Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101016754/fr1315sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101016754/fr1315IIsup2.hkl |
CCDC reference: 180140
All syntheses and manipulations of air-sensitive materials were carried out in an inert atmosphere (argon) glove box. NMR-scale reactions were conducted in Teflon-valve-sealed sample J-Young tubes. Solvents were first saturated with nitrogen and then dried by passage through activated alumina and Q-5TM catalyst prior to use. Deuterated NMR solvents were dried over sodium/potassium alloy and distilled and/or filtered prior to use. Me2Si(η5-2,3,4,6-Me4—C9H2) (C6H11N) Ti(CH3) (µ-CH3Al(C6F5)3) (I) was prepared from the reaction on Me2Si(η5-2,3,4,6-Me4—C9H2) (C6H11N) Ti(CH3)2 with Al(C6F5)3 in toluene or benzene at room temperature using a similar procedure as described previously by Chen et al. (2001). I was dissolved in benzene- d6 in a J-Young NMR tube and the solution was heated in an oil bath at 333 K for 12 h. The resulting dark red solution was stored at room temperature in a glove box for 5 d, after which time, dark red crystals of II had formed.
C—H distances of 0.98 and 0.99 Å were used for methyl and secondary C atoms respectively. A distance of 0.95 Å was used for aromatic C atoms. The H atoms thermal parameters were 1.2Ueq of the parent C; 1.5Ueq for the methyl atoms. The H atoms on C22 and C23 were obtained from a difference Fourier map and refined without any constraints. In addition to the complex, a molecule of benzene was found in a general position. Full data collection details are in the relevant -special-details section of the archived CIF and also reported elsewhere (Abboud et al., 1997).
Data collection: Bruker SMART (Bruker 1998); cell refinement: Bruker SMART & SAINT (Bruker 1998); data reduction: Bruker SHELXTL (Bruker 1998); program(s) used to solve structure: Bruker SHELXTL; program(s) used to refine structure: Bruker SHELXTL; molecular graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker SHELXTL.
C84H76Al4N2Si2Ti2·2(C6D6) | Z = 1 |
Mr = 2099.58 | F(000) = 1072 |
Triclinic, P1 | Dx = 1.489 Mg m−3 |
a = 12.8651 (7) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 13.7422 (7) Å | Cell parameters from 4099 reflections |
c = 15.2642 (9) Å | θ = 2.0–27.5° |
α = 70.595 (2)° | µ = 0.34 mm−1 |
β = 70.795 (2)° | T = 173 K |
γ = 71.944 (2)° | Needle, black |
V = 2341.9 (2) Å3 | 0.27 × 0.11 × 0.06 mm |
SMART CCD area detector diffractometer | 10542 independent reflections |
Radiation source: normal-focus sealed tube | 5884 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
ω scans | θmax = 27.5°, θmin = 1.7° |
Absorption correction: integration Integration based on measured indexed crystal faces, SHELXTL (Bruker 1998) | h = −15→16 |
Tmin = 0.925, Tmax = 0.985 | k = −10→17 |
15647 measured reflections | l = −17→19 |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | w = 1/[σ2(Fo2) + (0.0481P)2] where P = (Fo2 + 2Fc2)/3 |
10542 reflections | (Δ/σ)max < 0.001 |
636 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
C84H76Al4N2Si2Ti2·2(C6D6) | γ = 71.944 (2)° |
Mr = 2099.58 | V = 2341.9 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 12.8651 (7) Å | Mo Kα radiation |
b = 13.7422 (7) Å | µ = 0.34 mm−1 |
c = 15.2642 (9) Å | T = 173 K |
α = 70.595 (2)° | 0.27 × 0.11 × 0.06 mm |
β = 70.795 (2)° |
SMART CCD area detector diffractometer | 10542 independent reflections |
Absorption correction: integration Integration based on measured indexed crystal faces, SHELXTL (Bruker 1998) | 5884 reflections with I > 2σ(I) |
Tmin = 0.925, Tmax = 0.985 | Rint = 0.037 |
15647 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.123 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | Δρmax = 0.35 e Å−3 |
10542 reflections | Δρmin = −0.37 e Å−3 |
636 parameters |
Experimental. A hemisphere of frames, 0.3° in ω, was collected. The first 50 frames were remeasured at the end of data collection to monitor instrument and crystal stability. |
