Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104018840/fa1076sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104018840/fa1076Isup2.hkl |
CCDC reference: 251301
The title compound was synthesized from Cp''2TiMe and dry NH3 in n-hexane, in a manner similar to that used for (C5Me5)2Ti(NH2) (Brady et al., 1994). Dichroic (green and brown) crystals were grown by slow cooling of a saturated hexane solution to 193 K. The crystal was handled under a nitrogen atmosphere, mounted on a glass fiber with Paratone-N hydrocarbon oil and cooled to 133 (2) K for data collection.
H atoms on the trimethylsilyl groups, as well as those on the cyclopentadienyl rings, were included in calculated positions, with C—H distances in the range 0.95–0.98 Å, and refined using a riding model, with Uiso(H) = 1.5Ueq(C). Please check added text. The amide H atoms (H23A and H23B) were located using standard difference Fourier techniques and refined isotropically.
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
[Ti(C11H21Si2)2(NH2)] | F(000) = 1044 |
Mr = 482.84 | Dx = 1.128 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 5983 reflections |
a = 13.0945 (3) Å | θ = 2–51.2° |
b = 16.5699 (3) Å | µ = 0.48 mm−1 |
c = 13.1869 (2) Å | T = 133 K |
β = 96.488 (1)° | Block, dichroic (green/brown) |
V = 2842.90 (9) Å3 | 0.38 × 0.32 × 0.18 mm |
Z = 4 |
Bruker SMART 1K CCD area-detector diffractometer | 5071 independent reflections |
Radiation source: fine-focus sealed tube | 3874 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
ω scans | θmax = 26.1°, θmin = 2.0° |
Absorption correction: multi-scan (Blessing, 1995) | h = −16→13 |
Tmin = 0.839, Tmax = 0.919 | k = −20→18 |
13362 measured reflections | l = −15→14 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.13 | w = 1/[σ2(Fo2) + (0.0201P)2 + 5.0672P] where P = (Fo2 + 2Fc2)/3 |
5071 reflections | (Δ/σ)max < 0.001 |
273 parameters | Δρmax = 0.47 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
[Ti(C11H21Si2)2(NH2)] | V = 2842.90 (9) Å3 |
Mr = 482.84 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.0945 (3) Å | µ = 0.48 mm−1 |
b = 16.5699 (3) Å | T = 133 K |
c = 13.1869 (2) Å | 0.38 × 0.32 × 0.18 mm |
β = 96.488 (1)° |
Bruker SMART 1K CCD area-detector diffractometer | 5071 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 3874 reflections with I > 2σ(I) |
Tmin = 0.839, Tmax = 0.919 | Rint = 0.059 |
13362 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.13 | Δρmax = 0.47 e Å−3 |
5071 reflections | Δρmin = −0.32 e Å−3 |
273 parameters |
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 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 > 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 | ||
Ti1 | 0.01970 (4) | 0.22140 (4) | 0.85769 (5) | 0.01785 (16) | |
Si1 | −0.04813 (7) | 0.00459 (6) | 0.75035 (8) | 0.0241 (2) | |
Si2 | 0.30932 (7) | 0.19111 (6) | 0.90584 (8) | 0.0256 (2) | |
Si3 | 0.07909 (7) | 0.45105 (6) | 0.83708 (8) | 0.0234 (2) | |
Si4 | −0.25685 (7) | 0.23428 (6) | 0.91279 (8) | 0.0247 (2) | |
N1 | 0.0049 (3) | 0.2395 (2) | 0.7120 (3) | 0.0316 (8) | |
H23A | 0.019 (3) | 0.208 (3) | 0.665 (3) | 0.044 (13)* | |
H23B | −0.018 (3) | 0.283 (3) | 0.680 (3) | 0.050 (13)* | |
C1 | 0.0299 (2) | 0.0762 (2) | 0.8373 (3) | 0.0217 (8) | |
C2 | 0.1227 (2) | 0.11158 (19) | 0.8135 (3) | 0.0214 (8) | |
H2 | 0.1461 | 0.1097 | 0.7479 | 0.026* | |
C3 | 0.1763 (2) | 0.1501 (2) | 0.8998 (2) | 0.0211 (7) | |
