Chloridobis{N-[(dimethyl­amino)­dimethyl­sil­yl]-2,6-dimethyl­anilido-κ2N,N′}titanium(III)

Chen, J.

doi:10.1107/S1600536810025092

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page m866

https://doi.org/10.1107/S1600536810025092

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Chloridobis{N-[(dimethylamino)dimethylsilyl]-2,6-dimethylanilido-κ²N,N′}titanium(III)

Juan Chen ^a ^*

^aDepartment of Chemistry, Taiyuan Teachers College, Taiyuan 030031, People's Republic of China
^*Correspondence e-mail: sdbai@sxu.edu.cn

(Received 22 June 2010; accepted 26 June 2010; online 3 July 2010)

In the monomeric title titanium(III) compound, [Ti(C₁₂H₂₁N₂Si)₂Cl], the metal atom is surrounded by two N–silylated anilide ligands in an N,N′′-chelating mode. The two ends of the N—Si—N chelating unit exhibit different affinity to the metal center. The Ti—N_amine bond is longer than the Ti—N_anilide bond by about 0.29 Å. The two ligands are arranged trans to each other and the molecule demonstrates a pseudo-twofold rotation along the axis of the Ti—Cl bond. The five–coordinate Ti atom demonstrates a highly distorted trigonal-bipyramidal geometry.

Related literature

For related titanium compounds, see: Ovchinnikov et al. (1993 ); Chomitz et al. (2008 ). For amido titanium compounds as olefin polymerization catalyts, see: Alesso et al. (2008 ); Oakes et al. (2004 ); Tabernero et al. (2009 ). For catalytic applications of related N–silylated analido group-4-metal compounds towards olefin polymerization, see: Gibson et al. (1998 ); Hill & Hitchcock (2002 ); Yuan et al. (2010 ). For related organometallic compounds with analogous analido ligands, see: Schumann et al. (2000 ); Chen (2008 , 2009 ).

Experimental

Crystal data

[Ti(C₁₂H₂₁N₂Si)₂Cl]
M_r = 526.12
Monoclinic, C 2/c
a = 34.145 (5) Å
b = 9.2718 (15) Å
c = 20.909 (3) Å
β = 122.894 (2)°
V = 5558.2 (15) Å³
Z = 8
Mo Kα radiation
μ = 0.51 mm⁻¹
T = 213 K
0.40 × 0.30 × 0.15 mm

Data collection

Bruker SMART area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.814, T_max = 0.928
10981 measured reflections
4866 independent reflections
4473 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.072
wR(F²) = 0.168
S = 1.17
4866 reflections
289 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Selected bond lengths (Å)

Ti1—N1	1.989 (3)
Ti1—N3	1.995 (3)
Ti1—N2	2.282 (4)
Ti1—N4	2.291 (4)
Ti1—Cl1	2.3374 (13)

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); 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); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810025092/rk2217sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810025092/rk2217Isup2.hkl

checkCIF report

Comment top

Group 4 metal amides supported with the N–silylated anilido ligands were active catalysts for olefin polymerization (Gibson et al., 1998; Hill & Hitchcock, 2002). In particular, titanium amides were found to be more efficient and applicable (Alesso et al., 2008; Oakes et al., 2004; Tabernero et al., 2009). Therefore, the monoionic N–silylated anilido ligand bearing a pendant amino group was employed for synthesizing titanium compound. Analogous compounds with different metals including Zn (Schumann et al., 2000), Zr (Chen, 2009) and Fe (Chen, 2008) have been synthesized. Moreover, a group of zirconium amides with the similar ligand were reported showing good performance in ethylene polymerization (Yuan et al., 2010). It implied that the title titanium compound would behave better in catalysis application.

