{N-[Di­methyl(η⁵-2,3,4,6-tetra­methyl­indenyl)­silyl]­cyclo­butyl­amido-κN}(η⁴-1,4-di­phenyl-1,3-buta­diene)­titanium(II)

The titanium metal center in the title compound, [Ti(C₁₉H₂₇NSi)(C₁₆H₁₄)], is coordinated in a distorted tetrahedral geom­etry by a η⁵-indenyl ligand, a di­methyl­silyl-bridged N-cyclo­butyl­amido ligand and an s-cis-η⁴-1,4-di­phenyl-1,3-buta­diene ligand in a `prone' π-fashion, revealing a formal divalent Ti center.

S1. Comment

Constrained-geometry catalysts are a very important catalyst family which has had a major impact on homogeneous olefin polymerization technologies (Stevens et al., 1991; McKnight & Waymouth, 1998). In this catalyst family, constrained-geometry titanium(II)–diene complexes, in particular, offer structural diversity and unique olefin polymerization activity (Devore et al., 1995). A common procedure used for the preparation of a variety of constrained-geometry titanium–diene complexes is to react the corresponding dichloride precursor with two equivalents of ⁿBuLi in the presence of excess diene. In the course of structure–activity studies of the constrained-geometry catalysts having ancilliary (η⁵:η¹-C₅Me₄SiMe₂N^tBu), we found that when replacing ^tBu of the ^tBuN group in the ligand with less bulky secondary C atoms, such as cyclobutyl, the diene complex cannot be obtained with the common procedure. Considering the reactivity of the α-H atom of the N-cyclobutyl group, we found that the use of the milder ⁿBuMgBr reagent instead of ⁿBuLi successfully offered a desired titanium(II)–diene complex, viz. Me₂Si(η⁵-2,3,4,6-Me₄C₉H₂)(C₄H₇N)Ti(s-cis-η⁴-1, 4-Ph₂C₄H₄), (I), the structure of which is reported here.

The molecular structure of the title compound is depicted in Fig. 1 and selected geometric parameters are given in Table 1. The Ti metal center is coordinated in a distorted tetrahedral geometry by an η⁵-indenyl ligand, a dimethylsilyl-bridged N-cyclobutylamido ligand and a 1,4-diphenyl-1,3-butadiene ligand in a `prone' π-fashion (Dahlmann et al., 2000; Devore et al., 1995; Erker et al., 1985; Yasuda et al., 1985). A Cp—Ti—N angle (Cp is the centroid of the indenyl five-membered ring) of 110.40 (8)° reflects the openness of the coordination sphere about Ti.

The 1,4-diphenyl-1,3-butadiene ligand adopts an s-cis orientation with the diene being bound to Ti in a π-fashion. The two Ti—C(terminal) diene distances [Ti—C20 = 2.217 (2) Å and Ti—C23 = 2.233 (2) Å] differ from the two Ti—C(internal) diene distances [Ti—C21 = 2.295 (2) Å and Ti—C22 = 2.295 (2) Å] by only 0.070 Å. The very small C—C distance differences [C20—C21 = 1.416 (3) Å, C21—C22 = 1.397 (3) Å and C22—C23 = 1.419 (3) Å] in the diene ligand also support the assignment of a predominantly π-bound diene ligand (Dahlmann et al., 2000; Devore et al., 1995). A C20—C21—C22—C23 torsion angle of -0.6 (4)° reflects the coplanarity of these atoms.

The Ti—N distance of 1.963 (2) Å compares well with those in typical ^tBuN constrained-geometry Ti^II complexes (Dahlmann et al., 2000; Devore et al., 1995), but is considerably longer than in typical Ti^IV amide complexes (Lappert et al., 1980).

Related literature

For related literature, see: Abboud et al. (1997); Dahlmann et al. (2000); Devore et al. (1995); Erker et al. (1985); Lappert et al. (1980); McKnight & Waymouth (1998); Stevens et al. (1991); Yasuda et al. (1985).

S2. Experimental

Me₂Si(η⁵-2,3,4,6-Me₄C₉H₂)(C₄H₇N)Ti(1,4-Ph₂C₄H₄) was prepared from the reaction of Me₂Si(η⁵-2,3,4,6-Me₄C₉H₂)(C₄H₇N)TiCl₂ with two equivalents of ⁿBuMgBr in the presence of one equivalent of trans-1,4-diphenyl-1,3-butadiene in hexanes under inert atomospheric conditions, using a similar procedure to that described previously by Devore et al. (1995). The resulting dark-red solution was stored at 238 K in a glove-box for 5 d, after which time, dark crystals of the title complex had formed. The selected crystal was immersed in Paratone N oil and mounted on a thin glass fiber in a glove-box.

S3. Refinement

C—H distances of 0.98 and 0.99 Å were used for methyl and secondary H atoms, respectively. A distance of 0.95 Å was used for H atoms on Csp² atoms. The H-atom displacement parameters were set at 1.2U_eq (1.5U_eq for the methyl H atoms) of the parent C atom. The H atoms on atoms C20—C23, as well as the methyl H atoms on C10 and C11, were obtained from a difference Fourier map and refined without any constraints [C—H = 0.93 (2)–1.02 (3) Å]. 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: SMART (Bruker, 1998); cell refinement: SMART and SAINT (Bruker, 1998); data reduction: SHELXTL (Bruker, 1998); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. The molecular structure of (I), with 50% probability ellipsoids, showing the atom-numbering scheme.

{N-[Dimethyl(η⁵-1,2,5,7-tetramethylindenyl)silyl]cyclobutylamido-κN}- (η⁴-1,4-diphenyl-1,3-butadiene)titanium(II)

Crystal data

[Ti(C19H27NSi)(C16H14)]	F(000) = 1176
Mr = 551.68	Dx = 1.249 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.0726 (6) Å	Cell parameters from 4542 reflections
b = 20.509 (1) Å	θ = 2.0–27.5°
c = 13.9311 (8) Å	µ = 0.36 mm^−1
β = 112.020 (1)°	T = 173 K
V = 2932.9 (3) Å^3	Needle, black
Z = 4	0.19 × 0.15 × 0.09 mm

Data collection

Bruker SMART diffractometer	6740 independent reflections
Radiation source: normal-focus sealed tube	4070 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
ω scans	θmax = 27.5°, θmin = 1.9°
Absorption correction: analytical integration, based on measured indexed faces (SHELXTL; Sheldrick, 1998)	h = −14→13
Tmin = 0.931, Tmax = 0.973	k = −26→15
20107 measured reflections	l = −17→18

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0458P)^2] where P = (Fo^2 + 2Fc^2)/3
6740 reflections	(Δ/σ)max = 0.007
383 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

Experimental. All syntheses and manipulations of air-sensitive materials were carried out in an inert atmosphere (argon) glove box. 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.