C4 | 0.1136 (3) | 0.1376 (2) | 0.9799 (3) | 0.0221 (8) | |
H4 | 0.1289 | 0.1562 | 1.0481 | 0.027* | |
C5 | 0.0256 (3) | 0.0934 (2) | 0.9422 (3) | 0.0241 (8) | |
H5 | −0.0281 | 0.0777 | 0.9809 | 0.029* | |
C6 | 0.0103 (3) | 0.36520 (19) | 0.8918 (3) | 0.0209 (7) | |
C7 | −0.0894 (3) | 0.33583 (19) | 0.8549 (3) | 0.0220 (8) | |
H7 | −0.1272 | 0.3525 | 0.7927 | 0.026* | |
C8 | −0.1252 (2) | 0.2785 (2) | 0.9227 (3) | 0.0218 (7) | |
C9 | −0.0453 (3) | 0.2735 (2) | 1.0060 (3) | 0.0236 (8) | |
H9 | −0.0471 | 0.2411 | 1.0652 | 0.028* | |
C10 | 0.0364 (3) | 0.32421 (19) | 0.9866 (3) | 0.0233 (8) | |
H10 | 0.0991 | 0.3303 | 1.0297 | 0.028* | |
C11 | 0.3222 (3) | 0.2890 (2) | 0.9756 (3) | 0.0335 (9) | |
H11A | 0.2745 | 0.3284 | 0.9410 | 0.050* | |
H11B | 0.3928 | 0.3089 | 0.9768 | 0.050* | |
H11C | 0.3060 | 0.2811 | 1.0457 | 0.050* | |
C12 | 0.3983 (3) | 0.1167 (2) | 0.9758 (3) | 0.0421 (11) | |
H12A | 0.4693 | 0.1360 | 0.9776 | 0.063* | |
H12B | 0.3916 | 0.0645 | 0.9409 | 0.063* | |
H12C | 0.3808 | 0.1107 | 1.0458 | 0.063* | |
C13 | 0.3410 (3) | 0.2051 (2) | 0.7725 (3) | 0.0344 (9) | |
H13A | 0.2951 | 0.2458 | 0.7379 | 0.052* | |
H13B | 0.3322 | 0.1538 | 0.7356 | 0.052* | |
H13C | 0.4124 | 0.2232 | 0.7739 | 0.052* | |
C14 | 0.0186 (3) | −0.0950 (2) | 0.7648 (3) | 0.0321 (9) | |
H14A | −0.0193 | −0.1347 | 0.7202 | 0.048* | |
H14B | 0.0215 | −0.1129 | 0.8359 | 0.048* | |
H14C | 0.0885 | −0.0896 | 0.7460 | 0.048* | |
C15 | −0.0502 (4) | 0.0397 (3) | 0.6168 (3) | 0.0500 (12) | |
H15A | −0.0853 | −0.0005 | 0.5707 | 0.075* | |
H15B | 0.0204 | 0.0468 | 0.6006 | 0.075* | |
H15C | −0.0869 | 0.0912 | 0.6086 | 0.075* | |
C16 | −0.1822 (3) | −0.0083 (2) | 0.7822 (4) | 0.0433 (11) | |
H16A | −0.2197 | 0.0426 | 0.7703 | 0.065* | |
H16B | −0.1808 | −0.0237 | 0.8541 | 0.065* | |
H16C | −0.2166 | −0.0506 | 0.7390 | 0.065* | |
C17 | −0.0222 (3) | 0.5200 (2) | 0.7745 (3) | 0.0374 (10) | |
H17A | 0.0105 | 0.5670 | 0.7467 | 0.056* | |
H17B | −0.0669 | 0.5378 | 0.8249 | 0.056* | |
H17C | −0.0632 | 0.4912 | 0.7191 | 0.056* | |
C18 | 0.1574 (3) | 0.5047 (2) | 0.9436 (3) | 0.0361 (10) | |
H18A | 0.2041 | 0.4663 | 0.9816 | 0.054* | |
H18B | 0.1117 | 0.5283 | 0.9896 | 0.054* | |
H18C | 0.1974 | 0.5476 | 0.9156 | 0.054* | |
C19 | 0.1639 (3) | 0.4194 (2) | 0.7403 (3) | 0.0359 (10) | |
H19A | 0.1982 | 0.4668 | 0.7156 | 0.054* | |
H19B | 0.1226 | 0.3931 | 0.6831 | 0.054* | |
H19C | 0.2157 | 0.3814 | 0.7714 | 0.054* | |
C20 | −0.3418 (3) | 0.3054 (2) | 0.9748 (3) | 0.0359 (10) | |
H20A | −0.4127 | 0.2854 | 0.9654 | 0.054* | |
H20B | −0.3389 | 0.3589 | 0.9436 | 0.054* | |
H20C | −0.3183 | 0.3091 | 1.0479 | 0.054* | |
C21 | −0.3045 (3) | 0.2237 (2) | 0.7743 (3) | 0.0346 (9) | |
H21A | −0.2549 | 0.1923 | 0.7402 | 0.052* | |
H21B | −0.3125 | 0.2773 | 0.7431 | 0.052* | |
H21C | −0.3710 | 0.1959 | 0.7671 | 0.052* | |
C22 | −0.2569 (3) | 0.1359 (2) | 0.9812 (3) | 0.0359 (10) | |
H22A | −0.2126 | 0.0976 | 0.9503 | 0.054* | |
H22B | −0.3271 | 0.1147 | 0.9761 | 0.054* | |
H22C | −0.2310 | 0.1438 | 1.0532 | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ti1 | 0.0200 (3) | 0.0162 (3) | 0.0171 (3) | 0.0006 (2) | 0.0010 (2) | 0.0007 (3) |
Si1 | 0.0255 (5) | 0.0172 (5) | 0.0278 (6) | −0.0011 (4) | −0.0053 (4) | −0.0002 (4) |
Si2 | 0.0190 (5) | 0.0245 (5) | 0.0322 (6) | 0.0002 (4) | −0.0023 (4) | −0.0043 (4) |
Si3 | 0.0223 (5) | 0.0188 (5) | 0.0292 (6) | −0.0011 (4) | 0.0043 (4) | 0.0014 (4) |
Si4 | 0.0210 (5) | 0.0246 (5) | 0.0290 (6) | −0.0008 (4) | 0.0051 (4) | 0.0016 (4) |
