10 | 99.5 (2) | C17—C18—C19 | 104.1 (2) |
C8—C7—C6 | 103.8 (2) | C11—C19—C20 | 100.4 (2) |
C7—C8—C9 | 103.9 (2) | C11—C19—C18 | 104.9 (2) |
C1—C9—C10 | 100.1 (2) | C20—C19—C18 | 99.1 (2) |
C1—C9—C8 | 105.3 (2) | C16—C20—C19 | 95.8 (2) |
C10—C9—C8 | 99.8 (2) |
Cg1-Zr | 2.2361 (10) |
Cg2-Zr | 2.2352 (10) |
Cg1-Zr-Cg2 | 134.17 (4) |
Cg1-Zr-N1 | 99.06 (6) |
Cg1-Zr-N2 | 107.96 (6) |
Cg2-Zr-N1 | 107.47 (6) |
Cg2-Zr-N2 | 99.44 (6) |
Cg1 is the centroid of the C1-C5 ring. Cg2 is the centroid of the C11-C15 ring. |
`Constrained geometry' (CG) catalysts can be obtained via different methods. Group 4 ansa monocyclopentadienyl amido complexes can be synthesized by the amine-elimination reaction with excellent results (Hughes et al., 1993; Herrmann & Morawietz, 1994; Carpenetti et al., 1996). When use is made of the synthetic pathway first employed by Bercaw (Shapiro et al., 1990, 1994) and then by Okuda (Okuda, 1990; Okuda et al., 1995), the CG catalyst yield is strongly influenced by the degree of cyclopentadienyl (Cp) substitution. Unsubstituted Cp rings give ansa-Cp amido complexes in very low yield, whereas reactions with substituted Cp rings are quite efficient. We have demonstrated previously that the classical half-sandwich synthetic strategy can be readily adapted to the preparation of isodicyclopentadienyl amido zirconium dichloro complexes (Gentil et al., 2000) by reaction with solid zirconium tetrachloride. In this paper, we report the preparation and structure of the complex bis{N-(3,5-dimethylphenyl)-N-[(η5-isodicyclopentadien- 2-yl)dimethylsilyl]amido-κN}zirconium(II) diethyl ether solvate, obtained by the use of high amido dilithium salt concentrations relative to zirconium tetrachloride. \sch
Complex (I) has approximate C2 symmetry. The ligand has a constrained geometry, which is characterized by the small values of 94.46 (9) and 94.67 (9)°, respectively, for the N1—Si2—C3 and N2—Si1—C13 angles. Further evidence of the constrained nature of this ligand is seen in the displacement of each Si atom from its adjacent Cp ring: the angle between the Si1—C13 bond and its adjacent Cp ring is 25.8 (1)°, and the angle between the Si2—C3 bond and its adjacent Cp ring is 25.5 (1)°.
This Zr complex displays features characteristic of non-bridged isodicyclopentadienyl zirconium complexes (Gallucci et al., 1987; Gobley et al., 1998). The Cg1—Zr—Cg2 angle of 134.17 (4)°, where Cg1 and Cg2 are the centroids of the C1—C5 and C11—C15 rings, respectively, is slightly larger than the corresponding angles in (isodiCp)2ZrCl2 (129.0°) and (isodiCpPPh2)2ZrCl2 [129.02 (5)°]. The isodicyclopentadienyl ligands are found to be in a gauche-like configuration with respect to each other (Gobley et al., 1998).
The metal-Cring distances [2.461–2.623 (2) Å for atoms C1—C5 and 2.461–2.615 (2) Å for atoms C11—C15] are also larger than for the two above-mentioned isodicyclopentadienyl complexes. The shorter Zr—C ring distances involve atoms C3 and C13, which are both bonded to Si atoms. These short distances are likely to be due to the constrained geometry of this ligand. To the best of our knowledge, the Zr—C1 and Zr—C15 distances of 2.623 (2) and 2.615 (2) Å, respectively, are the largest observed for Zr—C bonds in isodicyclopentadienyl complexes. Both the Cp—Zr—Cp angle and the Zr—Cring distances are comparable with those in the doubly bridged amido spiro metallocene Zr[CpSi(CH3)2N-phenyl]2 reported by Herrmann et al. (1994).
As observed in all structures involving an isodicyclopentadienyl ligand with exo complexation, there is a slight bending in this ligand about the bond common to the Cp ring and the norbornane fragment, and this bending is in the endo direction. The dihedral angle between the least-squares planes defined by C1—C5 and C1—C5—C6—C9 is 10.6 (1)°, while the angle between the planes defined by C11—C15 and C11—C15—C16—C19 is 11.0 (1)°. These values are midway between those for an isodiCp half-sandwich zirconium complex [9.5 (1)° for exo-isodiCpSiMe2N-tBuZr(CH2SiMe3)2 (Gentil et al., 2000)] and a bis(isodiCp) zirconium dichloride complex [13.0 (3) and 14.1 (4)° for (isodiCpPPh2)2ZrCl2 (Gobley et al., 1998)].
The Zr—N bond lengths of 2.143 (2) Å for N1 and 2.135 (2) Å for N2 are longer than the Zr—N bond length of 2.086 (1) Å in the exo-isodiCpSiMe2N-tBuZr(CH2SiMe3)2 complex (Gentil et al., 2000), but are quite comparable with the Zr—N bond lengths of 2.142 (2) and 2.143 (2) Å in (η5-C5H4—CHMe-NPh-κN)2Zr (Kunz et al., 2002) and 2.137 (2) and 2.127 (2) Å in [η5-C5H4—Si(Me)2—NPh-κN]2Zr (Herrmann et al., 1994). The sums of the bond angles at the two N atoms are essentially 360° (360.0° for N1 and 359.9° for N2), indicative of trigonal-planar N atoms.