A Bruker SMART PLATFORM with a CCD area detector was used for data collection. The selected crystal was mounted on a thin glass fiber and bathed in a cold nitrogen stream for the duration of this study. 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. Three sets of 20 frames were collected covering three perpendicular sectors of space. Reflections from these frames were used to obtain an initial set of cell parameters. 1381 frames, 0.3° in ω, were measured in three separate runs. This provided a range of at least 2.4 to 3.6 redundancy level. The first 50 frames were remeasured at the end of data collections in order to monitor crystal and instrument stability and to enable crystal decay corrections. This procedure is different from using standardreflections as with conventional diffractometers. Thus the CIF items -diffrn-standards-number, -diffrn-standards-interval-time and -diffrn-standards-interval-time are neither produced nor needed. Program SAINT was used to integrate all frames and 8192 reflections were used to refine the cell 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.

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

	x	y	z	Uiso*/Ueq
Ti	0.54291 (4)	0.272935 (19)	0.63494 (3)	0.02444 (11)
Si	0.53023 (6)	0.19255 (3)	0.79841 (5)	0.02882 (16)
N1	0.42767 (17)	0.21588 (8)	0.67538 (13)	0.0254 (4)
C1	0.6683 (2)	0.24417 (11)	0.79705 (16)	0.0281 (5)
C2	0.7466 (2)	0.22813 (12)	0.73696 (17)	0.0341 (6)
C3	0.7827 (2)	0.28541 (13)	0.70004 (18)	0.0365 (6)
C4	0.7465 (3)	0.40900 (13)	0.73082 (19)	0.0430 (7)
C5	0.6883 (3)	0.44781 (13)	0.7797 (2)	0.0459 (7)
H5A	0.6986	0.4937	0.7767	0.055*
C6	0.6125 (2)	0.42359 (12)	0.83547 (18)	0.0385 (6)
C7	0.6001 (2)	0.35835 (11)	0.84316 (17)	0.0304 (5)
H7A	0.5481	0.3418	0.8785	0.037*
C8	0.6640 (2)	0.31427 (11)	0.79906 (15)	0.0271 (5)
C9	0.7346 (2)	0.34012 (12)	0.73911 (17)	0.0321 (5)
C10	0.4731 (3)	0.21363 (16)	0.9048 (2)	0.0404 (7)
H10A	0.432 (2)	0.2551 (12)	0.8964 (17)	0.032 (7)*
H10B	0.416 (3)	0.1807 (14)	0.911 (2)	0.067 (9)*
H10C	0.551 (3)	0.2130 (13)	0.973 (2)	0.071 (9)*
C11	0.5712 (3)	0.10433 (14)	0.8134 (2)	0.0454 (7)
H11A	0.566 (3)	0.0842 (13)	0.748 (2)	0.058 (8)*
H11B	0.509 (3)	0.0803 (13)	0.8317 (19)	0.051 (8)*
H11C	0.651 (3)	0.0983 (12)	0.867 (2)	0.048 (8)*
C12	0.2939 (2)	0.19578 (11)	0.62254 (16)	0.0278 (5)
H12A	0.2614	0.2139	0.5507	0.033*
C13	0.2535 (2)	0.12358 (11)	0.61712 (19)	0.0398 (6)
H13A	0.2426	0.1021	0.5507	0.048*
H13B	0.3094	0.0972	0.6768	0.048*
C14	0.1250 (3)	0.14548 (14)	0.6249 (2)	0.0494 (7)
H14A	0.0522	0.1502	0.5572	0.059*
H14B	0.0986	0.1190	0.6733	0.059*
C15	0.1916 (2)	0.20993 (13)	0.6710 (2)	0.0445 (7)
H15A	0.2279	0.2109	0.7476	0.053*
H15B	0.1375	0.2490	0.6422	0.053*
C16	0.7869 (3)	0.16054 (13)	0.7182 (2)	0.0490 (7)
H16A	0.8745	0.1512	0.7686	0.074*
H16B	0.7871	0.1580	0.6480	0.074*
H16C	0.7253	0.1286	0.7257	0.074*
C17	0.8739 (3)	0.28722 (15)	0.6413 (2)	0.0578 (9)
H17A	0.9638	0.2927	0.6904	0.087*
H17B	0.8502	0.3238	0.5925	0.087*
H17C	0.8665	0.2463	0.6032	0.087*
C18	0.8238 (3)	0.43774 (15)	0.6716 (2)	0.0673 (9)
H18A	0.8210	0.4854	0.6745	0.101*
H18B	0.7861	0.4234	0.5993	0.101*
H18C	0.9144	0.4230	0.7027	0.101*
C19	0.5455 (3)	0.47112 (13)	0.8818 (2)	0.0532 (8)
H19A	0.4977	0.4470	0.9171	0.080*
H19B	0.4846	0.4980	0.8267	0.080*
H19C	0.6108	0.4992	0.9317	0.080*
C20	0.5099 (2)	0.23085 (12)	0.48052 (16)	0.0291 (5)
H20	0.422 (2)	0.2268 (10)	0.4684 (16)	0.028 (6)*
C21	0.5469 (2)	0.29640 (12)	0.47512 (17)	0.0318 (6)
H21	0.626 (2)	0.3056 (10)	0.4642 (17)	0.035 (6)*
C22	0.4970 (2)	0.35083 (12)	0.50795 (17)	0.0325 (6)
H22	0.548 (2)	0.3904 (11)	0.5134 (16)	0.027 (6)*
C23	0.3999 (2)	0.35019 (12)	0.55152 (16)	0.0290 (5)
H23	0.336 (2)	0.3140 (10)	0.5279 (16)	0.029 (6)*
C24	0.5698 (2)	0.17466 (12)	0.44952 (16)	0.0306 (5)
C25	0.5279 (3)	0.11183 (13)	0.45826 (19)	0.0434 (7)