N1 | 0.049 (2) | 0.0250 (18) | 0.0202 (18) | 0.0087 (16) | 0.0007 (15) | 0.0014 (15) |
C1 | 0.0223 (18) | 0.0177 (17) | 0.024 (2) | 0.0020 (14) | −0.0014 (15) | 0.0016 (14) |
C2 | 0.0229 (18) | 0.0185 (17) | 0.0230 (19) | 0.0031 (14) | 0.0034 (15) | −0.0002 (14) |
C3 | 0.0233 (18) | 0.0182 (18) | 0.0207 (19) | 0.0035 (14) | −0.0026 (15) | 0.0011 (15) |
C4 | 0.0277 (19) | 0.0182 (17) | 0.0190 (19) | 0.0083 (15) | −0.0030 (15) | 0.0001 (14) |
C5 | 0.0248 (19) | 0.0179 (18) | 0.030 (2) | 0.0016 (15) | 0.0023 (15) | 0.0054 (15) |
C6 | 0.0240 (18) | 0.0137 (16) | 0.0255 (19) | 0.0008 (14) | 0.0046 (15) | −0.0029 (14) |
C7 | 0.0244 (18) | 0.0178 (17) | 0.0238 (19) | 0.0042 (14) | 0.0034 (15) | 0.0027 (14) |
C8 | 0.0213 (18) | 0.0203 (17) | 0.0242 (19) | 0.0046 (15) | 0.0044 (14) | −0.0011 (15) |
C9 | 0.0263 (19) | 0.0244 (19) | 0.0206 (19) | 0.0044 (15) | 0.0044 (15) | −0.0009 (15) |
C10 | 0.0259 (19) | 0.0172 (18) | 0.026 (2) | 0.0024 (15) | −0.0001 (15) | −0.0048 (15) |
C11 | 0.025 (2) | 0.036 (2) | 0.038 (2) | −0.0010 (17) | −0.0039 (17) | −0.0127 (18) |
C12 | 0.032 (2) | 0.037 (2) | 0.053 (3) | 0.0071 (19) | −0.012 (2) | −0.002 (2) |
C13 | 0.032 (2) | 0.030 (2) | 0.042 (2) | −0.0047 (17) | 0.0096 (18) | −0.0043 (18) |
C14 | 0.035 (2) | 0.0209 (19) | 0.038 (2) | −0.0004 (16) | −0.0046 (18) | −0.0030 (17) |
C15 | 0.084 (3) | 0.030 (2) | 0.031 (2) | −0.015 (2) | −0.012 (2) | −0.0005 (19) |
C16 | 0.028 (2) | 0.030 (2) | 0.070 (3) | 0.0014 (18) | −0.004 (2) | −0.012 (2) |
C17 | 0.035 (2) | 0.029 (2) | 0.048 (3) | −0.0016 (18) | 0.0021 (19) | 0.0155 (19) |
C18 | 0.041 (2) | 0.024 (2) | 0.043 (3) | −0.0046 (18) | 0.0019 (19) | 0.0002 (18) |
C19 | 0.033 (2) | 0.035 (2) | 0.042 (2) | −0.0029 (18) | 0.0124 (18) | 0.0025 (19) |
C20 | 0.025 (2) | 0.040 (2) | 0.044 (3) | 0.0005 (18) | 0.0083 (18) | −0.002 (2) |
C21 | 0.032 (2) | 0.038 (2) | 0.033 (2) | −0.0046 (18) | 0.0000 (17) | −0.0005 (19) |
C22 | 0.034 (2) | 0.033 (2) | 0.041 (2) | −0.0033 (18) | 0.0090 (18) | 0.0097 (19) |
Ti1—C1 | 2.426 (3) | C7—H7 | 0.9500 |
Ti1—C2 | 2.376 (3) | C8—C9 | 1.431 (5) |
Ti1—C3 | 2.377 (3) | C9—C10 | 1.406 (5) |
Ti1—C4 | 2.364 (3) | C9—H9 | 0.9500 |
Ti1—C5 | 2.393 (3) | C10—H10 | 0.9500 |
Ti1—C6 | 2.430 (3) | C11—H11A | 0.9800 |
Ti1—C7 | 2.372 (3) | C11—H11B | 0.9800 |
Ti1—C8 | 2.366 (3) | C11—H11C | 0.9800 |
Ti1—C9 | 2.382 (3) | C12—H12A | 0.9800 |
Ti1—C10 | 2.399 (3) | C12—H12B | 0.9800 |
Ti1—N1 | 1.933 (3) | C12—H12C | 0.9800 |
Ti1—Cg1 | 2.0611 (17) | C13—H13A | 0.9800 |
Ti1—Cg2 | 2.0623 (17) | C13—H13B | 0.9800 |
N1—H23A | 0.85 (4) | C13—H13C | 0.9800 |
N1—H23B | 0.87 (5) | C14—H14A | 0.9800 |
Si1—C15 | 1.851 (4) | C14—H14B | 0.9800 |
Si1—C16 | 1.863 (4) | C14—H14C | 0.9800 |
Si1—C14 | 1.866 (4) | C15—H15A | 0.9800 |
Si1—C1 | 1.872 (3) | C15—H15B | 0.9800 |
Si2—C11 | 1.863 (4) | C15—H15C | 0.9800 |
Si2—C3 | 1.863 (3) | C16—H16A | 0.9800 |
Si2—C13 | 1.866 (4) | C16—H16B | 0.9800 |
Si2—C12 | 1.867 (4) | C16—H16C | 0.9800 |
Si3—C19 | 1.860 (4) | C17—H17A | 0.9800 |
Si3—C18 | 1.868 (4) | C17—H17B | 0.9800 |
Si3—C17 | 1.870 (4) | C17—H17C | 0.9800 |
Si3—C6 | 1.871 (3) | C18—H18A | 0.9800 |
Si4—C22 | 1.862 (4) | C18—H18B | 0.9800 |
Si4—C8 | 1.864 (3) | C18—H18C | 0.9800 |
Si4—C21 | 1.870 (4) | C19—H19A | 0.9800 |
Si4—C20 | 1.871 (4) | C19—H19B | 0.9800 |
C1—C2 | 1.416 (5) | C19—H19C | 0.9800 |
C1—C5 | 1.420 (5) | C20—H20A | 0.9800 |
C2—C3 | 1.420 (5) | C20—H20B | 0.9800 |