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 | ||
Ti | 0.42688 (4) | 0.27710 (4) | 0.09256 (4) | 0.02225 (14) | |
Si | 0.29320 (7) | 0.14645 (7) | 0.25173 (6) | 0.0279 (2) | |
Al1 | 0.74041 (7) | 0.27090 (7) | 0.13527 (7) | 0.0259 (2) | |
Al2 | 0.58022 (7) | 0.41061 (7) | −0.00737 (7) | 0.0248 (2) | |
N1 | 0.33080 (19) | 0.26909 (18) | 0.21819 (17) | 0.0246 (6) | |
C1 | 0.3560 (2) | 0.1341 (2) | 0.1263 (2) | 0.0245 (7) | |
C2 | 0.3111 (3) | 0.2100 (2) | 0.0486 (2) | 0.0266 (7) | |
C3 | 0.3986 (3) | 0.2235 (2) | −0.0360 (2) | 0.0288 (7) | |
C4 | 0.6109 (3) | 0.1200 (3) | −0.0753 (2) | 0.0340 (8) | |
C5 | 0.6896 (3) | 0.0474 (3) | −0.0310 (3) | 0.0398 (9) | |
H5A | 0.7639 | 0.0281 | −0.0693 | 0.048* | |
C6 | 0.6672 (3) | −0.0012 (2) | 0.0690 (3) | 0.0351 (8) | |
C7 | 0.5604 (3) | 0.0220 (2) | 0.1261 (2) | 0.0306 (7) | |
H7A | 0.5443 | −0.0117 | 0.1928 | 0.037* | |
C8 | 0.4740 (3) | 0.0969 (2) | 0.0846 (2) | 0.0253 (7) | |
C9 | 0.5009 (3) | 0.1503 (2) | −0.0158 (2) | 0.0252 (7) | |
C10 | 0.3662 (3) | 0.0417 (3) | 0.3398 (2) | 0.0412 (9) | |
H10A | 0.3262 | 0.0495 | 0.4048 | 0.062* | |
H10B | 0.4440 | 0.0486 | 0.3252 | 0.062* | |
H10C | 0.3667 | −0.0282 | 0.3358 | 0.062* | |
C11 | 0.1416 (3) | 0.1458 (3) | 0.2997 (3) | 0.0466 (10) | |
H11A | 0.0982 | 0.2047 | 0.2594 | 0.070* | |
H11B | 0.1164 | 0.1536 | 0.3655 | 0.070* | |
H11C | 0.1297 | 0.0787 | 0.2997 | 0.070* | |
C12 | 0.1890 (3) | 0.2676 (3) | 0.0568 (3) | 0.0370 (8) | |
H12A | 0.1633 | 0.3031 | 0.1088 | 0.056* | |
H12B | 0.1428 | 0.2168 | 0.0708 | 0.056* | |
H12C | 0.1816 | 0.3204 | −0.0038 | 0.056* | |
C13 | 0.3834 (3) | 0.2940 (3) | −0.1326 (2) | 0.0403 (9) | |
H13A | 0.3739 | 0.2525 | −0.1695 | 0.060* | |
H13B | 0.4501 | 0.3239 | −0.1674 | 0.060* | |
H13C | 0.3163 | 0.3516 | −0.1236 | 0.060* | |
C14 | 0.6385 (3) | 0.1581 (3) | −0.1833 (2) | 0.0451 (9) | |
H14A | 0.7182 | 0.1281 | −0.2100 | 0.068* | |
H14B | 0.6246 | 0.2356 | −0.2025 | 0.068* | |
H14C | 0.5908 | 0.1353 | −0.2077 | 0.068* | |
C15 | 0.7619 (3) | −0.0795 (3) | 0.1094 (3) | 0.0488 (10) | |
H15A | 0.7340 | −0.1063 | 0.1789 | 0.073* | |
H15B | 0.8232 | −0.0446 | 0.0966 | 0.073* | |
H15C | 0.7902 | −0.1386 | 0.0792 | 0.073* | |
C16 | 0.3005 (3) | 0.3441 (2) | 0.2785 (2) | 0.0265 (7) | |
H16A | 0.342 (2) | 0.398 (2) | 0.248 (2) | 0.026 (8)* | |
C17 | 0.1769 (3) | 0.4012 (3) | 0.2910 (2) | 0.0353 (8) | |
H17A | 0.1295 | 0.3483 | 0.3200 | 0.042* | |
H17B | 0.1631 | 0.4413 | 0.2272 | 0.042* | |
C18 | 0.1424 (3) | 0.4774 (3) | 0.3547 (3) | 0.0429 (9) | |
H18A | 0.1827 | 0.5356 | 0.3219 | 0.051* | |
H18B | 0.0603 | 0.5088 | 0.3649 | 0.051* | |
C19 | 0.1697 (3) | 0.4211 (3) | 0.4510 (3) | 0.0505 (10) | |
H19A | 0.1223 | 0.3688 | 0.4873 | 0.061* | |
H19B | 0.1519 | 0.4732 | 0.4886 | 0.061* | |
C20 | 0.2934 (3) | 0.3649 (3) | 0.4382 (3) | 0.0498 (10) | |
H20A | 0.3078 | 0.3253 | 0.5019 | 0.060* | |
H20B | 0.3404 | 0.4182 | 0.4087 | 0.060* | |
C21 | 0.3277 (3) | 0.2884 (3) | 0.3751 (2) | 0.0407 (9) | |
H21A | 0.4098 | 0.2569 | 0.3650 | 0.049* | |
H21B | 0.2874 | 0.2302 | 0.4082 | 0.049* | |
C22 | 0.4071 (3) | 0.4421 (2) | 0.0064 (3) | 0.0259 (7) | |
H22A | 0.391 (2) | 0.447 (2) | −0.046 (2) | 0.030 (9)* | |
H22B | 0.342 (3) | 0.445 (2) | 0.058 (3) | 0.045 (10)* | |
C23 | 0.5945 (3) | 0.2806 (3) | 0.1029 (2) | 0.0263 (7) | |
H23A | 0.554 (3) | 0.271 (3) | 0.168 (3) | 0.046 (10)* | |
H23B | 0.622 (3) | 0.212 (3) | 0.090 (2) | 0.043 (10)* | |
C24 | 0.8564 (2) | 0.3095 (2) | 0.0121 (2) | 0.0277 (7) | |
C25 | 0.9052 (3) | 0.2426 (3) | −0.0477 (3) | 0.0353 (8) | |
C26 | 0.9856 (3) | 0.2634 (3) | −0.1331 (3) | 0.0404 (9) | |
C27 | 1.0228 (3) | 0.3547 (3) | −0.1613 (2) | 0.0376 (8) | |
C28 | 0.9770 (3) | 0.4250 (3) | −0.1054 (2) | 0.0348 (8) | |
C29 | 0.8954 (3) | 0.4011 (2) | −0.0212 (2) | 0.0296 (7) | |
C30 | 0.7947 (2) | 0.1235 (2) | 0.2128 (2) | 0.0280 (7) | |
C31 | 0.7203 (3) | 0.0709 (3) | 0.2882 (2) | 0.0331 (8) | |
C32 | 0.7517 (3) | −0.0254 (3) | 0.3506 (2) | 0.0392 (9) | |