H25A	0.4601	0.1058	0.4836	0.052*
C26	0.5828 (3)	0.05788 (13)	0.4310 (2)	0.0512 (7)
H26A	0.5530	0.0155	0.4386	0.061*
C27	0.6804 (3)	0.06510 (14)	0.3927 (2)	0.0495 (7)
H27A	0.7184	0.0280	0.3743	0.059*
C28	0.7218 (3)	0.12687 (13)	0.3816 (2)	0.0480 (7)
H28A	0.7884	0.1326	0.3549	0.058*
C29	0.6668 (3)	0.18069 (13)	0.40919 (19)	0.0407 (6)
H29A	0.6962	0.2230	0.4004	0.049*
C30	0.3498 (2)	0.40971 (11)	0.58318 (16)	0.0304 (5)
C31	0.2370 (3)	0.40653 (13)	0.60537 (19)	0.0419 (6)
H31A	0.1963	0.3655	0.6030	0.050*
C32	0.1830 (3)	0.46159 (15)	0.6307 (2)	0.0502 (7)
H32A	0.1051	0.4581	0.6440	0.060*
C33	0.2417 (3)	0.52136 (13)	0.6367 (2)	0.0480 (7)
H33A	0.2047	0.5592	0.6539	0.058*
C34	0.3542 (3)	0.52577 (13)	0.61760 (19)	0.0449 (7)
H34A	0.3958	0.5668	0.6227	0.054*
C35	0.4078 (2)	0.47088 (12)	0.59091 (18)	0.0376 (6)
H35A	0.4856	0.4750	0.5776	0.045*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ti	0.0222 (2)	0.0287 (2)	0.0222 (2)	−0.00113 (18)	0.00805 (15)	−0.00125 (17)
Si	0.0308 (4)	0.0266 (4)	0.0263 (3)	−0.0003 (3)	0.0075 (3)	0.0019 (3)
N1	0.0239 (10)	0.0261 (11)	0.0252 (9)	0.0000 (8)	0.0081 (8)	−0.0006 (7)
C1	0.0245 (13)	0.0317 (14)	0.0231 (11)	0.0020 (10)	0.0031 (9)	−0.0011 (9)
C2	0.0234 (12)	0.0441 (16)	0.0291 (12)	0.0040 (11)	0.0033 (10)	−0.0049 (11)
C3	0.0213 (13)	0.0543 (18)	0.0331 (13)	−0.0021 (11)	0.0091 (10)	−0.0061 (11)
C4	0.0432 (16)	0.0444 (17)	0.0371 (14)	−0.0204 (13)	0.0100 (12)	−0.0015 (12)
C5	0.0526 (18)	0.0266 (15)	0.0467 (16)	−0.0118 (12)	0.0049 (14)	−0.0013 (12)
C6	0.0416 (16)	0.0342 (16)	0.0307 (13)	0.0027 (12)	0.0032 (11)	−0.0065 (11)
C7	0.0320 (14)	0.0288 (14)	0.0281 (12)	−0.0008 (10)	0.0086 (10)	−0.0012 (10)
C8	0.0227 (12)	0.0326 (14)	0.0211 (11)	−0.0025 (10)	0.0026 (9)	−0.0043 (9)
C9	0.0225 (13)	0.0403 (15)	0.0290 (12)	−0.0080 (10)	0.0047 (10)	−0.0028 (10)
C10	0.0462 (17)	0.046 (2)	0.0306 (14)	−0.0092 (14)	0.0157 (13)	0.0013 (12)
C11	0.0436 (19)	0.0329 (17)	0.0489 (18)	0.0027 (13)	0.0049 (15)	0.0076 (13)
C12	0.0255 (13)	0.0321 (13)	0.0243 (11)	−0.0031 (10)	0.0076 (9)	0.0014 (9)
C13	0.0426 (16)	0.0318 (15)	0.0367 (14)	−0.0080 (11)	0.0053 (12)	0.0051 (11)
C14	0.0367 (16)	0.067 (2)	0.0430 (15)	−0.0186 (14)	0.0135 (13)	0.0071 (14)
C15	0.0309 (15)	0.066 (2)	0.0389 (14)	−0.0062 (12)	0.0154 (12)	−0.0090 (12)
C16	0.0401 (17)	0.0530 (19)	0.0492 (16)	0.0161 (13)	0.0113 (13)	−0.0087 (13)
C17	0.0306 (16)	0.098 (3)	0.0492 (17)	−0.0104 (15)	0.0204 (13)	−0.0154 (16)
C18	0.072 (2)	0.068 (2)	0.066 (2)	−0.0346 (18)	0.0306 (18)	0.0016 (16)
C19	0.069 (2)	0.0363 (17)	0.0449 (16)	0.0139 (14)	0.0106 (15)	−0.0085 (12)
C20	0.0258 (13)	0.0366 (15)	0.0245 (11)	−0.0007 (11)	0.0091 (10)	−0.0021 (10)
C21	0.0327 (14)	0.0399 (16)	0.0249 (12)	−0.0006 (11)	0.0133 (10)	−0.0006 (10)
C22	0.0357 (15)	0.0334 (15)	0.0284 (12)	−0.0022 (11)	0.0119 (11)	0.0014 (10)
C23	0.0319 (14)	0.0290 (14)	0.0257 (12)	−0.0019 (11)	0.0104 (10)	0.0015 (10)
C24	0.0320 (14)	0.0358 (15)	0.0234 (12)	0.0012 (10)	0.0098 (10)	−0.0020 (10)
C25	0.0542 (18)	0.0420 (17)	0.0439 (15)	−0.0041 (13)	0.0298 (14)	−0.0037 (12)
C26	0.070 (2)	0.0350 (17)	0.0571 (18)	−0.0043 (14)	0.0339 (16)	−0.0039 (13)
C27	0.062 (2)	0.0411 (18)	0.0512 (17)	0.0118 (14)	0.0274 (15)	−0.0065 (13)
C28	0.0477 (18)	0.0471 (19)	0.0601 (18)	0.0005 (13)	0.0330 (15)	−0.0097 (14)
C29	0.0446 (16)	0.0389 (16)	0.0456 (15)	−0.0008 (12)	0.0249 (13)	−0.0059 (12)
C30	0.0341 (14)	0.0323 (14)	0.0244 (12)	0.0025 (10)	0.0104 (10)	0.0017 (10)
C31	0.0436 (17)	0.0428 (17)	0.0445 (15)	−0.0053 (12)	0.0224 (13)	−0.0078 (12)
C32	0.0469 (18)	0.059 (2)	0.0554 (18)	0.0055 (14)	0.0310 (15)	−0.0065 (14)
C33	0.064 (2)	0.0417 (18)	0.0450 (16)	0.0174 (14)	0.0284 (15)	0.0018 (13)
C34	0.066 (2)	0.0306 (16)	0.0447 (16)	0.0051 (13)	0.0288 (15)	0.0059 (12)
C35	0.0443 (16)	0.0353 (16)	0.0386 (14)	0.0053 (12)	0.0217 (12)	0.0059 (11)

Geometric parameters (Å, º)