C2—H2 | 0.9500 | C20—H20C | 0.9800 |
C3—C4 | 1.423 (5) | C21—H21A | 0.9800 |
C4—C5 | 1.408 (5) | C21—H21B | 0.9800 |
C4—H4 | 0.9500 | C21—H21C | 0.9800 |
C5—H5 | 0.9500 | C22—H22A | 0.9800 |
C6—C7 | 1.426 (5) | C22—H22B | 0.9800 |
C6—C10 | 1.430 (5) | C22—H22C | 0.9800 |
C7—C8 | 1.420 (5) | ||
N1—Ti1—C4 | 139.00 (14) | C4—C5—C1 | 109.1 (3) |
N1—Ti1—C8 | 107.69 (14) | C4—C5—Ti1 | 71.66 (19) |
C4—Ti1—C8 | 111.38 (12) | C1—C5—Ti1 | 74.13 (19) |
N1—Ti1—C7 | 82.41 (14) | C4—C5—H5 | 125.5 |
C4—Ti1—C7 | 138.26 (12) | C1—C5—H5 | 125.5 |
C8—Ti1—C7 | 34.88 (11) | Ti1—C5—H5 | 120.5 |
N1—Ti1—C2 | 82.57 (14) | C7—C6—C10 | 104.8 (3) |
C4—Ti1—C2 | 56.74 (12) | C7—C6—Si3 | 126.2 (3) |
C8—Ti1—C2 | 153.59 (12) | C10—C6—Si3 | 128.3 (3) |
C7—Ti1—C2 | 164.97 (12) | C7—C6—Ti1 | 70.49 (18) |
N1—Ti1—C3 | 107.24 (14) | C10—C6—Ti1 | 71.56 (18) |
C4—Ti1—C3 | 34.94 (11) | Si3—C6—Ti1 | 129.59 (16) |
C8—Ti1—C3 | 145.07 (12) | C8—C7—C6 | 111.6 (3) |
C7—Ti1—C3 | 154.55 (12) | C8—C7—Ti1 | 72.34 (18) |
C2—Ti1—C3 | 34.77 (11) | C6—C7—Ti1 | 74.98 (18) |
N1—Ti1—C9 | 139.05 (14) | C8—C7—H7 | 124.2 |
C4—Ti1—C9 | 81.95 (12) | C6—C7—H7 | 124.2 |
C8—Ti1—C9 | 35.08 (11) | Ti1—C7—H7 | 120.0 |
C7—Ti1—C9 | 56.80 (12) | C7—C8—C9 | 104.9 (3) |
C2—Ti1—C9 | 138.12 (12) | C7—C8—Si4 | 125.9 (3) |
C3—Ti1—C9 | 111.54 (12) | C9—C8—Si4 | 128.4 (3) |
N1—Ti1—C5 | 126.51 (14) | C7—C8—Ti1 | 72.77 (18) |
C4—Ti1—C5 | 34.43 (11) | C9—C8—Ti1 | 73.06 (18) |
C8—Ti1—C5 | 99.81 (12) | Si4—C8—Ti1 | 126.17 (17) |
C7—Ti1—C5 | 134.69 (12) | C10—C9—C8 | 109.3 (3) |
C2—Ti1—C5 | 56.39 (12) | C10—C9—Ti1 | 73.55 (19) |
C3—Ti1—C5 | 57.95 (11) | C8—C9—Ti1 | 71.86 (19) |
C9—Ti1—C5 | 86.24 (12) | C10—C9—H9 | 125.4 |
N1—Ti1—C10 | 125.81 (14) | C8—C9—H9 | 125.4 |
C4—Ti1—C10 | 86.31 (12) | Ti1—C9—H9 | 120.9 |
C8—Ti1—C10 | 58.10 (12) | C9—C10—C6 | 109.4 (3) |
C7—Ti1—C10 | 56.61 (12) | C9—C10—Ti1 | 72.25 (19) |
C2—Ti1—C10 | 135.15 (12) | C6—C10—Ti1 | 74.00 (19) |
C3—Ti1—C10 | 100.39 (12) | C9—C10—H10 | 125.3 |
C9—Ti1—C10 | 34.20 (11) | C6—C10—H10 | 125.3 |
C5—Ti1—C10 | 107.68 (12) | Ti1—C10—H10 | 120.2 |
N1—Ti1—C1 | 92.54 (13) | Si2—C11—H11A | 109.5 |
C4—Ti1—C1 | 57.47 (11) | Si2—C11—H11B | 109.5 |
C8—Ti1—C1 | 119.54 (12) | H11A—C11—H11B | 109.5 |
C7—Ti1—C1 | 146.25 (12) | Si2—C11—H11C | 109.5 |
C2—Ti1—C1 | 34.28 (11) | H11A—C11—H11C | 109.5 |
C3—Ti1—C1 | 58.43 (11) | H11B—C11—H11C | 109.5 |
C9—Ti1—C1 | 118.66 (12) | Si2—C12—H12A | 109.5 |
C5—Ti1—C1 | 34.26 (11) | Si2—C12—H12B | 109.5 |
C10—Ti1—C1 | 141.35 (12) | H12A—C12—H12B | 109.5 |
N1—Ti1—C6 | 91.73 (14) | Si2—C12—H12C | 109.5 |
C4—Ti1—C6 | 118.89 (12) | H12A—C12—H12C | 109.5 |
C8—Ti1—C6 | 58.76 (11) | H12B—C12—H12C | 109.5 |
C7—Ti1—C6 | 34.52 (11) | Si2—C13—H13A | 109.5 |
C2—Ti1—C6 | 146.95 (12) | Si2—C13—H13B | 109.5 |
C3—Ti1—C6 | 120.29 (12) | H13A—C13—H13B | 109.5 |
C9—Ti1—C6 | 57.48 (12) | Si2—C13—H13C | 109.5 |
C5—Ti1—C6 | 141.47 (12) | H13A—C13—H13C | 109.5 |
C10—Ti1—C6 | 34.44 (11) | H13B—C13—H13C | 109.5 |
C1—Ti1—C6 | 175.72 (12) | Si1—C14—H14A | 109.5 |
C15—Si1—C16 | 109.7 (2) | Si1—C14—H14B | 109.5 |
C15—Si1—C14 | 109.3 (2) | H14A—C14—H14B | 109.5 |
C16—Si1—C14 | 108.53 (18) | Si1—C14—H14C | 109.5 |
C15—Si1—C1 | 109.40 (17) | H14A—C14—H14C | 109.5 |
C16—Si1—C1 | 113.40 (17) | H14B—C14—H14C | 109.5 |
C14—Si1—C1 | 106.33 (16) | Si1—C15—H15A | 109.5 |
C11—Si2—C3 | 111.73 (16) | Si1—C15—H15B | 109.5 |
C11—Si2—C13 | 109.86 (18) | H15A—C15—H15B | 109.5 |
C3—Si2—C13 | 108.16 (16) | Si1—C15—H15C | 109.5 |