C33 | 0.8636 (3) | −0.0725 (3) | 0.3397 (3) | 0.0435 (9) | |
C34 | 0.9423 (3) | −0.0245 (3) | 0.2673 (3) | 0.0388 (9) | |
C35 | 0.9067 (3) | 0.0700 (2) | 0.2054 (2) | 0.0341 (8) | |
C36 | 0.7193 (2) | 0.3602 (2) | 0.2226 (2) | 0.0266 (7) | |
C37 | 0.8110 (3) | 0.3566 (2) | 0.2529 (2) | 0.0302 (7) | |
C38 | 0.8089 (3) | 0.4103 (3) | 0.3149 (2) | 0.0335 (8) | |
C39 | 0.7079 (3) | 0.4748 (3) | 0.3500 (2) | 0.0391 (9) | |
C40 | 0.6129 (3) | 0.4808 (3) | 0.3239 (2) | 0.0369 (8) | |
C41 | 0.6207 (3) | 0.4244 (2) | 0.2622 (2) | 0.0294 (7) | |
C42 | 0.6697 (3) | 0.3775 (2) | −0.1289 (2) | 0.0322 (8) | |
H42A | 0.7222 | 0.4246 | −0.1623 | 0.048* | |
H42B | 0.6193 | 0.3875 | −0.1689 | 0.048* | |
H42C | 0.7124 | 0.3038 | −0.1165 | 0.048* | |
C43 | 0.1269 (5) | 0.8313 (4) | 0.4862 (4) | 0.0794 (16) | |
H43A | 0.0499 | 0.8675 | 0.4922 | 0.095* | |
C44 | 0.1737 (4) | 0.7564 (4) | 0.4342 (3) | 0.0729 (14) | |
H44A | 0.1287 | 0.7399 | 0.4051 | 0.087* | |
C45 | 0.2853 (4) | 0.7060 (4) | 0.4245 (3) | 0.0717 (14) | |
H45A | 0.3171 | 0.6540 | 0.3890 | 0.086* | |
C46 | 0.3522 (4) | 0.7297 (4) | 0.4657 (3) | 0.0699 (14) | |
H46A | 0.4300 | 0.6954 | 0.4575 | 0.084* | |
C47 | 0.3049 (5) | 0.8037 (4) | 0.5189 (3) | 0.0741 (14) | |
H47A | 0.3497 | 0.8204 | 0.5481 | 0.089* | |
C48 | 0.1925 (5) | 0.8532 (4) | 0.5293 (4) | 0.0822 (17) | |
H48A | 0.1596 | 0.9032 | 0.5669 | 0.099* | |
F1 | 0.87264 (17) | 0.14967 (15) | −0.02248 (15) | 0.0490 (5) | |
F2 | 1.02856 (18) | 0.19539 (17) | −0.18922 (16) | 0.0576 (6) | |
F3 | 1.10255 (17) | 0.37524 (18) | −0.24308 (15) | 0.0619 (7) | |
F4 | 1.00995 (17) | 0.51704 (16) | −0.13341 (15) | 0.0506 (6) | |
F5 | 0.85175 (15) | 0.47535 (14) | 0.02991 (13) | 0.0389 (5) | |
F6 | 0.60791 (15) | 0.11783 (15) | 0.30520 (14) | 0.0444 (5) | |
F7 | 0.67309 (18) | −0.07120 (17) | 0.42190 (15) | 0.0616 (7) | |
F8 | 0.89672 (19) | −0.16596 (16) | 0.40026 (16) | 0.0645 (7) | |
F9 | 1.05310 (16) | −0.07091 (16) | 0.25674 (17) | 0.0564 (6) | |
F10 | 0.98908 (14) | 0.11159 (15) | 0.13412 (15) | 0.0456 (5) | |
F11 | 0.91194 (14) | 0.29469 (15) | 0.21849 (14) | 0.0410 (5) | |
F12 | 0.90134 (16) | 0.40156 (17) | 0.34182 (15) | 0.0506 (6) | |
F13 | 0.70205 (19) | 0.52930 (17) | 0.41032 (15) | 0.0577 (6) | |
F14 | 0.51417 (17) | 0.54291 (17) | 0.35970 (16) | 0.0576 (6) | |
F15 | 0.52404 (14) | 0.43539 (15) | 0.23844 (14) | 0.0420 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ti | 0.0245 (3) | 0.0214 (3) | 0.0233 (3) | −0.0091 (2) | −0.0049 (2) | −0.0063 (2) |
Si | 0.0306 (5) | 0.0270 (5) | 0.0267 (5) | −0.0124 (4) | −0.0034 (4) | −0.0061 (4) |
Al1 | 0.0247 (5) | 0.0242 (5) | 0.0295 (5) | −0.0068 (4) | −0.0073 (4) | −0.0061 (4) |
Al2 | 0.0257 (5) | 0.0235 (5) | 0.0261 (5) | −0.0085 (4) | −0.0066 (4) | −0.0047 (4) |
N1 | 0.0266 (14) | 0.0250 (14) | 0.0243 (14) | −0.0085 (11) | −0.0066 (11) | −0.0063 (11) |
C1 | 0.0297 (17) | 0.0218 (16) | 0.0273 (17) | −0.0133 (13) | −0.0063 (14) | −0.0070 (13) |
C2 | 0.0307 (17) | 0.0242 (16) | 0.0336 (18) | −0.0108 (13) | −0.0119 (14) | −0.0105 (13) |
C3 | 0.0401 (19) | 0.0281 (17) | 0.0278 (18) | −0.0139 (15) | −0.0125 (15) | −0.0098 (14) |
C4 | 0.040 (2) | 0.0320 (19) | 0.036 (2) | −0.0173 (16) | −0.0016 (16) | −0.0150 (15) |
C5 | 0.0311 (19) | 0.038 (2) | 0.053 (2) | −0.0087 (16) | 0.0019 (17) | −0.0269 (18) |
C6 | 0.0319 (19) | 0.0250 (18) | 0.054 (2) | −0.0062 (15) | −0.0110 (17) | −0.0174 (16) |
C7 | 0.0363 (19) | 0.0232 (17) | 0.039 (2) | −0.0096 (14) | −0.0131 (16) | −0.0095 (14) |
C8 | 0.0317 (17) | 0.0218 (16) | 0.0269 (17) | −0.0081 (13) | −0.0069 (14) | −0.0106 (13) |
C9 | 0.0324 (17) | 0.0233 (16) | 0.0265 (17) | −0.0122 (14) | −0.0067 (14) | −0.0098 (13) |
C10 | 0.058 (2) | 0.034 (2) | 0.031 (2) | −0.0162 (18) | −0.0100 (17) | −0.0028 (15) |
C11 | 0.039 (2) | 0.051 (2) | 0.050 (2) | −0.0213 (18) | 0.0022 (18) | −0.0152 (18) |
C12 | 0.0349 (19) | 0.0343 (19) | 0.046 (2) | −0.0088 (15) | −0.0174 (17) | −0.0076 (16) |
