Trichlorido{2-[2-(η-cyclo-penta-dien-yl)-2-methyl-prop-yl]-1-trimethyl-silyl-1H-imidazole-κN}titanium(IV) tetra-hydro-furan hemisolvate.

The title compound, [Ti(C(15)H(23)N(2)Si)Cl(3)]·0.5C(4)H(8)O, has been prepared from {2-[2-(η(5)-cyclo-penta-dien-yl)-2-methyl-prop-yl]-1H-imidazolyl-κN(1)}bis-(N,N-diethyl-amido-κN)titanium(IV), (C(12)H(14)N(2))Ti(NEt(2))(2), by reaction with excess of Me(3)SiCl in tetra-hydro-furan (THF) at 353 K. The crystal structure contains THF as adduct solvent, disordered around a center of inversion. The presence of THF and the adduct ratio has been independently supported by (1)H NMR spectroscopy. The coordination polyhedron of the Ti atom is distorted square-pyramidal, assuming the cyclo-penta-dienyl (Cp) ring occupies one coordination site. The Ti, Si and CH(2) group C atoms only deviate slightly from the imidazole ring plane [by 0.021 (4), 0.133 (4) and 0.094 (4) Å, respectively]. Comparison of the principal geometric parameters with those of the few known structurally characterized analogues reveal small differences in bond lengths and angles at the Ti atom. The title complex is only stable in THF-d(8) in the presence of excess Me(3)SiCl, otherwise it exists in an equilibrium with equimolar amounts of dichlorido{2-[2-(η(5)-cyclo-penta-dien-yl)-2-methyl-prop-yl]-1H-imidazolyl-κN(3)}titanium(IV) and chloro-trimethyl-silane.

Related literature

For a description of cyclo­penta­dienes with pendant 1H-imidazol(in)-2-yl side-chain functional groups and group 4 transition metal complexes of general type [η5-Cp-(CPh2CH2)-imidazol(in)e)-κN 3]-M IVCl3 (M = Ti, Zr) , see: Krut’ko et al. (2006 ▶); Nie et al. (2008 ▶). For the geometric parameters of structurally characterized TiIV complexes of the similar η5-CpTiCl3-NR type, see: trichloro­{2-[2-(η5-cyclo­penta­dien­yl)-2,2-diphenyl­ethyl]-1-methyl-1H-imidazole-κN 3}titanium(IV), C23H21Cl3N2Ti (Krut’ko et al., 2006 ▶); trichloro­{1-[2-(η5-cyclo­penta­dien­yl)eth­yl]pyrrolidine-κN}titanium(IV), C11H16Cl3NTi (Herrmann et al., 1995 ▶); trichloro­[8-(η5-2,3,4,5-tetra­methyl­cyclo­penta­dien­yl)quinoline-κN]titanium(IV), C18H18Cl3NTi (Enders et al., 1997 ▶); trichloro­[8-(η5-2,3-dimethyl­cyclo­penta­dien­yl)quinoline-κN]titanium(IV), C16H14Cl3NTi (Enders et al., 1996 ▶). For the preparation of [2-[2-(η5-cyclo­penta­dien­yl)-2-methyl­prop­yl]-1H-imidazolyl-κN 1]bis­(N,N-di­ethyl­amido-κN)titanium(IV), (C12H14N2)Ti(NEt2)2, see: Wang et al. (2009 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

[Ti(C15H23N2Si)Cl3]·0.5C4H8O

M = 449.75

Monoclinic,

a = 8.8033 (9) Å

b = 11.8201 (11) Å

c = 21.481 (2) Å

β = 99.399 (1)°

V = 2205.2 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.81 mm−1

T = 293 K

0.29 × 0.21 × 0.14 mm

Data collection

Bruker SMART APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.798, T max = 0.894

10736 measured reflections

3869 independent reflections

2812 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.115

S = 1.02

3869 reflections

249 parameters

70 restraints

H-atom parameters constrained

Δρmax = 0.42 e Å−3

Δρmin = −0.27 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: SHELXTL, OLEX2 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810013772/nc2182sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810013772/nc2182Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Ti(C15H23N2Si)Cl3]·0.5C4H8O	F(000) = 936
Mr = 449.75	Dx = 1.355 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2833 reflections
a = 8.8033 (9) Å	θ = 2.6–24.1°
b = 11.8201 (11) Å	µ = 0.81 mm−1
c = 21.481 (2) Å	T = 293 K
β = 99.399 (1)°	Block, orange
V = 2205.2 (4) Å3	0.29 × 0.21 × 0.14 mm
Z = 4