Ti—N1	1.963 (2)	C14—H14B	0.9900
Ti—C20	2.217 (2)	C15—H15A	0.9900
Ti—C23	2.233 (2)	C15—H15B	0.9900
Ti—C1	2.242 (2)	C16—H16A	0.9800
Ti—C21	2.295 (2)	C16—H16B	0.9800
Ti—C22	2.295 (2)	C16—H16C	0.9800
Ti—C8	2.334 (2)	C17—H17A	0.9800
Ti—C2	2.355 (2)	C17—H17B	0.9800
Ti—C3	2.476 (2)	C17—H17C	0.9800
Ti—C9	2.490 (2)	C18—H18A	0.9800
Ti—Si	2.8572 (7)	C18—H18B	0.9800
Si—N1	1.7311 (18)	C18—H18C	0.9800
Si—C11	1.858 (3)	C19—H19A	0.9800
Si—C1	1.865 (2)	C19—H19B	0.9800
Si—C10	1.867 (3)	C19—H19C	0.9800
N1—C12	1.445 (3)	C20—C21	1.416 (3)
C1—C8	1.439 (3)	C20—C24	1.473 (3)
C1—C2	1.451 (3)	C20—H20	0.93 (2)
C2—C3	1.399 (3)	C21—C22	1.397 (3)
C2—C16	1.509 (3)	C21—H21	0.96 (2)
C3—C9	1.434 (3)	C22—C23	1.419 (3)
C3—C17	1.520 (3)	C22—H22	0.98 (2)
C4—C5	1.356 (4)	C23—C30	1.475 (3)
C4—C9	1.428 (3)	C23—H23	0.99 (2)
C4—C18	1.514 (4)	C24—C25	1.390 (3)
C5—C6	1.430 (4)	C24—C29	1.393 (3)
C5—H5A	0.9500	C25—C26	1.382 (3)
C6—C7	1.353 (3)	C25—H25A	0.9500
C6—C19	1.508 (3)	C26—C27	1.381 (4)
C7—C8	1.422 (3)	C26—H26A	0.9500
C7—H7A	0.9500	C27—C28	1.376 (4)
C8—C9	1.441 (3)	C27—H27A	0.9500
C10—H10A	0.95 (2)	C28—C29	1.383 (3)
C10—H10B	0.95 (3)	C28—H28A	0.9500
C10—H10C	1.02 (3)	C29—H29A	0.9500
C11—H11A	0.98 (3)	C30—C31	1.396 (3)
C11—H11B	0.96 (3)	C30—C35	1.395 (3)
C11—H11C	0.92 (3)	C31—C32	1.384 (3)
C12—C13	1.540 (3)	C31—H31A	0.9500
C12—C15	1.548 (3)	C32—C33	1.375 (4)
C12—H12A	1.0000	C32—H32A	0.9500
C13—C14	1.534 (4)	C33—C34	1.370 (4)
C13—H13A	0.9900	C33—H33A	0.9500
C13—H13B	0.9900	C34—C35	1.387 (3)
C14—C15	1.532 (4)	C34—H34A	0.9500
C14—H14A	0.9900	C35—H35A	0.9500
Cp—Ti—N1	110.40 (8)	H10B—C10—H10C	106 (2)
N1—Ti—C20	99.09 (8)	Si—C11—H11A	112.4 (16)
N1—Ti—C23	99.33 (8)	Si—C11—H11B	111.1 (16)
C20—Ti—C23	86.82 (8)	H11A—C11—H11B	104 (2)
N1—Ti—C1	77.16 (8)	Si—C11—H11C	109.9 (15)
C20—Ti—C1	133.59 (9)	H11A—C11—H11C	113 (2)
C23—Ti—C1	139.59 (8)	H11B—C11—H11C	107 (2)
N1—Ti—C21	130.89 (8)	N1—C12—C13	121.49 (19)
C20—Ti—C21	36.52 (8)	N1—C12—C15	120.16 (18)
C23—Ti—C21	67.30 (8)	C13—C12—C15	87.44 (18)
C1—Ti—C21	143.40 (9)	N1—C12—H12A	108.6
N1—Ti—C22	131.01 (8)	C13—C12—H12A	108.6
C20—Ti—C22	67.34 (9)	C15—C12—H12A	108.6
C23—Ti—C22	36.48 (8)	C14—C13—C12	88.56 (18)
C1—Ti—C22	146.56 (9)	C14—C13—H13A	113.9
C21—Ti—C22	35.44 (8)	C12—C13—H13A	113.9
N1—Ti—C8	97.59 (7)	C14—C13—H13B	113.9
C20—Ti—C8	156.50 (8)	C12—C13—H13B	113.9
C23—Ti—C8	106.67 (8)	H13A—C13—H13B	111.1
C1—Ti—C8	36.60 (8)	C15—C14—C13	88.21 (19)
C21—Ti—C8	131.41 (8)	C15—C14—H14A	113.9
C22—Ti—C8	112.47 (8)	C13—C14—H14A	113.9
N1—Ti—C2	99.94 (8)	C15—C14—H14B	113.9
C20—Ti—C2	101.88 (8)	C13—C14—H14B	113.9
C23—Ti—C2	157.27 (9)	H14A—C14—H14B	111.2
C1—Ti—C2	36.69 (8)	C14—C15—C12	88.37 (18)
C21—Ti—C2	107.75 (9)	C14—C15—H15A	113.9
C22—Ti—C2	128.47 (9)	C12—C15—H15A	113.9
C8—Ti—C2	58.80 (8)	C14—C15—H15B	113.9
N1—Ti—C3	132.80 (8)	C12—C15—H15B	113.9
C20—Ti—C3	99.18 (8)	H15A—C15—H15B	111.1
C23—Ti—C3	124.80 (9)	C2—C16—H16A	109.5
C1—Ti—C3	58.95 (8)	C2—C16—H16B	109.5
C21—Ti—C3	85.73 (8)	H16A—C16—H16B	109.5
C22—Ti—C3	96.18 (9)	C2—C16—H16C	109.5
C8—Ti—C3	57.33 (8)	H16A—C16—H16C	109.5
C2—Ti—C3	33.56 (8)	H16B—C16—H16C	109.5
N1—Ti—C9	131.79 (7)	C3—C17—H17A	109.5
C20—Ti—C9	125.12 (8)	C3—C17—H17B	109.5