The title compound was prepared by the metathetical reaction of TiCl₄(THF)₂ with [LiN(SiMe₂NMe₂)(2,6-Me₂C₆H₃)]₂. It is interesting that the valence of Ti has changed from IV to III. Similar situation could be found in Ovchinnikov's work (Ovchinnikov et al., 1993) and other - Chomitz et al., 2008). The driving factors for reduction will be investigated in further research. The suitable single–crystal of the title compound was obtained by recrystallization in toluene. Its molecular structure is shown in Fig. 1. In the monomeric molecular structure of title compound, the metal center is coordinated by two N–silylated anilido ligands. Each ligand has an N—Si—N chelating moiety, which is presumed to be a "quasi" conjugated unit owing to d···π–interaction between Si and N atoms. Two ligands are arranged in trans– to each other and obey the pseudo–C₂ symmetrical operation. Such arrangement makes Ti atom right in the triangular planes of N1···N3···Cl1 and N2···N4···Cl1. The five–coordinate Ti(III) center demonstrates a highly distorted trigonal–bipyramid geometry (N2– and N4–apical atoms). The configuration is as same as the Fe(III) compound reported previously (Chen, 2008), presumably due to the same valence. The metal center Ti is chelated with an average N—Ti—N bite angle of 74.18 (13)°. The corresponding N—Si—N of the ligand is constrained to be about 95.25 (16)°. The mean Ti—N_anilido bond is 1.992 (3)Å, whereas the mean Ti—N_amino bond is 2.286 (4)Å in the title compound. It suggests the former is much tighter than the latter. They are different from corresponding bond lengths 1.972 (4)Å and 2.356 (6)Å in a related amido Ti(III) compound reported by Chomitz et al. (2008).

Related literature top

For related titanium compounds, see: Ovchinnikov et al. (1993); Chomitz et al. (2008). For amido titanium compounds as olefin polymerization catalyts, see: Alesso et al. (2008); Oakes et al. (2004); Tabernero et al. (2009). For catalytic applications of related N–silylated analido group 4 metal compounds towards olefin polymerization, see: Gibson et al. (1998); Hill & Hitchcock (2002); Yuan et al. (2010). For related organometallic compounds with analogous analido ligands, see: Schumann et al. (2000); Chen (2008, 2009).

Experimental top

TiCl₄(THF)₂ (0.48 g, 1.45 mmol) was added into the solution of [LiN(SiMe₂NMe₂)(2,6-Me₂C₆H₃)]₂ (0.66 g, 1.45 mmol) in Et₂O (30 ml) at 273 K. The reaction mixture was warmed to room temperature and kept stirring for 12 h. It was dried in vacuum to remove all volatiles and the residue was extracted with CH₂Cl₂ (30 ml). Concentration of the filtrate under reduced pressure and recrystallization in toluene gave the title compound as purple crystals (yield 0.50 g, 66%).

Structure description top

For related titanium compounds, see: Ovchinnikov et al. (1993); Chomitz et al. (2008). For amido titanium compounds as olefin polymerization catalyts, see: Alesso et al. (2008); Oakes et al. (2004); Tabernero et al. (2009). For catalytic applications of related N–silylated analido group 4 metal compounds towards olefin polymerization, see: Gibson et al. (1998); Hill & Hitchcock (2002); Yuan et al. (2010). For related organometallic compounds with analogous analido ligands, see: Schumann et al. (2000); Chen (2008, 2009).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure, showing the atom–numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius.

Chloridobis{N-[(dimethylamino)dimethylsilyl]-2,6-dimethylanilido- κ²N,N'}titanium(III) top

Crystal data top

[Ti(C₁₂H₂₁N₂Si)₂Cl]	F(000) = 2248
M_r = 526.12	D_x = 1.258 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4223 reflections
a = 34.145 (5) Å	θ = 2.3–27.6°
b = 9.2718 (15) Å	µ = 0.51 mm⁻¹
c = 20.909 (3) Å	T = 213 K
β = 122.894 (2)°	Block, purple
V = 5558.2 (15) Å³	0.40 × 0.30 × 0.15 mm
Z = 8

Data collection top

Bruker SMART area-detector diffractometer	4866 independent reflections
Radiation source: fine–focus sealed tube	4473 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
φ and ω scans	θ_max = 25.0°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −40→40
T_min = 0.814, T_max = 0.928	k = −6→11
10981 measured reflections	l = −24→24

Refinement top

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)] = 0.072	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.168	H-atom parameters constrained
S = 1.17	w = 1/[σ²(F_o²) + (0.062P)² + 21.4919P] where P = (F_o² + 2F_c²)/3
4866 reflections	(Δ/σ)_max = 0.001
289 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

[Ti(C₁₂H₂₁N₂Si)₂Cl]	V = 5558.2 (15) Å³
M_r = 526.12	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 34.145 (5) Å	µ = 0.51 mm⁻¹
b = 9.2718 (15) Å	T = 213 K
c = 20.909 (3) Å	0.40 × 0.30 × 0.15 mm
β = 122.894 (2)°