C13 | 0.055 (2) | 0.042 (2) | 0.031 (2) | −0.0202 (18) | −0.0169 (17) | −0.0050 (16) |
C14 | 0.047 (2) | 0.053 (2) | 0.037 (2) | −0.0204 (19) | 0.0030 (17) | −0.0202 (18) |
C15 | 0.041 (2) | 0.038 (2) | 0.077 (3) | 0.0026 (17) | −0.025 (2) | −0.027 (2) |
C16 | 0.0304 (17) | 0.0256 (17) | 0.0273 (18) | −0.0104 (14) | −0.0063 (14) | −0.0088 (14) |
C17 | 0.0306 (18) | 0.036 (2) | 0.039 (2) | −0.0059 (15) | −0.0056 (15) | −0.0143 (16) |
C18 | 0.039 (2) | 0.043 (2) | 0.046 (2) | −0.0055 (17) | −0.0022 (17) | −0.0222 (18) |
C19 | 0.065 (3) | 0.048 (2) | 0.036 (2) | −0.015 (2) | 0.0038 (19) | −0.0216 (18) |
C20 | 0.073 (3) | 0.049 (2) | 0.035 (2) | −0.012 (2) | −0.019 (2) | −0.0186 (18) |
C21 | 0.050 (2) | 0.042 (2) | 0.035 (2) | −0.0046 (17) | −0.0140 (17) | −0.0175 (16) |
C22 | 0.0289 (18) | 0.0258 (17) | 0.0248 (18) | −0.0077 (14) | −0.0078 (16) | −0.0062 (14) |
C23 | 0.0279 (17) | 0.0260 (18) | 0.0256 (19) | −0.0073 (14) | −0.0077 (14) | −0.0054 (14) |
C24 | 0.0251 (16) | 0.0273 (17) | 0.0311 (18) | −0.0047 (14) | −0.0095 (14) | −0.0065 (14) |
C25 | 0.0325 (19) | 0.0329 (19) | 0.042 (2) | −0.0102 (15) | −0.0103 (16) | −0.0080 (16) |
C26 | 0.036 (2) | 0.044 (2) | 0.038 (2) | 0.0013 (17) | −0.0051 (17) | −0.0209 (17) |
C27 | 0.0288 (18) | 0.048 (2) | 0.0292 (19) | −0.0108 (16) | 0.0006 (15) | −0.0069 (16) |
C28 | 0.0309 (18) | 0.037 (2) | 0.036 (2) | −0.0137 (16) | −0.0103 (15) | −0.0011 (16) |
C29 | 0.0304 (17) | 0.0305 (18) | 0.0289 (18) | −0.0062 (14) | −0.0089 (15) | −0.0079 (14) |
C30 | 0.0278 (17) | 0.0269 (17) | 0.0317 (18) | −0.0044 (14) | −0.0112 (14) | −0.0083 (14) |
C31 | 0.0302 (18) | 0.0356 (19) | 0.0335 (19) | −0.0046 (15) | −0.0086 (15) | −0.0110 (15) |
C32 | 0.046 (2) | 0.040 (2) | 0.0285 (19) | −0.0174 (17) | −0.0081 (16) | 0.0008 (16) |
C33 | 0.054 (2) | 0.0284 (19) | 0.045 (2) | −0.0043 (17) | −0.0227 (19) | 0.0007 (16) |
C34 | 0.036 (2) | 0.0311 (19) | 0.050 (2) | −0.0022 (16) | −0.0174 (17) | −0.0092 (17) |
C35 | 0.0354 (19) | 0.0275 (18) | 0.042 (2) | −0.0127 (15) | −0.0092 (16) | −0.0082 (15) |
C36 | 0.0294 (17) | 0.0222 (16) | 0.0279 (17) | −0.0087 (13) | −0.0088 (14) | −0.0019 (13) |
C37 | 0.0274 (17) | 0.0323 (18) | 0.0317 (19) | −0.0097 (14) | −0.0068 (15) | −0.0072 (15) |
C38 | 0.0364 (19) | 0.039 (2) | 0.0305 (19) | −0.0167 (16) | −0.0119 (16) | −0.0046 (15) |
C39 | 0.061 (2) | 0.039 (2) | 0.0260 (19) | −0.0215 (19) | −0.0107 (17) | −0.0113 (16) |
C40 | 0.0359 (19) | 0.036 (2) | 0.035 (2) | −0.0042 (16) | −0.0048 (16) | −0.0126 (16) |
C41 | 0.0298 (18) | 0.0326 (18) | 0.0268 (18) | −0.0091 (15) | −0.0083 (14) | −0.0061 (14) |
C42 | 0.0346 (18) | 0.0279 (18) | 0.0339 (19) | −0.0098 (14) | −0.0066 (15) | −0.0071 (14) |
C43 | 0.078 (4) | 0.071 (3) | 0.060 (3) | −0.001 (3) | 0.003 (3) | −0.015 (3) |
C44 | 0.076 (3) | 0.078 (3) | 0.050 (3) | −0.001 (3) | −0.011 (2) | −0.017 (3) |
C45 | 0.088 (4) | 0.060 (3) | 0.045 (3) | 0.009 (3) | −0.013 (3) | −0.013 (2) |
C46 | 0.079 (3) | 0.056 (3) | 0.047 (3) | −0.004 (3) | −0.006 (3) | 0.001 (2) |
C47 | 0.106 (4) | 0.055 (3) | 0.051 (3) | −0.029 (3) | −0.009 (3) | −0.002 (2) |
C48 | 0.112 (5) | 0.052 (3) | 0.058 (3) | −0.018 (3) | 0.011 (3) | −0.016 (2) |
F1 | 0.0571 (13) | 0.0386 (12) | 0.0563 (14) | −0.0179 (10) | −0.0069 (11) | −0.0192 (10) |
F2 | 0.0571 (14) | 0.0587 (14) | 0.0548 (15) | −0.0043 (11) | −0.0025 (11) | −0.0315 (12) |
F3 | 0.0481 (13) | 0.0773 (16) | 0.0467 (14) | −0.0215 (12) | 0.0112 (11) | −0.0148 (12) |
F4 | 0.0525 (13) | 0.0509 (13) | 0.0495 (13) | −0.0309 (11) | −0.0052 (10) | −0.0040 (10) |
F5 | 0.0452 (11) | 0.0342 (11) | 0.0394 (12) | −0.0152 (9) | −0.0054 (9) | −0.0115 (9) |
F6 | 0.0304 (11) | 0.0480 (12) | 0.0429 (12) | −0.0074 (9) | −0.0058 (9) | −0.0013 (10) |
F7 | 0.0616 (14) | 0.0571 (14) | 0.0446 (14) | −0.0183 (12) | −0.0075 (11) | 0.0128 (11) |
F8 | 0.0708 (15) | 0.0410 (13) | 0.0633 (16) | −0.0034 (11) | −0.0292 (13) | 0.0136 (11) |
F9 | 0.0401 (12) | 0.0429 (13) | 0.0778 (17) | 0.0055 (10) | −0.0253 (11) | −0.0086 (11) |
