A dimeric constrained-geometry titanium complex linked by double Ti–CH₂–Al–CH₂ heterocycles

In the structure of bis({N-[di­methyl(1η⁵-2,3,4,6-tetra­methyl­in­den­yl)­silyl]­cyclo­hexyl­amido-1κN}(methyl-3κC)-di-μ₃-methyl­ene-1:2:3κ³C;1:3:3′κ³C-tris(pentafluorophenyl-2κC)titanium) benzene disolvate, [Me₂Si(η⁵-2,3,4,6-Me₄C₉H₂)(C₆H₁₁N)]Ti[(μ₃-CH₂)Al(C₆F₅)₃][AlMe(μ₃-CH₂)]₂ or [Ti₂(C₂₁H₇AlF₁₅)₂(C₂₁H₃₁NSi)₂]·2C₆D₆, the dimer is located on an inversion center, and the two Ti centers are linked by double Ti(μ₃-CH₂)Al(C₆F₅)₃AlMe(μ₃-CH₂) heterocycles. The electron-deficient Ti centers are further stabilized by two α-agostic interactions between Ti and one H atom of each bridging methyl­ene group.

S1. Comment

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).

S2. Experimental

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-5^TM 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.

S3. Refinement

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 1.2U_eq of the parent C; 1.5U_eq 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).

Computing details

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.

Figures

Fig. 1. Molecular structure of (I), with 40% probability displacement ellipsoids, showing the atom-numbering scheme. Atoms Al1 and Al1A (where A = 1 - x, 1 - y, -z) have three open bonds around them, each representing a –C6F5 group which are not shown for clarity. The benzene solvent molecule has also been removed for clarity.

(II)

Crystal data

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) Å^3	0.27 × 0.11 × 0.06 mm

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0481P)^2] where P = (Fo^2 + 2Fc^2)/3
10542 reflections	(Δ/σ)max < 0.001
636 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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—Al2^i	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—C22^i	2.086 (3)	C27—F3	1.339 (4)
Al2—Al2^i	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—Al2^i	80.52 (12)
C2—Ti—H23A	156.2 (8)	Al2—C22—Ti	82.62 (12)
C8—Ti—H23A	100.5 (8)	Al2^i—C22—Ti	140.60 (19)
C3—Ti—H23A	145.0 (9)	Al2—C22—H22A	113 (2)
C9—Ti—H23A	113.0 (9)	Al2^i—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)	Al2^i—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—C22^i	110.23 (14)	F2—C26—C25	121.3 (3)
C23—Al2—C22^i	123.53 (15)	C27—C26—C25	119.4 (3)
C22—Al2—C22^i	99.48 (12)	F3—C27—C26	120.2 (3)
C42—Al2—Al2^i	124.09 (11)	F3—C27—C28	120.6 (3)
C23—Al2—Al2^i	123.48 (12)	C26—C27—C28	119.2 (3)
C22—Al2—Al2^i	49.75 (9)	F4—C28—C27	120.1 (3)
C22^i—Al2—Al2^i	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)
C22^i—Al2—Ti	136.19 (10)	C24—C29—C28	124.4 (3)
Al2^i—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.