C11—Si2—C12 | 108.29 (18) | H15A—C15—H15C | 109.5 |
C3—Si2—C12 | 108.00 (17) | H15B—C15—H15C | 109.5 |
C13—Si2—C12 | 110.80 (19) | Si1—C16—H16A | 109.5 |
C19—Si3—C18 | 109.31 (18) | Si1—C16—H16B | 109.5 |
C19—Si3—C17 | 108.59 (19) | H16A—C16—H16B | 109.5 |
C18—Si3—C17 | 110.05 (18) | Si1—C16—H16C | 109.5 |
C19—Si3—C6 | 113.62 (16) | H16A—C16—H16C | 109.5 |
C18—Si3—C6 | 108.60 (17) | H16B—C16—H16C | 109.5 |
C17—Si3—C6 | 106.62 (16) | Si3—C17—H17A | 109.5 |
C22—Si4—C8 | 111.15 (16) | Si3—C17—H17B | 109.5 |
C22—Si4—C21 | 111.86 (19) | H17A—C17—H17B | 109.5 |
C8—Si4—C21 | 108.03 (16) | Si3—C17—H17C | 109.5 |
C22—Si4—C20 | 107.84 (18) | H17A—C17—H17C | 109.5 |
C8—Si4—C20 | 108.21 (16) | H17B—C17—H17C | 109.5 |
C21—Si4—C20 | 109.68 (18) | Si3—C18—H18A | 109.5 |
Ti1—N1—H23A | 128 (3) | Si3—C18—H18B | 109.5 |
Ti1—N1—H23B | 127 (3) | H18A—C18—H18B | 109.5 |
H23A—N1—H23B | 105 (4) | Si3—C18—H18C | 109.5 |
Cg1—Ti1—Cg2 | 137.90 (8) | H18A—C18—H18C | 109.5 |
Cg1—Ti1—N1 | 111.13 (12) | H18B—C18—H18C | 109.5 |
Cg2—Ti1—N1 | 110.97 (12) | Si3—C19—H19A | 109.5 |
C2—C1—C5 | 105.2 (3) | Si3—C19—H19B | 109.5 |
C2—C1—Si1 | 123.3 (3) | H19A—C19—H19B | 109.5 |
C5—C1—Si1 | 130.2 (3) | Si3—C19—H19C | 109.5 |
C2—C1—Ti1 | 70.95 (19) | H19A—C19—H19C | 109.5 |
C5—C1—Ti1 | 71.61 (19) | H19B—C19—H19C | 109.5 |
Si1—C1—Ti1 | 131.59 (16) | Si4—C20—H20A | 109.5 |
C1—C2—C3 | 111.5 (3) | Si4—C20—H20B | 109.5 |
C1—C2—Ti1 | 74.77 (19) | H20A—C20—H20B | 109.5 |
C3—C2—Ti1 | 72.63 (19) | Si4—C20—H20C | 109.5 |
C1—C2—H2 | 124.2 | H20A—C20—H20C | 109.5 |
C3—C2—H2 | 124.2 | H20B—C20—H20C | 109.5 |
Ti1—C2—H2 | 119.9 | Si4—C21—H21A | 109.5 |
C2—C3—C4 | 104.8 (3) | Si4—C21—H21B | 109.5 |
C2—C3—Si2 | 125.0 (3) | H21A—C21—H21B | 109.5 |
C4—C3—Si2 | 129.5 (2) | Si4—C21—H21C | 109.5 |
C2—C3—Ti1 | 72.60 (18) | H21A—C21—H21C | 109.5 |
C4—C3—Ti1 | 72.04 (18) | H21B—C21—H21C | 109.5 |
Si2—C3—Ti1 | 127.36 (16) | Si4—C22—H22A | 109.5 |
C5—C4—C3 | 109.4 (3) | Si4—C22—H22B | 109.5 |
C5—C4—Ti1 | 73.91 (19) | H22A—C22—H22B | 109.5 |
C3—C4—Ti1 | 73.01 (18) | Si4—C22—H22C | 109.5 |
C5—C4—H4 | 125.3 | H22A—C22—H22C | 109.5 |
C3—C4—H4 | 125.3 | H22B—C22—H22C | 109.5 |
Ti1—C4—H4 | 119.5 | ||
C15—Si1—C1—C2 | −40.2 (3) | C19—Si3—C6—C7 | −92.2 (3) |
C16—Si1—C1—C2 | −163.0 (3) | C18—Si3—C6—C7 | 145.9 (3) |
C14—Si1—C1—C2 | 77.8 (3) | C17—Si3—C6—C7 | 27.4 (3) |
C15—Si1—C1—C5 | 154.7 (3) | C19—Si3—C6—C10 | 99.2 (3) |
C16—Si1—C1—C5 | 31.9 (4) | C18—Si3—C6—C10 | −22.7 (4) |
C14—Si1—C1—C5 | −87.3 (3) | C17—Si3—C6—C10 | −141.2 (3) |
C15—Si1—C1—Ti1 | 53.3 (3) | C19—Si3—C6—Ti1 | 1.7 (3) |
C16—Si1—C1—Ti1 | −69.5 (3) | C18—Si3—C6—Ti1 | −120.2 (2) |
C14—Si1—C1—Ti1 | 171.3 (2) | C17—Si3—C6—Ti1 | 121.3 (2) |
N1—Ti1—C1—C2 | 72.9 (2) | N1—Ti1—C6—C7 | 73.9 (2) |
C4—Ti1—C1—C2 | −77.3 (2) | C4—Ti1—C6—C7 | −134.6 (2) |
C8—Ti1—C1—C2 | −175.13 (19) | C8—Ti1—C6—C7 | −35.79 (19) |
C7—Ti1—C1—C2 | 153.0 (2) | C2—Ti1—C6—C7 | 152.9 (2) |
C3—Ti1—C1—C2 | −35.86 (19) | C3—Ti1—C6—C7 | −174.92 (19) |
C9—Ti1—C1—C2 | −134.8 (2) | C9—Ti1—C6—C7 | −77.3 (2) |
C5—Ti1—C1—C2 | −114.1 (3) | C5—Ti1—C6—C7 | −99.6 (2) |
C10—Ti1—C1—C2 | −100.4 (2) | C10—Ti1—C6—C7 | −113.8 (3) |
N1—Ti1—C1—C5 | −173.1 (2) | N1—Ti1—C6—C10 | −172.3 (2) |
C4—Ti1—C1—C5 | 36.74 (19) | C4—Ti1—C6—C10 | −20.8 (2) |
C8—Ti1—C1—C5 | −61.1 (2) | C8—Ti1—C6—C10 | 78.0 (2) |
C7—Ti1—C1—C5 | −92.9 (3) | C7—Ti1—C6—C10 | 113.8 (3) |
C2—Ti1—C1—C5 | 114.1 (3) | C2—Ti1—C6—C10 | −93.3 (3) |
C3—Ti1—C1—C5 | 78.2 (2) | C3—Ti1—C6—C10 | −61.1 (2) |