F10 | 0.0301 (11) | 0.0405 (12) | 0.0582 (14) | −0.0097 (9) | −0.0077 (10) | −0.0043 (10) |
F11 | 0.0282 (10) | 0.0454 (12) | 0.0537 (13) | −0.0060 (9) | −0.0130 (9) | −0.0177 (10) |
F12 | 0.0496 (13) | 0.0658 (14) | 0.0529 (14) | −0.0218 (11) | −0.0266 (11) | −0.0144 (11) |
F13 | 0.0730 (15) | 0.0681 (15) | 0.0489 (14) | −0.0206 (12) | −0.0136 (11) | −0.0338 (12) |
F14 | 0.0482 (13) | 0.0633 (15) | 0.0629 (15) | 0.0022 (11) | −0.0061 (11) | −0.0398 (12) |
F15 | 0.0276 (10) | 0.0490 (12) | 0.0533 (13) | −0.0015 (9) | −0.0146 (9) | −0.0203 (10) |
Ti—N1 | 1.898 (2) | C17—H17B | 0.9900 |
Ti—C22 | 2.195 (3) | C18—C19 | 1.517 (5) |
Ti—C23 | 2.230 (3) | C18—H18A | 0.9900 |
Ti—C1 | 2.256 (3) | C18—H18B | 0.9900 |
Ti—C2 | 2.333 (3) | C19—C20 | 1.517 (5) |
Ti—C8 | 2.395 (3) | C19—H19A | 0.9900 |
Ti—C3 | 2.474 (3) | C19—H19B | 0.9900 |
Ti—C9 | 2.556 (3) | C20—C21 | 1.529 (5) |
Ti—Al2 | 2.826 (2) | C20—H20A | 0.9900 |
Ti—Si | 2.890 (2) | C20—H20B | 0.9900 |
Ti—H22B | 2.19 (3) | C21—H21A | 0.9900 |
Ti—H23A | 2.26 (3) | C21—H21B | 0.9900 |
Si—N1 | 1.762 (2) | C22—Al2i | 2.086 (3) |
Si—C11 | 1.846 (3) | C22—H22A | 0.87 (3) |
Si—C1 | 1.861 (3) | C22—H22B | 0.94 (3) |
Si—C10 | 1.863 (3) | C23—H23A | 0.94 (4) |
Al1—C36 | 2.000 (3) | C23—H23B | 0.95 (3) |
Al1—C24 | 2.007 (3) | C24—C29 | 1.376 (4) |
Al1—C30 | 2.016 (3) | C24—C25 | 1.376 (5) |
Al1—C23 | 2.048 (3) | C25—F1 | 1.361 (4) |
Al2—C42 | 1.950 (3) | C25—C26 | 1.379 (5) |
Al2—C23 | 2.015 (3) | C26—F2 | 1.347 (4) |
Al2—C22 | 2.085 (3) | C26—C27 | 1.366 (5) |
Al2—C22i | 2.086 (3) | C27—F3 | 1.339 (4) |
Al2—Al2i | 2.695 (2) | C27—C28 | 1.368 (5) |
N1—C16 | 1.486 (4) | C28—F4 | 1.347 (4) |
C1—C8 | 1.440 (4) | C28—C29 | 1.380 (4) |
C1—C2 | 1.443 (4) | C29—F5 | 1.360 (4) |
C2—C3 | 1.409 (4) | C30—C31 | 1.384 (4) |
C2—C12 | 1.508 (4) | C30—C35 | 1.387 (4) |
C3—C9 | 1.442 (4) | C31—F6 | 1.364 (3) |
C3—C13 | 1.507 (4) | C31—C32 | 1.380 (4) |
C4—C5 | 1.362 (5) | C32—F7 | 1.349 (4) |
C4—C9 | 1.429 (4) | C32—C33 | 1.362 (5) |
C4—C14 | 1.509 (5) | C33—F8 | 1.348 (4) |
C5—C6 | 1.417 (5) | C33—C34 | 1.370 (5) |
C5—H5A | 0.9500 | C34—F9 | 1.348 (4) |
C6—C7 | 1.369 (4) | C34—C35 | 1.374 (4) |
C6—C15 | 1.505 (5) | C35—F10 | 1.356 (3) |
C7—C8 | 1.420 (4) | C36—C41 | 1.381 (4) |
C7—H7A | 0.9500 | C36—C37 | 1.384 (4) |
C8—C9 | 1.438 (4) | C37—F11 | 1.360 (3) |
C10—H10A | 0.9800 | C37—C38 | 1.370 (5) |
C10—H10B | 0.9800 | C38—F12 | 1.341 (4) |
C10—H10C | 0.9800 | C38—C39 | 1.380 (5) |
C11—H11A | 0.9800 | C39—F13 | 1.338 (4) |
C11—H11B | 0.9800 | C39—C40 | 1.377 (5) |
C11—H11C | 0.9800 | C40—F14 | 1.350 (4) |
C12—H12A | 0.9800 | C40—C41 | 1.368 (5) |
C12—H12B | 0.9800 | C41—F15 | 1.358 (3) |
C12—H12C | 0.9800 | C42—H42A | 0.9800 |
C13—H13A | 0.9800 | C42—H42B | 0.9800 |
C13—H13B | 0.9800 | C42—H42C | 0.9800 |
C13—H13C | 0.9800 | C43—C48 | 1.375 (7) |
C14—H14A | 0.9800 | C43—C44 | 1.376 (7) |
C14—H14B | 0.9800 | C43—H43A | 0.9500 |
C14—H14C | 0.9800 | C44—C45 | 1.369 (6) |
C15—H15A | 0.9800 | C44—H44A | 0.9500 |
C15—H15B | 0.9800 | C45—C46 | 1.383 (7) |
C15—H15C | 0.9800 | C45—H45A | 0.9500 |
C16—C17 | 1.518 (4) | C46—C47 | 1.379 (6) |
C16—C21 | 1.518 (4) | C46—H46A | 0.9500 |
C16—H16A | 0.95 (3) | C47—C48 | 1.375 (7) |
C17—C18 | 1.531 (5) | C47—H47A | 0.9500 |
C17—H17A | 0.9900 | C48—H48A | 0.9500 |
N1—Ti—C22 | 110.38 (12) | H12A—C12—H12B | 109.5 |
N1—Ti—C23 | 105.62 (12) | C2—C12—H12C | 109.5 |
C22—Ti—C23 | 89.82 (12) | H12A—C12—H12C | 109.5 |
N1—Ti—C1 | 75.68 (11) | H12B—C12—H12C | 109.5 |
C22—Ti—C1 | 139.91 (12) | C3—C13—H13A | 109.5 |
C23—Ti—C1 | 127.82 (11) | C3—C13—H13B | 109.5 |
N1—Ti—C2 | 92.20 (11) | H13A—C13—H13B | 109.5 |
C22—Ti—C2 | 103.62 (12) | C3—C13—H13C | 109.5 |
C23—Ti—C2 | 152.51 (12) | H13A—C13—H13C | 109.5 |
C1—Ti—C2 | 36.60 (10) | H13B—C13—H13C | 109.5 |
N1—Ti—C8 | 101.73 (10) | C4—C14—H14A | 109.5 |
C22—Ti—C8 | 143.93 (12) | C4—C14—H14B | 109.5 |
C23—Ti—C8 | 97.12 (11) | H14A—C14—H14B | 109.5 |
C1—Ti—C8 | 35.90 (10) | C4—C14—H14C | 109.5 |
C2—Ti—C8 | 58.16 (10) | H14A—C14—H14C | 109.5 |