Data collection top

Bruker SMART area-detector diffractometer	4866 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4473 reflections with I > 2σ(I)
T_min = 0.814, T_max = 0.928	R_int = 0.033
10981 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.072	0 restraints
wR(F²) = 0.168	H-atom parameters constrained
S = 1.17	w = 1/[σ²(F_o²) + (0.062P)² + 21.4919P] where P = (F_o² + 2F_c²)/3
4866 reflections	Δρ_max = 0.47 e Å⁻³
289 parameters	Δρ_min = −0.48 e Å⁻³

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 (Å²) top

	x	y	z	U_iso*/U_eq
Ti1	0.15222 (2)	0.34275 (8)	0.06414 (4)	0.0231 (2)
Si1	0.14374 (4)	0.45890 (13)	0.18120 (7)	0.0284 (3)
Si2	0.12637 (4)	0.23530 (14)	−0.08132 (7)	0.0291 (3)
Cl1	0.23284 (4)	0.30582 (13)	0.13779 (7)	0.0399 (3)
N1	0.12378 (11)	0.3088 (4)	0.12435 (18)	0.0249 (7)
N2	0.15461 (11)	0.5585 (4)	0.11873 (19)	0.0278 (8)
N3	0.12846 (11)	0.4008 (4)	−0.04285 (18)	0.0266 (8)
N4	0.13576 (12)	0.1310 (4)	−0.0022 (2)	0.0302 (8)
C1	0.09894 (14)	0.1945 (4)	0.1318 (2)	0.0255 (9)
C2	0.12258 (15)	0.0776 (5)	0.1805 (2)	0.0310 (10)
C3	0.0969 (2)	−0.0339 (5)	0.1844 (3)	0.0461 (13)
H3A	0.1126	−0.1127	0.2166	0.055*
C4	0.0490 (2)	−0.0317 (6)	0.1420 (3)	0.0547 (15)
H4A	0.0321	−0.1075	0.1460	0.066*
C5	0.02597 (18)	0.0816 (6)	0.0941 (3)	0.0492 (14)
H5A	−0.0068	0.0823	0.0649	0.059*
C6	0.04990 (15)	0.1948 (5)	0.0877 (3)	0.0347 (10)
C7	0.17487 (16)	0.0709 (5)	0.2274 (3)	0.0430 (12)
H7A	0.1849	−0.0171	0.2572	0.064*
H7B	0.1871	0.1536	0.2612	0.064*
H7C	0.1864	0.0719	0.1940	0.064*
C8	0.02325 (15)	0.3130 (6)	0.0313 (3)	0.0456 (13)
H8A	−0.0099	0.2956	0.0064	0.068*
H8B	0.0314	0.3148	−0.0065	0.068*
H8C	0.0311	0.4050	0.0576	0.068*
C9	0.10009 (19)	0.5429 (6)	0.1969 (3)	0.0472 (13)
H9A	0.1148	0.5659	0.2504	0.071*
H9B	0.0746	0.4760	0.1814	0.071*
H9C	0.0882	0.6305	0.1669	0.071*
C10	0.19967 (18)	0.4424 (6)	0.2747 (3)	0.0453 (12)
H10A	0.1962	0.4827	0.3142	0.068*
H10B	0.2238	0.4945	0.2734	0.068*
H10C	0.2082	0.3415	0.2856	0.068*
C11	0.11430 (17)	0.6473 (5)	0.0631 (3)	0.0384 (11)
H11A	0.1152	0.7391	0.0861	0.058*
H11B	0.0856	0.5973	0.0481	0.058*
H11C	0.1157	0.6639	0.0186	0.058*
C12	0.19724 (17)	0.6475 (5)	0.1534 (3)	0.0409 (11)
H12A	0.1927	0.7351	0.1740	0.061*
H12B	0.2038	0.6722	0.1150	0.061*
H12C	0.2233	0.5937	0.1941	0.061*
C13	0.12235 (15)	0.5317 (5)	−0.0824 (2)	0.0293 (10)
C14	0.07746 (16)	0.5910 (5)	−0.1291 (2)	0.0354 (11)
C15	0.0718 (2)	0.7169 (6)	−0.1689 (3)	0.0481 (13)
H15A	0.0418	0.7561	−0.2004	0.058*
C16	0.1094 (2)	0.7862 (6)	−0.1633 (3)	0.0550 (15)
H16A	0.1050	0.8702	−0.1916	0.066*
C17	0.1533 (2)	0.7303 (5)	−0.1156 (3)	0.0440 (12)
H17A	0.1790	0.7789	−0.1104	0.053*
C18	0.16069 (17)	0.6047 (5)	−0.0751 (3)	0.0357 (11)
C19	0.03519 (16)	0.5235 (6)	−0.1355 (3)	0.0473 (13)
H19A	0.0077	0.5798	−0.1702	0.071*
H19B	0.0395	0.5215	−0.0857	0.071*
H19C	0.0313	0.4258	−0.1547	0.071*
C20	0.20968 (17)	0.5505 (6)	−0.0233 (3)	0.0490 (13)
H20A	0.2311	0.6145	−0.0262	0.074*