Bruker SMART APEXII diffractometer	3869 independent reflections
Radiation source: fine-focus sealed tube	2812 reflections with I > 2σ(I)
graphite	Rint = 0.031
Detector resolution: 8.333 pixels mm-1	θmax = 25.0°, θmin = 1.9°
phi and ω scans	h = −10→6
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −14→14
Tmin = 0.798, Tmax = 0.894	l = −24→25
10736 measured reflections

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0702P)2] where P = (Fo2 + 2Fc2)/3
3869 reflections	(Δ/σ)max < 0.001
249 parameters	Δρmax = 0.42 e Å−3
70 restraints	Δρmin = −0.27 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	Occ. (<1)
Ti1	0.43495 (6)	0.55311 (4)	0.32607 (2)	0.03818 (17)
Cl1	0.38088 (10)	0.37906 (7)	0.37034 (4)	0.0627 (3)
Cl2	0.67102 (10)	0.47125 (8)	0.31535 (5)	0.0702 (3)
Cl3	0.57958 (10)	0.71852 (7)	0.35301 (4)	0.0566 (2)
Si1	0.00773 (10)	0.73534 (8)	0.49770 (4)	0.0542 (3)
N1	0.1676 (2)	0.67619 (19)	0.46582 (10)	0.0396 (5)
N2	0.3202 (2)	0.61390 (19)	0.40069 (10)	0.0391 (5)
C1	0.1772 (3)	0.6447 (2)	0.40551 (12)	0.0352 (6)
C2	0.3137 (3)	0.6600 (3)	0.50049 (13)	0.0491 (8)
H2	0.3426	0.6725	0.5435	0.059*
C3	0.4050 (3)	0.6234 (3)	0.46088 (13)	0.0487 (8)
H3	0.5092	0.6069	0.4719	0.058*
C4	0.0459 (3)	0.6406 (2)	0.35326 (12)	0.0401 (7)
H4B	−0.0408	0.6794	0.3663	0.048*
H4A	0.0164	0.5623	0.3451	0.048*
C5	0.0790 (3)	0.6941 (3)	0.29174 (13)	0.0424 (7)
C6	−0.0695 (4)	0.6866 (3)	0.24248 (14)	0.0637 (10)
H6B	−0.0565	0.7290	0.2056	0.096*
H6C	−0.1542	0.7172	0.2601	0.096*
H6A	−0.0902	0.6089	0.2311	0.096*
C7	0.1269 (4)	0.8181 (3)	0.30352 (16)	0.0567 (8)
H7B	0.2190	0.8216	0.3343	0.085*
H7C	0.0460	0.8586	0.3188	0.085*
H7A	0.1457	0.8517	0.2648	0.085*
C8	−0.1419 (4)	0.6251 (4)	0.4950 (2)	0.0828 (12)
H8A	−0.1668	0.5961	0.4528	0.124*
H8C	−0.2325	0.6572	0.5075	0.124*
H8B	−0.1043	0.5648	0.5232	0.124*
C9	−0.0605 (5)	0.8622 (3)	0.45119 (18)	0.0730 (11)
H9B	0.0263	0.9042	0.4418	0.110*
H9C	−0.1193	0.9089	0.4751	0.110*
H9A	−0.1241	0.8396	0.4126	0.110*
C10	0.0866 (5)	0.7784 (5)	0.57934 (18)	0.1059 (17)
H10A	0.1331	0.7143	0.6024	0.159*
H10C	0.0050	0.8071	0.5996	0.159*
H10B	0.1627	0.8364	0.5785	0.159*
C11	0.2036 (3)	0.6279 (3)	0.26614 (12)	0.0424 (7)
C12	0.3285 (4)	0.6727 (3)	0.24110 (13)	0.0528 (8)
H12	0.3546	0.7489	0.2402	0.063*
C13	0.4073 (4)	0.5834 (4)	0.21778 (15)	0.0704 (11)
H13	0.4951	0.5897	0.1991	0.084*
C14	0.3307 (5)	0.4838 (4)	0.22756 (16)	0.0705 (11)
H14	0.3578	0.4115	0.2162	0.085*
C15	0.2056 (4)	0.5111 (3)	0.25741 (14)	0.0535 (8)
H15	0.1356	0.4599	0.2694	0.064*
O1	0.3332 (13)	0.9741 (12)	0.4938 (7)	0.206 (4)	0.50
C21	0.3746 (18)	1.0279 (16)	0.4404 (6)	0.205 (5)	0.50
H21B	0.3099	1.0935	0.4290	0.246*	0.50
H21A	0.3621	0.9763	0.4048	0.246*	0.50
C22	0.5356 (19)	1.0621 (16)	0.4569 (7)	0.199 (5)	0.50
H22B	0.5489	1.1392	0.4433	0.239*	0.50
H22A	0.6009	1.0129	0.4367	0.239*	0.50
C23	0.5763 (17)	1.0534 (16)	0.5268 (8)	0.201 (5)	0.50
H23A	0.6671	1.0067	0.5385	0.241*	0.50
H23B	0.5964	1.1277	0.5455	0.241*	0.50
C24	0.443 (2)	1.0019 (16)	0.5477 (6)	0.195 (5)	0.50
H24A	0.4741	0.9342	0.5720	0.234*	0.50
H24B	0.3984	1.0542	0.5744	0.234*	0.50