N1—Ti—C3 | 126.11 (10) | H14B—C14—H14C | 109.5 |
C22—Ti—C3 | 90.28 (12) | C6—C15—H15A | 109.5 |
C23—Ti—C3 | 124.29 (12) | C6—C15—H15B | 109.5 |
C1—Ti—C3 | 58.92 (10) | H15A—C15—H15B | 109.5 |
C2—Ti—C3 | 33.92 (10) | C6—C15—H15C | 109.5 |
C8—Ti—C3 | 56.75 (10) | H15A—C15—H15C | 109.5 |
N1—Ti—C9 | 132.84 (10) | H15B—C15—H15C | 109.5 |
C22—Ti—C9 | 110.55 (12) | N1—C16—C17 | 110.8 (3) |
C23—Ti—C9 | 96.90 (12) | N1—C16—C21 | 111.4 (3) |
C1—Ti—C9 | 57.96 (10) | C17—C16—C21 | 111.1 (3) |
C2—Ti—C9 | 56.06 (10) | N1—C16—H16A | 110.6 (18) |
C8—Ti—C9 | 33.57 (9) | C17—C16—H16A | 105.4 (17) |
C3—Ti—C9 | 33.27 (10) | C21—C16—H16A | 107.4 (18) |
N1—Ti—Al2 | 127.24 (8) | C16—C17—C18 | 112.0 (3) |
C22—Ti—Al2 | 47.02 (9) | C16—C17—H17A | 109.2 |
C23—Ti—Al2 | 45.09 (8) | C18—C17—H17A | 109.2 |
C1—Ti—Al2 | 155.64 (8) | C16—C17—H17B | 109.2 |
C2—Ti—Al2 | 134.83 (8) | C18—C17—H17B | 109.2 |
C8—Ti—Al2 | 121.46 (8) | H17A—C17—H17B | 107.9 |
C3—Ti—Al2 | 103.61 (7) | C19—C18—C17 | 111.3 (3) |
C9—Ti—Al2 | 97.94 (7) | C19—C18—H18A | 109.4 |
N1—Ti—Si | 36.24 (7) | C17—C18—H18A | 109.4 |
C22—Ti—Si | 138.37 (9) | C19—C18—H18B | 109.4 |
C23—Ti—Si | 118.34 (9) | C17—C18—H18B | 109.4 |
C1—Ti—Si | 40.07 (8) | H18A—C18—H18B | 108.0 |
C2—Ti—Si | 65.89 (8) | C18—C19—C20 | 111.0 (3) |
C8—Ti—Si | 66.89 (7) | C18—C19—H19A | 109.4 |
C3—Ti—Si | 96.67 (7) | C20—C19—H19A | 109.4 |
C9—Ti—Si | 96.62 (7) | C18—C19—H19B | 109.4 |
Al2—Ti—Si | 159.25 (3) | C20—C19—H19B | 109.4 |
N1—Ti—H22B | 86.6 (9) | H19A—C19—H19B | 108.0 |
C22—Ti—H22B | 24.8 (9) | C19—C20—C21 | 111.8 (3) |
C23—Ti—H22B | 103.3 (9) | C19—C20—H20A | 109.3 |
C1—Ti—H22B | 128.6 (9) | C21—C20—H20A | 109.3 |
C2—Ti—H22B | 98.4 (9) | C19—C20—H20B | 109.3 |
C8—Ti—H22B | 155.0 (9) | C21—C20—H20B | 109.3 |
C3—Ti—H22B | 99.3 (9) | H20A—C20—H20B | 107.9 |
C9—Ti—H22B | 127.9 (9) | C16—C21—C20 | 111.4 (3) |
Al2—Ti—H22B | 67.3 (9) | C16—C21—H21A | 109.3 |
Si—Ti—H22B | 113.9 (9) | C20—C21—H21A | 109.3 |
N1—Ti—H23A | 81.4 (9) | C16—C21—H21B | 109.3 |
C22—Ti—H23A | 100.1 (8) | C20—C21—H21B | 109.3 |
C23—Ti—H23A | 24.3 (9) | H21A—C21—H21B | 108.0 |
C1—Ti—H23A | 119.9 (8) | Al2—C22—Al2i | 80.52 (12) |
C2—Ti—H23A | 156.2 (8) | Al2—C22—Ti | 82.62 (12) |
C8—Ti—H23A | 100.5 (8) | Al2i—C22—Ti | 140.60 (19) |
C3—Ti—H23A | 145.0 (9) | Al2—C22—H22A | 113 (2) |
C9—Ti—H23A | 113.0 (9) | Al2i—C22—H22A | 110 (2) |
Al2—Ti—H23A | 63.3 (9) | Ti—C22—H22A | 109 (2) |
Si—Ti—H23A | 97.3 (9) | Al2—C22—H22B | 135 (2) |
H22B—Ti—H23A | 104.0 (12) | Al2i—C22—H22B | 90 (2) |
N1—Si—C11 | 117.41 (14) | Ti—C22—H22B | 77.5 (19) |
N1—Si—C1 | 90.05 (12) | H22A—C22—H22B | 111 (3) |
C11—Si—C1 | 115.67 (16) | Al2—C23—Al1 | 105.01 (14) |
N1—Si—C10 | 113.95 (14) | Al2—C23—Ti | 83.33 (12) |
C11—Si—C10 | 106.15 (16) | Al1—C23—Ti | 170.69 (18) |
C1—Si—C10 | 113.41 (15) | Al2—C23—H23A | 129 (2) |
N1—Si—Ti | 39.54 (8) | Al1—C23—H23A | 92 (2) |
C11—Si—Ti | 135.78 (13) | Ti—C23—H23A | 80 (2) |
C1—Si—Ti | 51.30 (9) | Al2—C23—H23B | 119 (2) |
C10—Si—Ti | 117.78 (11) | Al1—C23—H23B | 92 (2) |
C36—Al1—C24 | 111.13 (13) | Ti—C23—H23B | 87 (2) |
C36—Al1—C30 | 102.56 (13) | H23A—C23—H23B | 107 (3) |
C24—Al1—C30 | 111.12 (13) | C29—C24—C25 | 113.6 (3) |
C36—Al1—C23 | 113.48 (14) | C29—C24—Al1 | 125.5 (2) |
C24—Al1—C23 | 108.44 (14) | C25—C24—Al1 | 120.9 (2) |
C30—Al1—C23 | 110.06 (13) | F1—C25—C24 | 118.9 (3) |
C42—Al2—C23 | 110.69 (14) | F1—C25—C26 | 116.8 (3) |
C42—Al2—C22 | 112.25 (15) | C24—C25—C26 | 124.2 (3) |
C23—Al2—C22 | 99.24 (13) | F2—C26—C27 | 119.3 (3) |
C42—Al2—C22i | 110.23 (14) | F2—C26—C25 | 121.3 (3) |
C23—Al2—C22i | 123.53 (15) | C27—C26—C25 | 119.4 (3) |
C22—Al2—C22i | 99.48 (12) | F3—C27—C26 | 120.2 (3) |
C42—Al2—Al2i | 124.09 (11) | F3—C27—C28 | 120.6 (3) |
C23—Al2—Al2i | 123.48 (12) | C26—C27—C28 | 119.2 (3) |
C22—Al2—Al2i | 49.75 (9) | F4—C28—C27 | 120.1 (3) |
C22i—Al2—Al2i | 49.73 (9) | F4—C28—C29 | 120.8 (3) |
C42—Al2—Ti | 110.81 (10) | C27—C28—C29 | 119.1 (3) |
C23—Al2—Ti | 51.58 (9) | F5—C29—C24 | 119.5 (3) |