C23—Ti—C9	101.16 (9)	H17A—C17—H17B	109.5
C1—Ti—C9	59.19 (8)	C3—C17—H17C	109.5
C21—Ti—C9	97.30 (8)	H17A—C17—H17C	109.5
C22—Ti—C9	87.60 (8)	H17B—C17—H17C	109.5
C8—Ti—C9	34.58 (7)	C4—C18—H18A	109.5
C2—Ti—C9	56.64 (9)	C4—C18—H18B	109.5
C3—Ti—C9	33.57 (8)	H18A—C18—H18B	109.5
N1—Ti—Si	36.48 (5)	C4—C18—H18C	109.5
C20—Ti—Si	120.61 (6)	H18A—C18—H18C	109.5
C23—Ti—Si	125.95 (6)	H18B—C18—H18C	109.5
C1—Ti—Si	40.72 (6)	C6—C19—H19A	109.5
C21—Ti—Si	156.78 (7)	C6—C19—H19B	109.5
C22—Ti—Si	162.42 (6)	H19A—C19—H19B	109.5
C8—Ti—Si	67.09 (6)	C6—C19—H19C	109.5
C2—Ti—Si	67.41 (6)	H19A—C19—H19C	109.5
C3—Ti—Si	97.70 (6)	H19B—C19—H19C	109.5
C9—Ti—Si	98.08 (6)	C21—C20—C24	123.8 (2)
N1—Si—C11	114.99 (12)	C21—C20—Ti	74.71 (13)
N1—Si—C1	93.96 (9)	C24—C20—Ti	131.35 (16)
C11—Si—C1	112.79 (13)	C21—C20—H20	112.4 (13)
N1—Si—C10	115.47 (12)	C24—C20—H20	115.7 (13)
C11—Si—C10	106.09 (15)	Ti—C20—H20	89.5 (13)
C1—Si—C10	113.56 (12)	C22—C21—C20	125.7 (2)
N1—Si—Ti	42.39 (6)	C22—C21—Ti	72.29 (13)
C11—Si—Ti	124.66 (11)	C20—C21—Ti	68.77 (12)
C1—Si—Ti	51.62 (6)	C22—C21—H21	113.0 (13)
C10—Si—Ti	129.16 (10)	C20—C21—H21	119.6 (13)
C12—N1—Si	126.30 (14)	Ti—C21—H21	123.0 (14)
C12—N1—Ti	132.56 (14)	C21—C22—C23	126.1 (2)
Si—N1—Ti	101.14 (9)	C21—C22—Ti	72.27 (14)
C8—C1—C2	105.59 (19)	C23—C22—Ti	69.40 (13)
C8—C1—Si	122.26 (16)	C21—C22—H22	113.6 (13)
C2—C1—Si	123.12 (17)	C23—C22—H22	119.0 (12)
C8—C1—Ti	75.18 (12)	Ti—C22—H22	124.3 (12)
C2—C1—Ti	75.91 (12)	C22—C23—C30	123.4 (2)
Si—C1—Ti	87.66 (9)	C22—C23—Ti	74.12 (14)
C3—C2—C1	109.7 (2)	C30—C23—Ti	134.78 (15)
C3—C2—C16	124.3 (2)	C22—C23—H23	115.0 (12)
C1—C2—C16	126.0 (2)	C30—C23—H23	114.8 (13)
C3—C2—Ti	77.98 (14)	Ti—C23—H23	85.3 (13)
C1—C2—Ti	67.40 (12)	C25—C24—C29	116.8 (2)
C16—C2—Ti	122.17 (16)	C25—C24—C20	119.9 (2)
C2—C3—C9	108.6 (2)	C29—C24—C20	123.3 (2)
C2—C3—C17	123.9 (2)	C26—C25—C24	121.5 (2)
C9—C3—C17	127.0 (2)	C26—C25—H25A	119.2
C2—C3—Ti	68.46 (13)	C24—C25—H25A	119.2
C9—C3—Ti	73.74 (13)	C27—C26—C25	120.6 (3)
C17—C3—Ti	130.00 (17)	C27—C26—H26A	119.7
C5—C4—C9	117.7 (2)	C25—C26—H26A	119.7
C5—C4—C18	121.1 (3)	C28—C27—C26	119.0 (2)
C9—C4—C18	121.2 (3)	C28—C27—H27A	120.5
C4—C5—C6	123.7 (2)	C26—C27—H27A	120.5
C4—C5—H5A	118.2	C27—C28—C29	120.3 (2)
C6—C5—H5A	118.2	C27—C28—H28A	119.9
C7—C6—C5	118.9 (2)	C29—C28—H28A	119.9
C7—C6—C19	121.6 (2)	C28—C29—C24	121.9 (2)
C5—C6—C19	119.4 (2)	C28—C29—H29A	119.1
C6—C7—C8	120.8 (2)	C24—C29—H29A	119.1
C6—C7—H7A	119.6	C31—C30—C35	116.7 (2)
C8—C7—H7A	119.6	C31—C30—C23	119.7 (2)
C7—C8—C1	132.0 (2)	C35—C30—C23	123.6 (2)
C7—C8—C9	118.8 (2)	C32—C31—C30	121.8 (2)
C1—C8—C9	109.10 (19)	C32—C31—H31A	119.1
C7—C8—Ti	117.26 (15)	C30—C31—H31A	119.1
C1—C8—Ti	68.22 (11)	C33—C32—C31	120.2 (3)
C9—C8—Ti	78.65 (12)	C33—C32—H32A	119.9
C4—C9—C3	133.2 (2)	C31—C32—H32A	119.9
C4—C9—C8	119.8 (2)	C34—C33—C32	119.4 (2)
C3—C9—C8	106.9 (2)	C34—C33—H33A	120.3
C4—C9—Ti	125.78 (16)	C32—C33—H33A	120.3
C3—C9—Ti	72.69 (13)	C33—C34—C35	120.7 (3)
C8—C9—Ti	66.77 (12)	C33—C34—H34A	119.7
Si—C10—H10A	113.3 (13)	C35—C34—H34A	119.7
Si—C10—H10B	110.0 (16)	C34—C35—C30	121.3 (2)
H10A—C10—H10B	110 (2)	C34—C35—H35A	119.4
Si—C10—H10C	108.3 (16)	C30—C35—H35A	119.4
H10A—C10—H10C	109 (2)