	U11	U22	U33	U12	U13	U23
Ti1	0.0335 (3)	0.0417 (3)	0.0402 (3)	0.0018 (2)	0.0084 (2)	−0.0042 (2)
Cl1	0.0673 (6)	0.0486 (5)	0.0696 (6)	−0.0078 (4)	0.0033 (4)	0.0064 (4)
Cl2	0.0459 (5)	0.0750 (6)	0.0929 (7)	0.0117 (4)	0.0209 (4)	−0.0205 (5)
Cl3	0.0591 (5)	0.0518 (5)	0.0609 (5)	−0.0144 (4)	0.0157 (4)	−0.0023 (4)
Si1	0.0444 (5)	0.0776 (6)	0.0435 (5)	0.0092 (5)	0.0156 (4)	−0.0045 (4)
N1	0.0353 (13)	0.0528 (14)	0.0313 (12)	0.0003 (11)	0.0075 (10)	0.0005 (10)
N2	0.0299 (12)	0.0521 (14)	0.0358 (12)	0.0034 (11)	0.0065 (10)	−0.0004 (10)
C1	0.0330 (15)	0.0366 (14)	0.0373 (15)	0.0003 (11)	0.0092 (11)	0.0052 (11)
C2	0.0371 (17)	0.072 (2)	0.0363 (16)	0.0007 (15)	0.0012 (13)	−0.0022 (15)
C3	0.0305 (16)	0.074 (2)	0.0390 (16)	0.0047 (15)	−0.0018 (13)	0.0020 (15)
C4	0.0325 (15)	0.0500 (17)	0.0373 (15)	−0.0022 (13)	0.0041 (12)	0.0015 (13)
C5	0.0356 (16)	0.0548 (18)	0.0367 (15)	0.0058 (13)	0.0061 (12)	0.0057 (13)
C6	0.0438 (18)	0.105 (3)	0.0392 (17)	0.0132 (19)	−0.0028 (14)	0.0103 (17)
C7	0.066 (2)	0.0485 (18)	0.059 (2)	0.0106 (16)	0.0195 (17)	0.0141 (15)
C8	0.054 (2)	0.104 (3)	0.098 (3)	0.003 (2)	0.033 (2)	0.024 (2)
C9	0.070 (2)	0.064 (2)	0.086 (3)	0.0130 (19)	0.016 (2)	−0.011 (2)
C10	0.094 (3)	0.174 (5)	0.052 (2)	0.028 (3)	0.019 (2)	−0.029 (3)
C11	0.0385 (16)	0.0572 (18)	0.0300 (14)	0.0030 (14)	0.0013 (12)	0.0018 (13)
C12	0.054 (2)	0.069 (2)	0.0370 (16)	0.0061 (17)	0.0123 (14)	0.0125 (15)
C13	0.062 (2)	0.112 (3)	0.0396 (18)	0.021 (2)	0.0170 (17)	−0.002 (2)
C14	0.075 (3)	0.083 (3)	0.049 (2)	0.020 (2)	−0.0031 (18)	−0.0266 (19)
C15	0.0491 (19)	0.059 (2)	0.0475 (17)	0.0001 (16)	−0.0070 (15)	−0.0126 (15)
O1	0.195 (6)	0.228 (7)	0.195 (6)	0.011 (6)	0.036 (5)	−0.014 (6)
C21	0.199 (7)	0.212 (7)	0.203 (7)	−0.002 (6)	0.031 (6)	0.017 (6)
C22	0.203 (7)	0.199 (8)	0.193 (7)	−0.014 (6)	0.024 (6)	0.008 (6)
C23	0.206 (7)	0.199 (7)	0.199 (7)	−0.014 (6)	0.039 (6)	−0.005 (6)
C24	0.188 (7)	0.211 (7)	0.187 (7)	−0.007 (6)	0.038 (6)	−0.011 (6)