H20B	0.2122	0.4543	−0.0388	0.074*
H20C	0.2173	0.5478	0.0287	0.074*
C21	0.17307 (18)	0.1982 (6)	−0.0987 (3)	0.0476 (13)
H21A	0.1593	0.1624	−0.1502	0.071*
H21B	0.1942	0.1264	−0.0628	0.071*
H21C	0.1901	0.2864	−0.0924	0.071*
C22	0.06979 (18)	0.1932 (6)	−0.1711 (3)	0.0499 (13)
H22A	0.0756	0.1580	−0.2089	0.075*
H22B	0.0509	0.2799	−0.1900	0.075*
H22C	0.0535	0.1200	−0.1612	0.075*
C23	0.17362 (19)	0.0209 (6)	0.0299 (3)	0.0484 (13)
H23A	0.1629	−0.0638	−0.0026	0.073*
H23B	0.1819	−0.0059	0.0806	0.073*
H23C	0.2007	0.0606	0.0325	0.073*
C24	0.09293 (18)	0.0616 (6)	−0.0162 (3)	0.0447 (13)
H24A	0.0875	−0.0273	−0.0443	0.067*
H24B	0.0667	0.1260	−0.0455	0.067*
H24C	0.0965	0.0403	0.0321	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ti1	0.0230 (4)	0.0245 (4)	0.0225 (4)	−0.0011 (3)	0.0128 (3)	0.0006 (3)
Si1	0.0335 (6)	0.0254 (6)	0.0285 (6)	−0.0036 (5)	0.0184 (5)	−0.0021 (5)
Si2	0.0284 (6)	0.0325 (7)	0.0267 (6)	−0.0002 (5)	0.0153 (5)	−0.0005 (5)
Cl1	0.0239 (5)	0.0453 (7)	0.0430 (7)	0.0024 (5)	0.0133 (5)	0.0003 (5)
N1	0.0232 (17)	0.0258 (19)	0.0262 (17)	−0.0005 (14)	0.0138 (15)	0.0010 (15)
N2	0.0294 (18)	0.0220 (19)	0.0297 (18)	−0.0025 (15)	0.0146 (16)	−0.0010 (15)
N3	0.0267 (18)	0.0282 (19)	0.0234 (17)	−0.0012 (15)	0.0126 (15)	0.0037 (15)
N4	0.035 (2)	0.0255 (19)	0.0329 (19)	−0.0025 (16)	0.0204 (17)	−0.0018 (16)
C1	0.033 (2)	0.024 (2)	0.026 (2)	−0.0014 (18)	0.0208 (19)	−0.0013 (18)
C2	0.042 (3)	0.025 (2)	0.028 (2)	−0.0020 (19)	0.021 (2)	−0.0024 (19)
C3	0.069 (4)	0.030 (3)	0.038 (3)	−0.007 (2)	0.028 (3)	0.001 (2)
C4	0.072 (4)	0.044 (3)	0.056 (3)	−0.030 (3)	0.039 (3)	−0.002 (3)
C5	0.039 (3)	0.061 (4)	0.047 (3)	−0.024 (3)	0.023 (2)	−0.005 (3)
C6	0.034 (2)	0.038 (3)	0.036 (2)	−0.005 (2)	0.022 (2)	−0.004 (2)
C7	0.048 (3)	0.034 (3)	0.040 (3)	0.012 (2)	0.019 (2)	0.011 (2)
C8	0.023 (2)	0.052 (3)	0.052 (3)	0.003 (2)	0.014 (2)	0.003 (3)
C9	0.065 (3)	0.037 (3)	0.060 (3)	−0.003 (3)	0.047 (3)	−0.011 (3)
C10	0.055 (3)	0.039 (3)	0.031 (2)	−0.012 (2)	0.017 (2)	−0.004 (2)
C11	0.046 (3)	0.030 (3)	0.038 (3)	0.005 (2)	0.023 (2)	0.006 (2)
C12	0.042 (3)	0.033 (3)	0.046 (3)	−0.012 (2)	0.022 (2)	−0.007 (2)
C13	0.039 (2)	0.029 (2)	0.020 (2)	0.0034 (19)	0.0163 (19)	0.0016 (18)
C14	0.046 (3)	0.035 (3)	0.026 (2)	0.007 (2)	0.020 (2)	0.002 (2)
C15	0.060 (3)	0.044 (3)	0.034 (3)	0.021 (3)	0.022 (3)	0.012 (2)
C16	0.097 (5)	0.031 (3)	0.054 (3)	0.008 (3)	0.052 (4)	0.011 (3)
C17	0.068 (4)	0.029 (3)	0.051 (3)	−0.003 (2)	0.043 (3)	−0.002 (2)
C18	0.048 (3)	0.032 (3)	0.035 (2)	−0.005 (2)	0.028 (2)	−0.005 (2)
C19	0.039 (3)	0.055 (3)	0.042 (3)	0.016 (2)	0.018 (2)	0.008 (3)
C20	0.043 (3)	0.050 (3)	0.057 (3)	−0.018 (2)	0.029 (3)	−0.003 (3)
C21	0.054 (3)	0.049 (3)	0.054 (3)	−0.001 (3)	0.039 (3)	−0.003 (3)
C22	0.046 (3)	0.053 (3)	0.039 (3)	−0.002 (3)	0.015 (2)	−0.010 (3)
C23	0.062 (3)	0.036 (3)	0.044 (3)	0.017 (2)	0.026 (3)	0.007 (2)
C24	0.060 (3)	0.042 (3)	0.047 (3)	−0.023 (3)	0.039 (3)	−0.015 (2)