C20—Ti—Si—N1	−60.56 (11)	C23—Ti—C8—C7	31.23 (19)
C23—Ti—Si—N1	49.90 (11)	C1—Ti—C8—C7	−127.2 (2)
C1—Ti—Si—N1	176.71 (12)	C21—Ti—C8—C7	105.39 (18)
C21—Ti—Si—N1	−68.89 (19)	C22—Ti—C8—C7	69.56 (19)
C22—Ti—Si—N1	52.1 (2)	C2—Ti—C8—C7	−168.0 (2)
C8—Ti—Si—N1	144.38 (10)	C3—Ti—C8—C7	152.3 (2)
C2—Ti—Si—N1	−151.30 (11)	C9—Ti—C8—C7	116.7 (2)
C3—Ti—Si—N1	−166.05 (10)	Si—Ti—C8—C7	−91.37 (17)
C9—Ti—Si—N1	160.05 (10)	N1—Ti—C8—C1	56.25 (13)
N1—Ti—Si—C11	90.24 (15)	C20—Ti—C8—C1	−78.7 (2)
C20—Ti—Si—C11	29.69 (15)	C23—Ti—C8—C1	158.41 (13)
C23—Ti—Si—C11	140.14 (15)	C21—Ti—C8—C1	−127.43 (14)
C1—Ti—Si—C11	−93.05 (15)	C22—Ti—C8—C1	−163.26 (13)
C21—Ti—Si—C11	21.4 (2)	C2—Ti—C8—C1	−40.81 (13)
C22—Ti—Si—C11	142.3 (2)	C3—Ti—C8—C1	−80.54 (14)
C8—Ti—Si—C11	−125.37 (14)	C9—Ti—C8—C1	−116.08 (19)
C2—Ti—Si—C11	−61.05 (14)	Si—Ti—C8—C1	35.81 (11)
C3—Ti—Si—C11	−75.81 (14)	N1—Ti—C8—C9	172.34 (13)
C9—Ti—Si—C11	−109.71 (14)	C20—Ti—C8—C9	37.4 (3)
N1—Ti—Si—C1	−176.71 (12)	C23—Ti—C8—C9	−85.51 (15)
C20—Ti—Si—C1	122.73 (11)	C1—Ti—C8—C9	116.08 (19)
C23—Ti—Si—C1	−126.82 (12)	C21—Ti—C8—C9	−11.35 (18)
C21—Ti—Si—C1	114.40 (19)	C22—Ti—C8—C9	−47.17 (16)
C22—Ti—Si—C1	−124.6 (2)	C2—Ti—C8—C9	75.28 (15)
C8—Ti—Si—C1	−32.33 (10)	C3—Ti—C8—C9	35.54 (13)
C2—Ti—Si—C1	31.99 (11)	Si—Ti—C8—C9	151.89 (14)
C3—Ti—Si—C1	17.24 (11)	C5—C4—C9—C3	−179.2 (3)
C9—Ti—Si—C1	−16.66 (11)	C18—C4—C9—C3	−0.6 (4)
N1—Ti—Si—C10	−86.00 (15)	C5—C4—C9—C8	−0.8 (3)
C20—Ti—Si—C10	−146.56 (14)	C18—C4—C9—C8	177.8 (2)
C23—Ti—Si—C10	−36.11 (15)	C5—C4—C9—Ti	80.7 (3)
C1—Ti—Si—C10	90.71 (16)	C18—C4—C9—Ti	−100.6 (3)
C21—Ti—Si—C10	−154.9 (2)	C2—C3—C9—C4	176.9 (2)
C22—Ti—Si—C10	−33.9 (3)	C17—C3—C9—C4	5.0 (4)
C8—Ti—Si—C10	58.38 (14)	Ti—C3—C9—C4	−123.2 (3)
C2—Ti—Si—C10	122.70 (14)	C2—C3—C9—C8	−1.7 (3)
C3—Ti—Si—C10	107.95 (14)	C17—C3—C9—C8	−173.6 (2)
C9—Ti—Si—C10	74.05 (14)	Ti—C3—C9—C8	58.21 (15)
C11—Si—N1—C12	64.9 (2)	C2—C3—C9—Ti	−59.88 (16)
C1—Si—N1—C12	−177.70 (18)	C17—C3—C9—Ti	128.2 (2)
C10—Si—N1—C12	−59.2 (2)	C7—C8—C9—C4	4.2 (3)
Ti—Si—N1—C12	179.7 (2)	C1—C8—C9—C4	−178.9 (2)
C11—Si—N1—Ti	−114.85 (13)	Ti—C8—C9—C4	119.2 (2)
C1—Si—N1—Ti	2.58 (10)	C7—C8—C9—C3	−177.04 (19)
C10—Si—N1—Ti	121.05 (12)	C1—C8—C9—C3	−0.1 (2)
C20—Ti—N1—C12	−49.1 (2)	Ti—C8—C9—C3	−62.03 (16)
C23—Ti—N1—C12	39.2 (2)	C7—C8—C9—Ti	−115.01 (19)
C1—Ti—N1—C12	178.1 (2)	C1—C8—C9—Ti	61.96 (14)
C21—Ti—N1—C12	−28.8 (2)	N1—Ti—C9—C4	−121.2 (2)
C22—Ti—N1—C12	18.7 (2)	C20—Ti—C9—C4	86.3 (2)
C8—Ti—N1—C12	147.55 (19)	C23—Ti—C9—C4	−7.7 (2)
C2—Ti—N1—C12	−152.93 (19)	C1—Ti—C9—C4	−149.5 (2)
C3—Ti—N1—C12	−160.68 (17)	C21—Ti—C9—C4	60.5 (2)
C9—Ti—N1—C12	153.38 (17)	C22—Ti—C9—C4	26.3 (2)
Si—Ti—N1—C12	−179.7 (2)	C8—Ti—C9—C4	−110.9 (3)
C20—Ti—N1—Si	130.62 (9)	C2—Ti—C9—C4	167.0 (2)
C23—Ti—N1—Si	−141.14 (9)	C3—Ti—C9—C4	131.3 (3)
C1—Ti—N1—Si	−2.20 (8)	Si—Ti—C9—C4	−136.94 (19)
C21—Ti—N1—Si	150.89 (9)	N1—Ti—C9—C3	107.54 (15)
C22—Ti—N1—Si	−161.58 (9)	C20—Ti—C9—C3	−45.01 (17)
C8—Ti—N1—Si	−32.76 (9)	C23—Ti—C9—C3	−139.01 (14)
C2—Ti—N1—Si	26.76 (10)	C1—Ti—C9—C3	79.19 (15)
C3—Ti—N1—Si	19.00 (14)	C21—Ti—C9—C3	−70.80 (15)
C9—Ti—N1—Si	−26.93 (13)	C22—Ti—C9—C3	−104.96 (14)
N1—Si—C1—C8	68.60 (18)	C8—Ti—C9—C3	117.8 (2)