Ti1—N2	2.153 (2)	C7—H7A	0.9600
Ti1—C14	2.315 (3)	C8—H8A	0.9600
Ti1—C13	2.327 (3)	C8—H8C	0.9600
Ti1—Cl2	2.3377 (10)	C8—H8B	0.9600
Ti1—Cl1	2.3475 (9)	C9—H9B	0.9600
Ti1—C15	2.350 (3)	C9—H9C	0.9600
Ti1—Cl3	2.3533 (9)	C9—H9A	0.9600
Ti1—C12	2.377 (3)	C10—H10A	0.9600
Ti1—C11	2.394 (3)	C10—H10C	0.9600
Si1—N1	1.804 (2)	C10—H10B	0.9600
Si1—C8	1.847 (4)	C11—C15	1.394 (4)
Si1—C9	1.847 (4)	C11—C12	1.404 (4)
Si1—C10	1.849 (4)	C12—C13	1.399 (5)
N1—C1	1.364 (3)	C12—H12	0.9300
N1—C2	1.390 (3)	C13—C14	1.390 (5)
N2—C1	1.330 (3)	C13—H13	0.9300
N2—C3	1.388 (3)	C14—C15	1.399 (5)
C1—C4	1.474 (4)	C14—H14	0.9300
C2—C3	1.335 (4)	C15—H15	0.9300
C2—H2	0.9300	O1—C21	1.410 (6)
C3—H3	0.9300	O1—C24	1.421 (6)
C4—C5	1.535 (4)	C21—C22	1.460 (6)
C4—H4B	0.9700	C21—H21B	0.9700
C4—H4A	0.9700	C21—H21A	0.9700
C5—C11	1.522 (4)	C22—C23	1.489 (6)
C5—C7	1.534 (4)	C22—H22B	0.9700
C5—C6	1.544 (4)	C22—H22A	0.9700
C6—H6B	0.9600	C23—C24	1.456 (6)
C6—H6C	0.9600	C23—H23A	0.9700
C6—H6A	0.9600	C23—H23B	0.9700
C7—H7B	0.9600	C24—H24A	0.9700
C7—H7C	0.9600	C24—H24B	0.9700
N2—Ti1—C14	129.38 (12)	H7B—C7—H7C	109.5
N2—Ti1—C13	135.04 (11)	C5—C7—H7A	109.5
C14—Ti1—C13	34.86 (13)	H7B—C7—H7A	109.5
N2—Ti1—Cl2	138.10 (6)	H7C—C7—H7A	109.5
C14—Ti1—Cl2	89.41 (10)	Si1—C8—H8A	109.5
C13—Ti1—Cl2	85.12 (9)	Si1—C8—H8C	109.5
N2—Ti1—Cl1	80.79 (7)	H8A—C8—H8C	109.5
C14—Ti1—Cl1	89.07 (11)	Si1—C8—H8B	109.5
C13—Ti1—Cl1	123.02 (12)	H8A—C8—H8B	109.5
Cl2—Ti1—Cl1	85.38 (4)	H8C—C8—H8B	109.5
N2—Ti1—C15	94.48 (10)	Si1—C9—H9B	109.5
C14—Ti1—C15	34.89 (12)	Si1—C9—H9C	109.5
C13—Ti1—C15	57.74 (14)	H9B—C9—H9C	109.5
Cl2—Ti1—C15	122.49 (8)	Si1—C9—H9A	109.5
Cl1—Ti1—C15	81.89 (9)	H9B—C9—H9A	109.5
N2—Ti1—Cl3	80.82 (7)	H9C—C9—H9A	109.5
C14—Ti1—Cl3	129.55 (12)	Si1—C10—H10A	109.5
C13—Ti1—Cl3	94.70 (12)	Si1—C10—H10C	109.5
Cl2—Ti1—Cl3	85.07 (4)	H10A—C10—H10C	109.5
Cl1—Ti1—Cl3	139.98 (4)	Si1—C10—H10B	109.5
C15—Ti1—Cl3	134.78 (9)	H10A—C10—H10B	109.5
N2—Ti1—C12	101.49 (10)	H10C—C10—H10B	109.5
C14—Ti1—C12	57.36 (13)	C15—C11—C12	107.1 (3)
C13—Ti1—C12	34.59 (12)	C15—C11—C5	125.7 (3)
Cl2—Ti1—C12	114.57 (8)	C12—C11—C5	126.9 (3)
Cl1—Ti1—C12	138.74 (9)	C15—C11—Ti1	71.21 (16)
C15—Ti1—C12	56.85 (12)	C12—C11—Ti1	72.22 (17)
Cl3—Ti1—C12	79.88 (9)	C5—C11—Ti1	126.58 (18)
N2—Ti1—C11	79.37 (9)	C13—C12—C11	108.5 (3)
C14—Ti1—C11	57.56 (11)	C13—C12—Ti1	70.76 (19)
C13—Ti1—C11	57.62 (11)	C11—C12—Ti1	73.55 (16)
Cl2—Ti1—C11	142.36 (7)	C13—C12—H12	125.7
Cl1—Ti1—C11	109.31 (8)	C11—C12—H12	125.7
C15—Ti1—C11	34.16 (10)	Ti1—C12—H12	121.6
Cl3—Ti1—C11	101.76 (8)	C14—C13—C12	107.7 (3)
C12—Ti1—C11	34.23 (10)	C14—C13—Ti1	72.1 (2)
N1—Si1—C8	108.14 (16)	C12—C13—Ti1	74.65 (18)
N1—Si1—C9	108.33 (15)	C14—C13—H13	126.2