C9—Ti1—C1—C5 | −20.7 (2) | C9—Ti1—C6—C10 | 36.43 (19) |
C10—Ti1—C1—C5 | 13.6 (3) | C5—Ti1—C6—C10 | 14.2 (3) |
N1—Ti1—C1—Si1 | −45.2 (2) | N1—Ti1—C6—Si3 | −47.4 (2) |
C4—Ti1—C1—Si1 | 164.6 (3) | C4—Ti1—C6—Si3 | 104.1 (2) |
C8—Ti1—C1—Si1 | 66.9 (3) | C8—Ti1—C6—Si3 | −157.1 (3) |
C7—Ti1—C1—Si1 | 35.0 (4) | C7—Ti1—C6—Si3 | −121.3 (3) |
C2—Ti1—C1—Si1 | −118.0 (3) | C2—Ti1—C6—Si3 | 31.6 (4) |
C3—Ti1—C1—Si1 | −153.9 (3) | C3—Ti1—C6—Si3 | 63.8 (2) |
C9—Ti1—C1—Si1 | 107.2 (2) | C9—Ti1—C6—Si3 | 161.4 (3) |
C5—Ti1—C1—Si1 | 127.9 (3) | C5—Ti1—C6—Si3 | 139.1 (2) |
C10—Ti1—C1—Si1 | 141.6 (2) | C10—Ti1—C6—Si3 | 124.9 (3) |
C5—C1—C2—C3 | 0.0 (4) | C10—C6—C7—C8 | −0.2 (4) |
Si1—C1—C2—C3 | −168.3 (2) | Si3—C6—C7—C8 | −171.0 (2) |
Ti1—C1—C2—C3 | 63.9 (2) | Ti1—C6—C7—C8 | 63.6 (2) |
C5—C1—C2—Ti1 | −63.9 (2) | C10—C6—C7—Ti1 | −63.9 (2) |
Si1—C1—C2—Ti1 | 127.8 (2) | Si3—C6—C7—Ti1 | 125.4 (3) |
N1—Ti1—C2—C1 | −105.7 (2) | N1—Ti1—C7—C8 | 136.6 (2) |
C4—Ti1—C2—C1 | 79.6 (2) | C4—Ti1—C7—C8 | −49.4 (3) |
C8—Ti1—C2—C1 | 9.6 (4) | C2—Ti1—C7—C8 | 134.2 (4) |
C7—Ti1—C2—C1 | −103.2 (5) | C3—Ti1—C7—C8 | −108.8 (3) |
C3—Ti1—C2—C1 | 118.9 (3) | C9—Ti1—C7—C8 | −39.53 (19) |
C9—Ti1—C2—C1 | 68.9 (3) | C5—Ti1—C7—C8 | 1.2 (3) |
C5—Ti1—C2—C1 | 38.11 (19) | C10—Ti1—C7—C8 | −80.7 (2) |
C10—Ti1—C2—C1 | 119.4 (2) | C1—Ti1—C7—C8 | 53.5 (3) |
C6—Ti1—C2—C1 | 172.6 (2) | C6—Ti1—C7—C8 | −119.0 (3) |
N1—Ti1—C2—C3 | 135.4 (2) | N1—Ti1—C7—C6 | −104.3 (2) |
C4—Ti1—C2—C3 | −39.26 (19) | C4—Ti1—C7—C6 | 69.6 (3) |
C8—Ti1—C2—C3 | −109.4 (3) | C8—Ti1—C7—C6 | 119.0 (3) |
C7—Ti1—C2—C3 | 137.8 (4) | C2—Ti1—C7—C6 | −106.8 (5) |
C9—Ti1—C2—C3 | −50.0 (3) | C3—Ti1—C7—C6 | 10.3 (4) |
C5—Ti1—C2—C3 | −80.8 (2) | C9—Ti1—C7—C6 | 79.5 (2) |
C10—Ti1—C2—C3 | 0.5 (3) | C5—Ti1—C7—C6 | 120.2 (2) |
C1—Ti1—C2—C3 | −118.9 (3) | C10—Ti1—C7—C6 | 38.30 (19) |
C6—Ti1—C2—C3 | 53.7 (3) | C1—Ti1—C7—C6 | 172.5 (2) |
C1—C2—C3—C4 | 0.2 (4) | C6—C7—C8—C9 | 1.3 (4) |
Ti1—C2—C3—C4 | 65.4 (2) | Ti1—C7—C8—C9 | 66.5 (2) |
C1—C2—C3—Si2 | 170.9 (2) | C6—C7—C8—Si4 | 172.2 (2) |
Ti1—C2—C3—Si2 | −123.8 (3) | Ti1—C7—C8—Si4 | −122.6 (3) |
C1—C2—C3—Ti1 | −65.2 (2) | C6—C7—C8—Ti1 | −65.3 (2) |
C11—Si2—C3—C2 | 140.2 (3) | C22—Si4—C8—C7 | 157.3 (3) |
C13—Si2—C3—C2 | 19.1 (3) | C21—Si4—C8—C7 | 34.2 (3) |
C12—Si2—C3—C2 | −100.8 (3) | C20—Si4—C8—C7 | −84.5 (3) |
C11—Si2—C3—C4 | −51.4 (4) | C22—Si4—C8—C9 | −34.0 (4) |
C13—Si2—C3—C4 | −172.4 (3) | C21—Si4—C8—C9 | −157.0 (3) |
C12—Si2—C3—C4 | 67.6 (3) | C20—Si4—C8—C9 | 84.3 (3) |
C11—Si2—C3—Ti1 | 45.9 (3) | C22—Si4—C8—Ti1 | 62.9 (3) |
C13—Si2—C3—Ti1 | −75.2 (2) | C21—Si4—C8—Ti1 | −60.2 (2) |
C12—Si2—C3—Ti1 | 164.9 (2) | C20—Si4—C8—Ti1 | −178.9 (2) |
N1—Ti1—C3—C2 | −46.8 (2) | N1—Ti1—C8—C7 | −45.6 (2) |
C4—Ti1—C3—C2 | 112.5 (3) | C4—Ti1—C8—C7 | 147.1 (2) |
C8—Ti1—C3—C2 | 132.9 (2) | C2—Ti1—C8—C7 | −155.3 (3) |
C7—Ti1—C3—C2 | −156.1 (3) | C3—Ti1—C8—C7 | 134.7 (2) |
C9—Ti1—C3—C2 | 146.63 (19) | C9—Ti1—C8—C7 | 112.1 (3) |
C5—Ti1—C3—C2 | 75.9 (2) | C5—Ti1—C8—C7 | −179.1 (2) |
C10—Ti1—C3—C2 | −179.6 (2) | C10—Ti1—C8—C7 | 76.1 (2) |
C1—Ti1—C3—C2 | 35.36 (19) | C1—Ti1—C8—C7 | −149.13 (19) |
C6—Ti1—C3—C2 | −149.40 (19) | C6—Ti1—C8—C7 | 35.42 (19) |
N1—Ti1—C3—C4 | −159.3 (2) | N1—Ti1—C8—C9 | −157.7 (2) |
C8—Ti1—C3—C4 | 20.4 (3) | C4—Ti1—C8—C9 | 35.0 (2) |
C7—Ti1—C3—C4 | 91.4 (3) | C7—Ti1—C8—C9 | −112.1 (3) |
C2—Ti1—C3—C4 | −112.5 (3) | C2—Ti1—C8—C9 | 92.6 (3) |
C9—Ti1—C3—C4 | 34.1 (2) | C3—Ti1—C8—C9 | 22.6 (3) |
C5—Ti1—C3—C4 | −36.58 (19) | C5—Ti1—C8—C9 | 68.8 (2) |