C11—Si—C1—C8	−172.16 (18)	C2—Ti—C9—C3	35.68 (13)
C10—Si—C1—C8	−51.4 (2)	Si—Ti—C9—C3	91.76 (13)
Ti—Si—C1—C8	70.82 (16)	N1—Ti—C9—C8	−10.21 (18)
N1—Si—C1—C2	−73.71 (19)	C20—Ti—C9—C8	−162.77 (13)
C11—Si—C1—C2	45.5 (2)	C23—Ti—C9—C8	103.24 (14)
C10—Si—C1—C2	166.26 (19)	C1—Ti—C9—C8	−38.57 (13)
Ti—Si—C1—C2	−71.49 (17)	C21—Ti—C9—C8	171.44 (14)
N1—Si—C1—Ti	−2.22 (8)	C22—Ti—C9—C8	137.29 (14)
C11—Si—C1—Ti	117.01 (12)	C2—Ti—C9—C8	−82.08 (15)
C10—Si—C1—Ti	−122.25 (12)	C3—Ti—C9—C8	−117.8 (2)
N1—Ti—C1—C8	−122.29 (13)	Si—Ti—C9—C8	−25.99 (13)
C20—Ti—C1—C8	147.33 (13)	Si—N1—C12—C13	−48.5 (3)
C23—Ti—C1—C8	−32.94 (19)	Ti—N1—C12—C13	131.17 (19)
C21—Ti—C1—C8	92.72 (17)	Si—N1—C12—C15	58.7 (3)
C22—Ti—C1—C8	28.9 (2)	Ti—N1—C12—C15	−121.6 (2)
C2—Ti—C1—C8	110.67 (18)	N1—C12—C13—C14	144.5 (2)
C3—Ti—C1—C8	75.75 (13)	C15—C12—C13—C14	20.30 (18)
C9—Ti—C1—C8	36.41 (12)	C12—C13—C14—C15	−20.5 (2)
Si—Ti—C1—C8	−124.29 (15)	C13—C14—C15—C12	20.40 (18)
N1—Ti—C1—C2	127.04 (15)	N1—C12—C15—C14	−145.7 (2)
C20—Ti—C1—C2	36.66 (19)	C13—C12—C15—C14	−20.34 (18)
C23—Ti—C1—C2	−143.61 (15)	N1—Ti—C20—C21	153.89 (14)
C21—Ti—C1—C2	−17.9 (2)	C23—Ti—C20—C21	54.94 (15)
C22—Ti—C1—C2	−81.8 (2)	C1—Ti—C20—C21	−125.24 (15)
C8—Ti—C1—C2	−110.67 (18)	C22—Ti—C20—C21	23.09 (14)
C3—Ti—C1—C2	−34.92 (13)	C8—Ti—C20—C21	−71.4 (3)
C9—Ti—C1—C2	−74.26 (14)	C2—Ti—C20—C21	−103.86 (15)
Si—Ti—C1—C2	125.03 (17)	C3—Ti—C20—C21	−69.82 (15)
N1—Ti—C1—Si	2.00 (8)	C9—Ti—C20—C21	−46.48 (17)
C20—Ti—C1—Si	−88.37 (13)	Si—Ti—C20—C21	−174.49 (12)
C23—Ti—C1—Si	91.36 (14)	N1—Ti—C20—C24	−84.3 (2)
C21—Ti—C1—Si	−142.98 (12)	C23—Ti—C20—C24	176.8 (2)
C22—Ti—C1—Si	153.18 (12)	C1—Ti—C20—C24	−3.4 (3)
C8—Ti—C1—Si	124.29 (15)	C21—Ti—C20—C24	121.9 (3)
C2—Ti—C1—Si	−125.03 (17)	C22—Ti—C20—C24	144.9 (2)
C3—Ti—C1—Si	−159.95 (12)	C8—Ti—C20—C24	50.4 (3)
C9—Ti—C1—Si	160.70 (12)	C2—Ti—C20—C24	18.0 (2)
C8—C1—C2—C3	−2.7 (2)	C3—Ti—C20—C24	52.0 (2)
Si—C1—C2—C3	144.79 (17)	C9—Ti—C20—C24	75.4 (2)
Ti—C1—C2—C3	67.14 (17)	Si—Ti—C20—C24	−52.6 (2)
C8—C1—C2—C16	175.9 (2)	C24—C20—C21—C22	−177.0 (2)
Si—C1—C2—C16	−36.6 (3)	Ti—C20—C21—C22	−47.1 (2)
Ti—C1—C2—C16	−114.2 (2)	C24—C20—C21—Ti	−129.9 (2)
C8—C1—C2—Ti	−69.89 (14)	N1—Ti—C21—C22	106.28 (16)
Si—C1—C2—Ti	77.65 (15)	C20—Ti—C21—C22	141.4 (2)
N1—Ti—C2—C3	−169.69 (13)	C23—Ti—C21—C22	23.74 (14)
C20—Ti—C2—C3	88.74 (15)	C1—Ti—C21—C22	−121.45 (17)
C23—Ti—C2—C3	−22.1 (3)	C8—Ti—C21—C22	−68.88 (18)
C1—Ti—C2—C3	−117.5 (2)	C2—Ti—C21—C22	−132.59 (15)
C21—Ti—C2—C3	51.39 (15)	C3—Ti—C21—C22	−106.93 (15)
C22—Ti—C2—C3	18.35 (18)	C9—Ti—C21—C22	−75.35 (15)
C8—Ti—C2—C3	−76.78 (14)	Si—Ti—C21—C22	153.47 (14)
C9—Ti—C2—C3	−35.69 (13)	N1—Ti—C21—C20	−35.09 (18)
Si—Ti—C2—C3	−152.84 (15)	C23—Ti—C21—C20	−117.63 (16)
N1—Ti—C2—C1	−52.20 (14)	C1—Ti—C21—C20	97.18 (18)
C20—Ti—C2—C1	−153.77 (14)	C22—Ti—C21—C20	−141.4 (2)
C23—Ti—C2—C1	95.4 (2)	C8—Ti—C21—C20	149.74 (14)
C21—Ti—C2—C1	168.88 (14)	C2—Ti—C21—C20	86.03 (15)
C22—Ti—C2—C1	135.84 (14)	C3—Ti—C21—C20	111.70 (15)
C8—Ti—C2—C1	40.71 (13)	C9—Ti—C21—C20	143.28 (14)
C3—Ti—C2—C1	117.5 (2)	Si—Ti—C21—C20	12.1 (3)
C9—Ti—C2—C1	81.80 (14)	C20—C21—C22—C23	−0.6 (4)
Si—Ti—C2—C1	−35.35 (12)	Ti—C21—C22—C23	−46.4 (2)
N1—Ti—C2—C16	67.2 (2)	C20—C21—C22—Ti	45.8 (2)