C8—Si1—C9	112.84 (18)	C12—C13—H13	126.2
N1—Si1—C10	105.75 (16)	Ti1—C13—H13	119.0
C8—Si1—C10	112.3 (2)	C13—C14—C15	108.1 (3)
C9—Si1—C10	109.1 (2)	C13—C14—Ti1	73.0 (2)
C1—N1—C2	106.0 (2)	C15—C14—Ti1	73.94 (17)
C1—N1—Si1	129.77 (19)	C13—C14—H14	125.9
C2—N1—Si1	124.11 (19)	C15—C14—H14	125.9
C1—N2—C3	106.1 (2)	Ti1—C14—H14	118.9
C1—N2—Ti1	135.58 (18)	C11—C15—C14	108.6 (3)
C3—N2—Ti1	118.30 (18)	C11—C15—Ti1	74.63 (16)
N2—C1—N1	110.8 (2)	C14—C15—Ti1	71.16 (19)
N2—C1—C4	124.5 (2)	C11—C15—H15	125.7
N1—C1—C4	124.7 (2)	C14—C15—H15	125.7
C3—C2—N1	107.7 (2)	Ti1—C15—H15	120.2
C3—C2—H2	126.2	C21—O1—C24	109.0 (5)
N1—C2—H2	126.2	O1—C21—C22	107.3 (5)
C2—C3—N2	109.4 (2)	O1—C21—H21B	110.3
C2—C3—H3	125.3	C22—C21—H21B	110.3
N2—C3—H3	125.3	O1—C21—H21A	110.3
C1—C4—C5	114.0 (2)	C22—C21—H21A	110.3
C1—C4—H4B	108.8	H21B—C21—H21A	108.5
C5—C4—H4B	108.8	C21—C22—C23	106.8 (5)
C1—C4—H4A	108.8	C21—C22—H22B	110.4
C5—C4—H4A	108.8	C23—C22—H22B	110.4
H4B—C4—H4A	107.7	C21—C22—H22A	110.4
C11—C5—C7	110.8 (2)	C23—C22—H22A	110.4
C11—C5—C4	110.4 (2)	H22B—C22—H22A	108.6
C7—C5—C4	109.7 (2)	C24—C23—C22	105.4 (5)
C11—C5—C6	107.6 (2)	C24—C23—H23A	110.7
C7—C5—C6	110.3 (3)	C22—C23—H23A	110.7
C4—C5—C6	107.9 (2)	C24—C23—H23B	110.7
C5—C6—H6B	109.5	C22—C23—H23B	110.7
C5—C6—H6C	109.5	H23A—C23—H23B	108.8
H6B—C6—H6C	109.5	O1—C24—C23	108.8 (5)
C5—C6—H6A	109.5	O1—C24—H24A	109.9
H6B—C6—H6A	109.5	C23—C24—H24A	109.9
H6C—C6—H6A	109.5	O1—C24—H24B	109.9
C5—C7—H7B	109.5	C23—C24—H24B	109.9
C5—C7—H7C	109.5	H24A—C24—H24B	108.3
C8—Si1—N1—C1	68.5 (3)	N2—Ti1—C12—C13	−167.7 (2)
C9—Si1—N1—C1	−54.1 (3)	C14—Ti1—C12—C13	−38.0 (2)
C10—Si1—N1—C1	−171.0 (3)	Cl2—Ti1—C12—C13	34.1 (3)
C8—Si1—N1—C2	−115.4 (3)	Cl1—Ti1—C12—C13	−78.6 (3)
C9—Si1—N1—C2	121.9 (3)	C15—Ti1—C12—C13	−79.9 (3)
C10—Si1—N1—C2	5.1 (3)	Cl3—Ti1—C12—C13	113.9 (2)
C14—Ti1—N2—C1	−14.3 (3)	C11—Ti1—C12—C13	−117.0 (3)
C13—Ti1—N2—C1	32.8 (3)	N2—Ti1—C12—C11	−50.70 (19)
Cl2—Ti1—N2—C1	−167.8 (2)	C14—Ti1—C12—C11	79.0 (2)
Cl1—Ti1—N2—C1	−95.4 (3)	C13—Ti1—C12—C11	117.0 (3)
C15—Ti1—N2—C1	−14.4 (3)	Cl2—Ti1—C12—C11	151.15 (15)
Cl3—Ti1—N2—C1	120.3 (3)	Cl1—Ti1—C12—C11	38.4 (2)
C12—Ti1—N2—C1	42.7 (3)	C15—Ti1—C12—C11	37.15 (17)
C11—Ti1—N2—C1	16.4 (3)	Cl3—Ti1—C12—C11	−129.07 (18)
C14—Ti1—N2—C3	163.4 (2)	C11—C12—C13—C14	0.7 (4)
C13—Ti1—N2—C3	−149.5 (2)	Ti1—C12—C13—C14	65.0 (2)
Cl2—Ti1—N2—C3	9.9 (3)	C11—C12—C13—Ti1	−64.3 (2)
Cl1—Ti1—N2—C3	82.3 (2)	N2—Ti1—C13—C14	−97.7 (3)
C15—Ti1—N2—C3	163.3 (2)	Cl2—Ti1—C13—C14	96.0 (2)
Cl3—Ti1—N2—C3	−62.0 (2)	Cl1—Ti1—C13—C14	14.7 (3)
C12—Ti1—N2—C3	−139.6 (2)	C15—Ti1—C13—C14	−37.7 (2)
C11—Ti1—N2—C3	−165.9 (2)	Cl3—Ti1—C13—C14	−179.4 (2)
C3—N2—C1—N1	1.5 (3)	C12—Ti1—C13—C14	−114.8 (3)