C10—Ti1—C3—C4 | 67.9 (2) | C10—Ti1—C8—C9 | −36.02 (19) |
C1—Ti1—C3—C4 | −77.1 (2) | C1—Ti1—C8—C9 | 98.8 (2) |
C6—Ti1—C3—C4 | 98.1 (2) | C6—Ti1—C8—C9 | −76.7 (2) |
N1—Ti1—C3—Si2 | 74.3 (2) | N1—Ti1—C8—Si4 | 76.7 (2) |
C4—Ti1—C3—Si2 | −126.4 (3) | C4—Ti1—C8—Si4 | −90.6 (2) |
C8—Ti1—C3—Si2 | −106.0 (2) | C7—Ti1—C8—Si4 | 122.3 (3) |
C7—Ti1—C3—Si2 | −35.0 (4) | C2—Ti1—C8—Si4 | −33.0 (4) |
C2—Ti1—C3—Si2 | 121.1 (3) | C3—Ti1—C8—Si4 | −103.0 (2) |
C9—Ti1—C3—Si2 | −92.3 (2) | C9—Ti1—C8—Si4 | −125.6 (3) |
C5—Ti1—C3—Si2 | −163.0 (3) | C5—Ti1—C8—Si4 | −56.8 (2) |
C10—Ti1—C3—Si2 | −58.5 (2) | C10—Ti1—C8—Si4 | −161.6 (3) |
C1—Ti1—C3—Si2 | 156.5 (3) | C1—Ti1—C8—Si4 | −26.8 (3) |
C6—Ti1—C3—Si2 | −28.3 (3) | C6—Ti1—C8—Si4 | 157.7 (3) |
C2—C3—C4—C5 | −0.3 (4) | C7—C8—C9—C10 | −1.8 (4) |
Si2—C3—C4—C5 | −170.5 (2) | Si4—C8—C9—C10 | −172.4 (2) |
Ti1—C3—C4—C5 | 65.5 (2) | Ti1—C8—C9—C10 | 64.5 (2) |
C2—C3—C4—Ti1 | −65.8 (2) | C7—C8—C9—Ti1 | −66.3 (2) |
Si2—C3—C4—Ti1 | 124.0 (3) | Si4—C8—C9—Ti1 | 123.1 (3) |
N1—Ti1—C4—C5 | −85.7 (3) | N1—Ti1—C9—C10 | −83.8 (3) |
C8—Ti1—C4—C5 | 75.7 (2) | C4—Ti1—C9—C10 | 95.3 (2) |
C7—Ti1—C4—C5 | 103.5 (2) | C8—Ti1—C9—C10 | −117.3 (3) |
C2—Ti1—C4—C5 | −77.6 (2) | C7—Ti1—C9—C10 | −78.0 (2) |
C3—Ti1—C4—C5 | −116.7 (3) | C2—Ti1—C9—C10 | 104.4 (2) |
C9—Ti1—C4—C5 | 95.1 (2) | C3—Ti1—C9—C10 | 76.4 (2) |
C10—Ti1—C4—C5 | 129.2 (2) | C5—Ti1—C9—C10 | 129.7 (2) |
C1—Ti1—C4—C5 | −36.56 (19) | C1—Ti1—C9—C10 | 141.17 (19) |
C6—Ti1—C4—C5 | 140.8 (2) | C6—Ti1—C9—C10 | −36.68 (19) |
N1—Ti1—C4—C3 | 31.0 (3) | N1—Ti1—C9—C8 | 33.5 (3) |
C8—Ti1—C4—C3 | −167.63 (19) | C4—Ti1—C9—C8 | −147.4 (2) |
C7—Ti1—C4—C3 | −139.8 (2) | C7—Ti1—C9—C8 | 39.29 (19) |
C2—Ti1—C4—C3 | 39.06 (19) | C2—Ti1—C9—C8 | −138.3 (2) |
C9—Ti1—C4—C3 | −148.2 (2) | C3—Ti1—C9—C8 | −166.30 (19) |
C5—Ti1—C4—C3 | 116.7 (3) | C5—Ti1—C9—C8 | −113.0 (2) |
C10—Ti1—C4—C3 | −114.1 (2) | C10—Ti1—C9—C8 | 117.3 (3) |
C1—Ti1—C4—C3 | 80.1 (2) | C1—Ti1—C9—C8 | −101.5 (2) |
C6—Ti1—C4—C3 | −102.5 (2) | C6—Ti1—C9—C8 | 80.7 (2) |
C3—C4—C5—C1 | 0.3 (4) | C8—C9—C10—C6 | 1.8 (4) |
Ti1—C4—C5—C1 | 65.2 (2) | Ti1—C9—C10—C6 | 65.2 (2) |
C3—C4—C5—Ti1 | −64.9 (2) | C8—C9—C10—Ti1 | −63.4 (2) |
C2—C1—C5—C4 | −0.2 (4) | C7—C6—C10—C9 | −0.9 (4) |
Si1—C1—C5—C4 | 167.0 (3) | Si3—C6—C10—C9 | 169.6 (2) |
Ti1—C1—C5—C4 | −63.6 (2) | Ti1—C6—C10—C9 | −64.1 (2) |
C2—C1—C5—Ti1 | 63.4 (2) | C7—C6—C10—Ti1 | 63.1 (2) |
Si1—C1—C5—Ti1 | −129.4 (3) | Si3—C6—C10—Ti1 | −126.4 (3) |
N1—Ti1—C5—C4 | 125.5 (2) | N1—Ti1—C10—C9 | 126.5 (2) |
C8—Ti1—C5—C4 | −113.7 (2) | C4—Ti1—C10—C9 | −81.1 (2) |
C7—Ti1—C5—C4 | −114.4 (2) | C8—Ti1—C10—C9 | 36.97 (19) |
C2—Ti1—C5—C4 | 78.7 (2) | C7—Ti1—C10—C9 | 78.6 (2) |
C3—Ti1—C5—C4 | 37.14 (19) | C2—Ti1—C10—C9 | −113.5 (2) |
C9—Ti1—C5—C4 | −81.2 (2) | C3—Ti1—C10—C9 | −113.2 (2) |
C10—Ti1—C5—C4 | −54.2 (2) | C5—Ti1—C10—C9 | −53.7 (2) |
C1—Ti1—C5—C4 | 116.9 (3) | C1—Ti1—C10—C9 | −61.7 (3) |
C6—Ti1—C5—C4 | −62.6 (3) | C6—Ti1—C10—C9 | 117.0 (3) |
N1—Ti1—C5—C1 | 8.6 (3) | N1—Ti1—C10—C6 | 9.5 (3) |
C4—Ti1—C5—C1 | −116.9 (3) | C4—Ti1—C10—C6 | 161.9 (2) |
C8—Ti1—C5—C1 | 129.4 (2) | C8—Ti1—C10—C6 | −80.1 (2) |
C7—Ti1—C5—C1 | 128.7 (2) | C7—Ti1—C10—C6 | −38.40 (19) |
C2—Ti1—C5—C1 | −38.13 (19) | C2—Ti1—C10—C6 | 129.5 (2) |
C3—Ti1—C5—C1 | −79.7 (2) | C3—Ti1—C10—C6 | 129.7 (2) |
C9—Ti1—C5—C1 | 161.9 (2) | C9—Ti1—C10—C6 | −117.0 (3) |
C10—Ti1—C5—C1 | −171.10 (19) | C5—Ti1—C10—C6 | −170.77 (19) |
C6—Ti1—C5—C1 | −179.47 (19) | C1—Ti1—C10—C6 | −178.79 (19) |