C20—Ti—C2—C16	−34.4 (2)	N1—Ti—C22—C21	−105.91 (16)
C23—Ti—C2—C16	−145.2 (2)	C20—Ti—C22—C21	−23.74 (14)
C1—Ti—C2—C16	119.4 (3)	C23—Ti—C22—C21	−141.3 (2)
C21—Ti—C2—C16	−71.7 (2)	C1—Ti—C22—C21	112.62 (18)
C22—Ti—C2—C16	−104.8 (2)	C8—Ti—C22—C21	130.79 (14)
C8—Ti—C2—C16	160.1 (2)	C2—Ti—C22—C21	63.58 (18)
C3—Ti—C2—C16	−123.1 (3)	C3—Ti—C22—C21	73.66 (15)
C9—Ti—C2—C16	−158.8 (2)	C9—Ti—C22—C21	106.16 (15)
Si—Ti—C2—C16	84.0 (2)	Si—Ti—C22—C21	−144.35 (19)
C1—C2—C3—C9	2.8 (3)	N1—Ti—C22—C23	35.43 (18)
C16—C2—C3—C9	−175.9 (2)	C20—Ti—C22—C23	117.60 (16)
Ti—C2—C3—C9	63.22 (16)	C1—Ti—C22—C23	−106.03 (18)
C1—C2—C3—C17	175.0 (2)	C21—Ti—C22—C23	141.3 (2)
C16—C2—C3—C17	−3.7 (4)	C8—Ti—C22—C23	−87.87 (15)
Ti—C2—C3—C17	−124.6 (2)	C2—Ti—C22—C23	−155.08 (14)
C1—C2—C3—Ti	−60.44 (15)	C3—Ti—C22—C23	−145.00 (14)
C16—C2—C3—Ti	120.9 (2)	C9—Ti—C22—C23	−112.50 (15)
N1—Ti—C3—C2	13.91 (18)	Si—Ti—C22—C23	−3.0 (3)
C20—Ti—C3—C2	−97.67 (14)	C21—C22—C23—C30	−179.0 (2)
C23—Ti—C3—C2	169.81 (13)	Ti—C22—C23—C30	133.6 (2)
C1—Ti—C3—C2	38.22 (13)	C21—C22—C23—Ti	47.4 (2)
C21—Ti—C3—C2	−131.73 (15)	N1—Ti—C23—C22	−153.68 (14)
C22—Ti—C3—C2	−165.65 (14)	C20—Ti—C23—C22	−54.99 (15)
C8—Ti—C3—C2	81.57 (15)	C1—Ti—C23—C22	125.21 (16)
C9—Ti—C3—C2	118.2 (2)	C21—Ti—C23—C22	−23.12 (14)
Si—Ti—C3—C2	25.17 (14)	C8—Ti—C23—C22	105.43 (14)
N1—Ti—C3—C9	−104.30 (15)	C2—Ti—C23—C22	58.6 (3)
C20—Ti—C3—C9	144.13 (14)	C3—Ti—C23—C22	43.99 (17)
C23—Ti—C3—C9	51.61 (16)	C9—Ti—C23—C22	70.20 (15)
C1—Ti—C3—C9	−79.99 (14)	Si—Ti—C23—C22	178.88 (11)
C21—Ti—C3—C9	110.06 (15)	N1—Ti—C23—C30	84.7 (2)
C22—Ti—C3—C9	76.15 (14)	C20—Ti—C23—C30	−176.6 (2)
C8—Ti—C3—C9	−36.63 (13)	C1—Ti—C23—C30	3.6 (3)
C2—Ti—C3—C9	−118.2 (2)	C21—Ti—C23—C30	−144.8 (3)
Si—Ti—C3—C9	−93.03 (13)	C22—Ti—C23—C30	−121.6 (3)
N1—Ti—C3—C17	130.7 (2)	C8—Ti—C23—C30	−16.2 (3)
C20—Ti—C3—C17	19.2 (3)	C2—Ti—C23—C30	−63.0 (3)
C23—Ti—C3—C17	−73.4 (3)	C3—Ti—C23—C30	−77.6 (2)
C1—Ti—C3—C17	155.0 (3)	C9—Ti—C23—C30	−51.4 (2)
C21—Ti—C3—C17	−14.9 (2)	Si—Ti—C23—C30	57.2 (3)
C22—Ti—C3—C17	−48.8 (2)	C21—C20—C24—C25	179.5 (2)
C8—Ti—C3—C17	−161.6 (3)	Ti—C20—C24—C25	79.9 (3)
C2—Ti—C3—C17	116.8 (3)	C21—C20—C24—C29	−1.7 (3)
C9—Ti—C3—C17	−125.0 (3)	Ti—C20—C24—C29	−101.3 (3)
Si—Ti—C3—C17	142.0 (2)	C29—C24—C25—C26	1.8 (4)
C9—C4—C5—C6	−2.3 (4)	C20—C24—C25—C26	−179.3 (2)
C18—C4—C5—C6	179.1 (2)	C24—C25—C26—C27	−0.8 (4)
C4—C5—C6—C7	1.9 (4)	C25—C26—C27—C28	−0.3 (4)
C4—C5—C6—C19	−176.5 (2)	C26—C27—C28—C29	0.5 (4)
C5—C6—C7—C8	1.7 (3)	C27—C28—C29—C24	0.6 (4)
C19—C6—C7—C8	−180.0 (2)	C25—C24—C29—C28	−1.7 (4)
C6—C7—C8—C1	179.2 (2)	C20—C24—C29—C28	179.5 (2)
C6—C7—C8—C9	−4.6 (3)	C22—C23—C30—C31	167.0 (2)
C6—C7—C8—Ti	−96.4 (2)	Ti—C23—C30—C31	−91.9 (3)
C2—C1—C8—C7	178.1 (2)	C22—C23—C30—C35	−11.9 (4)
Si—C1—C8—C7	30.2 (3)	Ti—C23—C30—C35	89.3 (3)
Ti—C1—C8—C7	107.7 (2)	C35—C30—C31—C32	1.9 (4)
C2—C1—C8—C9	1.7 (2)	C23—C30—C31—C32	−177.0 (2)
Si—C1—C8—C9	−146.21 (16)	C30—C31—C32—C33	−1.3 (4)
Ti—C1—C8—C9	−68.74 (15)	C31—C32—C33—C34	−0.2 (4)
C2—C1—C8—Ti	70.42 (14)	C32—C33—C34—C35	1.0 (4)
Si—C1—C8—Ti	−77.47 (14)	C33—C34—C35—C30	−0.3 (4)
N1—Ti—C8—C7	−70.93 (18)	C31—C30—C35—C34	−1.1 (3)
C20—Ti—C8—C7	154.2 (2)	C23—C30—C35—C34	177.8 (2)