Ti1—N2—C1—N1	179.43 (18)	C11—Ti1—C13—C14	−78.4 (2)
C3—N2—C1—C4	−176.1 (3)	N2—Ti1—C13—C12	17.2 (3)
Ti1—N2—C1—C4	1.8 (4)	C14—Ti1—C13—C12	114.8 (3)
C2—N1—C1—N2	−2.0 (3)	Cl2—Ti1—C13—C12	−149.2 (2)
Si1—N1—C1—N2	174.59 (19)	Cl1—Ti1—C13—C12	129.5 (2)
C2—N1—C1—C4	175.6 (3)	C15—Ti1—C13—C12	77.1 (2)
Si1—N1—C1—C4	−7.8 (4)	Cl3—Ti1—C13—C12	−64.6 (2)
C1—N1—C2—C3	1.7 (3)	C11—Ti1—C13—C12	36.4 (2)
Si1—N1—C2—C3	−175.2 (2)	C12—C13—C14—C15	−0.6 (4)
N1—C2—C3—N2	−0.8 (4)	Ti1—C13—C14—C15	66.2 (2)
C1—N2—C3—C2	−0.4 (3)	C12—C13—C14—Ti1	−66.7 (2)
Ti1—N2—C3—C2	−178.8 (2)	N2—Ti1—C14—C13	115.0 (2)
N2—C1—C4—C5	−48.5 (4)	Cl2—Ti1—C14—C13	−82.3 (2)
N1—C1—C4—C5	134.2 (3)	Cl1—Ti1—C14—C13	−167.7 (2)
C1—C4—C5—C11	64.3 (3)	C15—Ti1—C14—C13	115.2 (3)
C1—C4—C5—C7	−58.2 (3)	Cl3—Ti1—C14—C13	0.8 (3)
C1—C4—C5—C6	−178.4 (2)	C12—Ti1—C14—C13	37.7 (2)
C7—C5—C11—C15	171.9 (3)	C11—Ti1—C14—C13	78.6 (2)
C4—C5—C11—C15	50.2 (4)	N2—Ti1—C14—C15	−0.2 (3)
C6—C5—C11—C15	−67.4 (4)	C13—Ti1—C14—C15	−115.2 (3)
C7—C5—C11—C12	−15.0 (4)	Cl2—Ti1—C14—C15	162.5 (2)
C4—C5—C11—C12	−136.8 (3)	Cl1—Ti1—C14—C15	77.1 (2)
C6—C5—C11—C12	105.7 (3)	Cl3—Ti1—C14—C15	−114.4 (2)
C7—C5—C11—Ti1	79.7 (3)	C12—Ti1—C14—C15	−77.5 (2)
C4—C5—C11—Ti1	−42.1 (3)	C11—Ti1—C14—C15	−36.6 (2)
C6—C5—C11—Ti1	−159.6 (2)	C12—C11—C15—C14	0.2 (3)
N2—Ti1—C11—C15	−114.7 (2)	C5—C11—C15—C14	174.4 (3)
C14—Ti1—C11—C15	37.4 (2)	Ti1—C11—C15—C14	−63.5 (2)
C13—Ti1—C11—C15	79.0 (2)	C12—C11—C15—Ti1	63.77 (19)
Cl2—Ti1—C11—C15	69.8 (2)	C5—C11—C15—Ti1	−122.1 (3)
Cl1—Ti1—C11—C15	−38.5 (2)	C13—C14—C15—C11	0.2 (4)
Cl3—Ti1—C11—C15	167.10 (18)	Ti1—C14—C15—C11	65.8 (2)
C12—Ti1—C11—C15	115.8 (3)	C13—C14—C15—Ti1	−65.6 (2)
N2—Ti1—C11—C12	129.50 (19)	N2—Ti1—C15—C11	63.58 (19)
C14—Ti1—C11—C12	−78.4 (2)	C14—Ti1—C15—C11	−116.3 (3)
C13—Ti1—C11—C12	−36.8 (2)	C13—Ti1—C15—C11	−78.6 (2)
Cl2—Ti1—C11—C12	−45.9 (2)	Cl2—Ti1—C15—C11	−137.18 (15)
Cl1—Ti1—C11—C12	−154.28 (17)	Cl1—Ti1—C15—C11	143.60 (18)
C15—Ti1—C11—C12	−115.8 (3)	Cl3—Ti1—C15—C11	−17.9 (2)
Cl3—Ti1—C11—C12	51.32 (19)	C12—Ti1—C15—C11	−37.23 (17)
N2—Ti1—C11—C5	6.3 (2)	N2—Ti1—C15—C14	179.9 (2)
C14—Ti1—C11—C5	158.4 (3)	C13—Ti1—C15—C14	37.7 (2)
C13—Ti1—C11—C5	−160.0 (3)	Cl2—Ti1—C15—C14	−20.9 (3)
Cl2—Ti1—C11—C5	−169.14 (18)	Cl1—Ti1—C15—C14	−100.1 (2)
Cl1—Ti1—C11—C5	82.5 (2)	Cl3—Ti1—C15—C14	98.4 (2)
C15—Ti1—C11—C5	121.0 (3)	C12—Ti1—C15—C14	79.1 (2)
Cl3—Ti1—C11—C5	−71.9 (2)	C11—Ti1—C15—C14	116.3 (3)
C12—Ti1—C11—C5	−123.2 (3)	C24—O1—C21—C22	17 (2)
C15—C11—C12—C13	−0.6 (3)	O1—C21—C22—C23	−14 (2)
C5—C11—C12—C13	−174.7 (3)	C21—C22—C23—C24	6(2)
Ti1—C11—C12—C13	62.5 (2)	C21—O1—C24—C23	−13 (2)
C15—C11—C12—Ti1	−63.10 (19)	C22—C23—C24—O1	4(2)
C5—C11—C12—Ti1	122.8 (3)