C22—Al2—Ti | 50.36 (9) | F5—C29—C28 | 116.1 (3) |
C22i—Al2—Ti | 136.19 (10) | C24—C29—C28 | 124.4 (3) |
Al2i—Al2—Ti | 93.72 (4) | C31—C30—C35 | 113.1 (3) |
C16—N1—Si | 127.1 (2) | C31—C30—Al1 | 121.0 (2) |
C16—N1—Ti | 128.52 (19) | C35—C30—Al1 | 125.4 (2) |
Si—N1—Ti | 104.22 (13) | F6—C31—C32 | 116.7 (3) |
C8—C1—C2 | 105.8 (3) | F6—C31—C30 | 118.6 (3) |
C8—C1—Si | 125.6 (2) | C32—C31—C30 | 124.7 (3) |
C2—C1—Si | 120.7 (2) | F7—C32—C33 | 120.6 (3) |
C8—C1—Ti | 77.32 (16) | F7—C32—C31 | 120.6 (3) |
C2—C1—Ti | 74.62 (16) | C33—C32—C31 | 118.8 (3) |
Si—C1—Ti | 88.62 (12) | F8—C33—C32 | 120.0 (3) |
C3—C2—C1 | 109.9 (3) | F8—C33—C34 | 120.1 (3) |
C3—C2—C12 | 124.9 (3) | C32—C33—C34 | 119.9 (3) |
C1—C2—C12 | 125.2 (3) | F9—C34—C33 | 119.8 (3) |
C3—C2—Ti | 78.53 (17) | F9—C34—C35 | 121.0 (3) |
C1—C2—Ti | 68.78 (16) | C33—C34—C35 | 119.2 (3) |
C12—C2—Ti | 118.5 (2) | F10—C35—C34 | 116.0 (3) |
C2—C3—C9 | 108.0 (3) | F10—C35—C30 | 119.8 (3) |
C2—C3—C13 | 125.1 (3) | C34—C35—C30 | 124.3 (3) |
C9—C3—C13 | 126.6 (3) | C41—C36—C37 | 113.2 (3) |
C2—C3—Ti | 67.55 (17) | C41—C36—Al1 | 128.0 (2) |
C9—C3—Ti | 76.46 (17) | C37—C36—Al1 | 118.7 (2) |
C13—C3—Ti | 126.5 (2) | F11—C37—C38 | 116.9 (3) |
C5—C4—C9 | 117.1 (3) | F11—C37—C36 | 117.6 (3) |
C5—C4—C14 | 120.1 (3) | C38—C37—C36 | 125.5 (3) |
C9—C4—C14 | 122.6 (3) | F12—C38—C37 | 122.0 (3) |
C4—C5—C6 | 123.8 (3) | F12—C38—C39 | 119.8 (3) |
C4—C5—H5A | 118.1 | C37—C38—C39 | 118.2 (3) |
C6—C5—H5A | 118.1 | F13—C39—C40 | 120.4 (3) |
C7—C6—C5 | 119.8 (3) | F13—C39—C38 | 120.3 (3) |
C7—C6—C15 | 121.5 (3) | C40—C39—C38 | 119.2 (3) |
C5—C6—C15 | 118.7 (3) | F14—C40—C41 | 121.6 (3) |
C6—C7—C8 | 119.4 (3) | F14—C40—C39 | 118.8 (3) |
C6—C7—H7A | 120.3 | C41—C40—C39 | 119.5 (3) |
C8—C7—H7A | 120.3 | F15—C41—C40 | 116.2 (3) |
C7—C8—C9 | 119.6 (3) | F15—C41—C36 | 119.4 (3) |
C7—C8—C1 | 131.1 (3) | C40—C41—C36 | 124.3 (3) |
C9—C8—C1 | 109.2 (3) | Al2—C42—H42A | 109.5 |
C7—C8—Ti | 120.0 (2) | Al2—C42—H42B | 109.5 |
C9—C8—Ti | 79.35 (17) | H42A—C42—H42B | 109.5 |
C1—C8—Ti | 66.77 (15) | Al2—C42—H42C | 109.5 |
C4—C9—C8 | 120.0 (3) | H42A—C42—H42C | 109.5 |
C4—C9—C3 | 132.9 (3) | H42B—C42—H42C | 109.5 |
C8—C9—C3 | 107.0 (3) | C48—C43—C44 | 119.5 (5) |
C4—C9—Ti | 130.8 (2) | C48—C43—H43A | 120.2 |
C8—C9—Ti | 67.08 (16) | C44—C43—H43A | 120.2 |
C3—C9—Ti | 70.27 (16) | C45—C44—C43 | 119.8 (5) |
Si—C10—H10A | 109.5 | C45—C44—H44A | 120.1 |
Si—C10—H10B | 109.5 | C43—C44—H44A | 120.1 |
H10A—C10—H10B | 109.5 | C44—C45—C46 | 120.9 (5) |
Si—C10—H10C | 109.5 | C44—C45—H45A | 119.6 |
H10A—C10—H10C | 109.5 | C46—C45—H45A | 119.6 |
H10B—C10—H10C | 109.5 | C47—C46—C45 | 119.3 (5) |
Si—C11—H11A | 109.5 | C47—C46—H46A | 120.4 |
Si—C11—H11B | 109.5 | C45—C46—H46A | 120.4 |
H11A—C11—H11B | 109.5 | C48—C47—C46 | 119.6 (5) |
Si—C11—H11C | 109.5 | C48—C47—H47A | 120.2 |
H11A—C11—H11C | 109.5 | C46—C47—H47A | 120.2 |
H11B—C11—H11C | 109.5 | C43—C48—C47 | 120.9 (5) |
C2—C12—H12A | 109.5 | C43—C48—H48A | 119.6 |
C2—C12—H12B | 109.5 | C47—C48—H48A | 119.6 |
Symmetry code: (i) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C84H76Al4N2Si2Ti2·2(C6D6) |
Mr | 2099.58 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 12.8651 (7), 13.7422 (7), 15.2642 (9) |
α, β, γ (°) | 70.595 (2), 70.795 (2), 71.944 (2) |
V (Å3) | 2341.9 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.34 |
Crystal size (mm) | 0.27 × 0.11 × 0.06 |
Data collection | |
Diffractometer | SMART CCD area detector diffractometer |
Absorption correction | Integration Integration based on measured indexed crystal faces, SHELXTL (Bruker 1998) |
Tmin, Tmax | 0.925, 0.985 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15647, 10542, 5884 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.123, 0.96 |
No. of reflections | 10542 |
No. of parameters | 636 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.35, −0.37 |
Computer programs: Bruker SMART (Bruker 1998), Bruker SMART & SAINT (Bruker 1998), Bruker SHELXTL (Bruker 1998), Bruker SHELXTL.