Experimental details
Crystal data | |
Chemical formula | [Ti(C11H21Si2)2(NH2)] |
Mr | 482.84 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 133 |
a, b, c (Å) | 13.0945 (3), 16.5699 (3), 13.1869 (2) |
β (°) | 96.488 (1) |
V (Å3) | 2842.90 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.48 |
Crystal size (mm) | 0.38 × 0.32 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART 1K CCD area-detector diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.839, 0.919 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13362, 5071, 3874 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.620 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.113, 1.13 |
No. of reflections | 5071 |
No. of parameters | 273 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.47, −0.32 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.
Ti1—C1 | 2.426 (3) | Ti1—C9 | 2.382 (3) |
Ti1—C2 | 2.376 (3) | Ti1—C10 | 2.399 (3) |
Ti1—C3 | 2.377 (3) | Ti1—N1 | 1.933 (3) |
Ti1—C4 | 2.364 (3) | Ti1—Cg1 | 2.0611 (17) |
Ti1—C5 | 2.393 (3) | Ti1—Cg2 | 2.0623 (17) |
Ti1—C6 | 2.430 (3) | N1—H23A | 0.85 (4) |
Ti1—C7 | 2.372 (3) | N1—H23B | 0.87 (5) |
Ti1—C8 | 2.366 (3) | ||
Ti1—N1—H23A | 128 (3) | Cg1—Ti1—Cg2 | 137.90 (8) |
Ti1—N1—H23B | 127 (3) | Cg1—Ti1—N1 | 111.13 (12) |
H23A—N1—H23B | 105 (4) | Cg2—Ti1—N1 | 110.97 (12) |
The title compound, [Cp''2Ti(NH2)], (I) [Cp'' is 1,3-bis(trimethylsilyl)cyclopentadienyl] crystallizes in the primitive monoclinic space group P21/n with four discrete molecules in the unit cell. Selected distances and angles are given in Table 1. Fig. 1 shows the molecular geometry and the atom-numbering scheme. \sch
The Ti center is coordinated by two virtually planar 1,3-bis(trimethylsilyl)cyclopentadienyl rings in a staggered conformation relative to each other, and by an NH2 group. The angle between the cyclopentadienyl ligands, Cg1—Ti—Cg2, is 137.90 (8)° (the cyclopentadienyl ligands are represented by their centroids, Cg1 and Cg2). The distances between the Ti atom and Cg1 and Cg2 are 2.0611 (17) and 2.0623 (17) Å, respectively. These are comparable with values found for other Cp2TiNR2 derivatives (Brady et al., 1994; Lukens et al., 1996; Feldman & Calabrese, 1991).
The amide group is located within an open wedge formed by the sterically demanding trimethylsilyl groups, allowing the least steric bulk and a proper orientation for the filled p orbital to interact with the empty b2 orbital of the Cp''2Ti fragment, enabling the NH2 moiety to act as a π donor. This is also reflected in the small Cp(centroid)-Ti—N—H torsion angle of only 6.4° and the quite short Ti—N distance of 1.933 (3) Å. Similar N—M π bonding is also observed in [(η5-C5Me5)2Ti(NH2)] [Ti—N 1.944 (2) Å; Brady et al., 1994), [(η5-C5Me5)2Ti(NHMe)] [Ti—N 1.955 (2) Å; Lukens et al., 1996] and [(η5-C5Me5)2Hf(NHMe)] (Hillhouse et al., 1988), as evidenced by a similar orientation of the amide group as well as short (Ti,Hf)—N distances.
The influence of steric bulk versus electronic effects is demonstrated in bis(pentamethylcyclopentadienyl)titanium(III) N-methyl-N-phenylamide (Feldman & Calabrese, 1991), in which the amide ligand adopts a perpendicular orientation to the plane formed by the Ti atom and the two cyclopentadienyl ring centroids, preventing the p orbital from interacting with the b2 orbital of the [(η5-C5Me5)2Ti] fragment. Therefore, the Ti—N distance [2.054 (2) Å] is elongated compared with that of (I).