	(I)	(III)	(IV)	(V)	(VI)
Ti1—N2	2.153 (2)	2.163 (2)	2.357 (1)	2.274 (4)	2.261 (2)
Ti1—Cl1	2.3475 (9)	2.3513 (8)	2.3217 (4)	2.322 (2)	2.331 (1)
Ti1—Cl2	2.3377 (10)	2.3486 (8)	2.3729 (5)	2.326 (2)	2.338 (1)
Ti1—Cl3	2.3533 (9)	2.3340 (8)	2.2895 (5)	2.300 (2)	2.307 (1)
Ti1···Cpcent	2.030 (1)	2.036	2.025	2.035	2.047
Ti1···PL1	2.029 (1)	2.034 (1)	2.025	2.034	2.046
Ti1···PL2	0.022 (5)	0.608		0.175	0.215
N2—Ti1···Cpcent	111.2 (1)a	110.20	99.66	101.44	101.64
Cl1—Ti1···Cpcent	109.2 (1)a	110.08	116.37	116.68	113.90
Cl2—Ti1···Cpcent	110.69 (9)a	109.75	107.63	109.28	109.73
Cl3—Ti1···Cpcent	110.58 (9)a	110.93	114.71	113.76	115.56
Cl1—Ti1—N2	80.79 (7)	79.24 (6)	82.57 (2)	78.64	80.32
Cl2—Ti1—N2	138.10 (6)	140.05 (6)	152.70 (3)	149.27	148.63
Cl3—Ti1—N2	80.82 (7)	81.19 (6)	83.45 (2)	80.23	78.94
Cl2—Ti1—Cl1	85.38 (4)	86.06 (3)	85.18 (2)	87.84	87.14
Cl2—Ti1—Cl3	85.07 (4)	86.01 (3)	85.30 (2)	86.95	87.20
Cl3—Ti1—Cl1	139.98 (4)	138.52 (3)	128.55 (2)	128.07	129.12
PL1–PL2	81.0 (1)	78.335		82.491	85.895