Ti—N1 | 1.898 (2) | Ti—H22B | 2.19 (3) |
Ti—C22 | 2.195 (3) | Ti—H23A | 2.26 (3) |
Ti—C23 | 2.230 (3) | Al1—C23 | 2.048 (3) |
Ti—C1 | 2.256 (3) | Al2—C42 | 1.950 (3) |
Ti—C2 | 2.333 (3) | Al2—C23 | 2.015 (3) |
Ti—C8 | 2.395 (3) | Al2—C22 | 2.085 (3) |
Ti—C3 | 2.474 (3) | Al2—C22i | 2.086 (3) |
Ti—C9 | 2.556 (3) | Al2—Al2i | 2.695 (2) |
N1—Ti—C22 | 110.38 (12) | Al2i—C22—Ti | 140.60 (19) |
N1—Ti—C23 | 105.62 (12) | Ti—C22—H22B | 77.5 (19) |
C22—Ti—C23 | 89.82 (12) | Al2—C23—Ti | 83.33 (12) |
C22—Al2—C22i | 99.48 (12) | Ti—C23—H23A | 80 (2) |
Al2—C22—Ti | 82.62 (12) |
Symmetry code: (i) −x+1, −y+1, −z. |
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Catalyst decomposition of activated metallocene and constrained geometry complexes is a key contribution to catalyst activity decay in catalytic homogeneous olefin polymerization (Chen & Marks, 2000). We were interested in the thermal stability of an activated catalyst, Me2Si(η5-2,3,4,6-Me4—C9H2)(C6H11N)Ti(CH3) (µ-CH3Al(C6F5)3)·(C6D6) (I), an example of the constrained geometry catalyst family (McKnight & Waymouth, 1998). Upon heating a C6D6 solution of (I) in a sealed NMR tube under Ar atmosphere at 333 K for 12 h, we have found that the dimer (II) is formed, the structure of which is reported here.
The molecular structure of the compound (II) is depicted in Fig.1 and selected geometric parameters are given in Table 1. Complex (II) crystallizes as a dimer having an inversion center. Each Ti metal center is coordinated in a distorted tetrahedral geometry [N1—Ti—C22 = 110.4 (2), N1—Ti—C23 = 105.6 (2), C22—Ti—C23 = 89.8 (2)°] by the η5-substituted indenyl ligand, dimethylsilyl bridged N-cyclohexyl amide, and two anionic methylene ligands. The openness of the coordination sphere about Ti is manifested by an obtuse Cp(centroid)-Ti—N angle of 108.1 (2)°. In addition to the above ligands coordinated to Ti, one of each bridging methylene H atoms (H22B and H23A) exhibit relatively close contacts to Ti, with Ti—H22B and Ti—H23A distances of 2.19 (3) and 2.26 (3) Å and acute Ti—C22—H22B and Ti—C23—H23A angles of 77 (2) and 80 (2)°, indicative of two α-agostic interactions to each Ti.
Two bridging methylene ligands are unsymmetrically bound to Ti with distances of 2.195 (3) and 2.230 (3) Å for Ti—C22 and Ti—C23, respectively, which are approximately 0.2 Å (average) longer than Ti(µ-CH2) distances in [(Cy2N)2Ti(µ-CH2)]2 (Scoles et al., 1994). These distances are slightly shorter than the Ti—CH3 bond in [CpTi(µ2-Me)(µ2-NPiPr3)(µ4-C)(µ2-AlMe2)2(AlMe2)] but substantially longer than the Ti—C (carbide) bond in the same molecule (Kickham et al., 2000). Linking the two Ti centers are three fused four-membered metallacycles with torsion angles of 126.5 (2) and 144.3 (2)° for C23—Al2—C22—Al2A and Ti—C22—Al2—C22A, respectively (Al2A and C22A are derived from Al2 and C22 by the symmetry 1 - x, 1 - y, -z). The middle four-membered ring is coplanar (C22—Al2—C22A—Al2A = 0°) while the other two adopt a 'puckered' conformation [Ti—C22—Al2—C23 = -17.8 (2)°]. Due to the presence of strain that arises from the metallacycles, the geometry at the Al center on the ring (Al2) is that of a highly distorted tetrahedron. The largest deviations from tetrahedral geometry are found in the obtuse C22—Al2—C23 angle of 99.2 (2)° and the significantly larger C23—Al2—C22A angle of 123.5 (2)°.
There is Al(C6F5)3 group attached to C23 (and C23A) and the Ti—C23—Al1 vector is close to linearity with angle of 170.7 (2)°, suggesting some degree of dipole-dipole component to the ion-ion interaction in this complex. Compared to the Ti—C22 bond distance, the Ti—C23 bond is only slightly elongated by the attached strongly Lewis acidic Al(C6F5)3 group, presumably due to the metallacycles formation. The C23—Al(C6F5)3 distance of 2.048 (3) Å is comparable to those in the anion µ-CH3—Al(C6F5)3- [2.084 (2) and 2.059 (2) Å] in a 'doubly activated' ansa-zirconocene complex (Chen, 2000) and to that in the µ-CH3—Al(C6F5)3- (2.033 (3) Å) in a 'constrained geometry' Ti complex (Chen et al., 2001).