Table 1

Geometrical parameters (Å, °) of the environment of the Ti atom in the title compound compared with those of related structures

	(I)	(III)	(IV)	(V)	(VI)
Ti1—N2	2.153 (2)	2.163 (2)	2.357 (1)	2.274 (4)	2.261 (2)
Ti1—Cl1	2.3475 (9)	2.3513 (8)	2.3217 (4)	2.322 (2)	2.331 (1)
Ti1—Cl2	2.3377 (10)	2.3486 (8)	2.3729 (5)	2.326 (2)	2.338 (1)
Ti1—Cl3	2.3533 (9)	2.3340 (8)	2.2895 (5)	2.300 (2)	2.307 (1)
Ti1⋯Cpcent	2.030 (1)	2.036	2.025	2.035	2.047
Ti1⋯PL1	2.029 (1)	2.034 (1)	2.025	2.034	2.046
Ti1⋯PL2	0.022 (5)	0.608		0.175	0.215
N2—Ti1⋯Cpcent	111.2 (1)a	110.20	99.66	101.44	101.64
Cl1—Ti1⋯Cpcent	109.2 (1)a	110.08	116.37	116.68	113.90
Cl2—Ti1⋯Cpcent	110.69 (9)a	109.75	107.63	109.28	109.73
Cl3—Ti1⋯Cpcent	110.58 (9)a	110.93	114.71	113.76	115.56
Cl1—Ti1—N2	80.79 (7)	79.24 (6)	82.57 (2)	78.64	80.32
Cl2—Ti1—N2	138.10 (6)	140.05 (6)	152.70 (3)	149.27	148.63
Cl3—Ti1—N2	80.82 (7)	81.19 (6)	83.45 (2)	80.23	78.94
Cl2—Ti1—Cl1	85.38 (4)	86.06 (3)	85.18 (2)	87.84	87.14
Cl2—Ti1—Cl3	85.07 (4)	86.01 (3)	85.30 (2)	86.95	87.20
Cl3—Ti1—Cl1	139.98 (4)	138.52 (3)	128.55 (2)	128.07	129.12
PL1–PL2	81.0 (1)	78.335		82.491	85.895

Notes: (a) the angle between the Ti1—N2 bond and the normal to PL1; (I) this work; (III) Krut’ko et al. (2006 ▶); (IV) Herrmann et al. (1995 ▶); (V) Enders et al. (1997 ▶); (VI) Enders et al. (1996 ▶). PL1 and Cpcent denote the C11–C15 Cp ring r.m.s. plane and centroid, respectively, while PL2 denotes an r.m.s. plane through the non-H atoms of a heterocyclic ring.