Geometric parameters (Å, º) top

Ti1—N1	1.989 (3)	C10—H10A	0.9700
Ti1—N3	1.995 (3)	C10—H10B	0.9700
Ti1—N2	2.282 (4)	C10—H10C	0.9700
Ti1—N4	2.291 (4)	C11—H11A	0.9700
Ti1—Cl1	2.3374 (13)	C11—H11B	0.9700
Si1—N1	1.713 (4)	C11—H11C	0.9700
Si1—N2	1.795 (4)	C12—H12A	0.9700
Si1—C10	1.855 (5)	C12—H12B	0.9700
Si1—C9	1.861 (5)	C12—H12C	0.9700
Si2—N3	1.716 (4)	C13—C18	1.406 (6)
Si2—N4	1.789 (4)	C13—C14	1.407 (6)
Si2—C21	1.851 (5)	C14—C15	1.386 (7)
Si2—C22	1.863 (5)	C14—C19	1.511 (7)
N1—C1	1.418 (5)	C15—C16	1.383 (8)
N2—C12	1.476 (5)	C15—H15A	0.9400
N2—C11	1.479 (6)	C16—C17	1.374 (8)
N3—C13	1.419 (5)	C16—H16A	0.9400
N4—C24	1.474 (6)	C17—C18	1.380 (7)
N4—C23	1.490 (6)	C17—H17A	0.9400
C1—C2	1.403 (6)	C18—C20	1.502 (7)
C1—C6	1.406 (6)	C19—H19A	0.9700
C2—C3	1.387 (6)	C19—H19B	0.9700
C2—C7	1.500 (6)	C19—H19C	0.9700
C3—C4	1.374 (8)	C20—H20A	0.9700
C3—H3A	0.9400	C20—H20B	0.9700
C4—C5	1.367 (8)	C20—H20C	0.9700
C4—H4A	0.9400	C21—H21A	0.9700
C5—C6	1.381 (6)	C21—H21B	0.9700
C5—H5A	0.9400	C21—H21C	0.9700
C6—C8	1.501 (7)	C22—H22A	0.9700
C7—H7A	0.9700	C22—H22B	0.9700
C7—H7B	0.9700	C22—H22C	0.9700
C7—H7C	0.9700	C23—H23A	0.9700
C8—H8A	0.9700	C23—H23B	0.9700
C8—H8B	0.9700	C23—H23C	0.9700
C8—H8C	0.9700	C24—H24A	0.9700
C9—H9A	0.9700	C24—H24B	0.9700
C9—H9B	0.9700	C24—H24C	0.9700
C9—H9C	0.9700

N1—Ti1—N3	135.36 (14)	H8B—C8—H8C	109.5
N1—Ti1—N2	73.69 (13)	Si1—C9—H9A	109.5
N3—Ti1—N2	101.94 (14)	Si1—C9—H9B	109.5
N1—Ti1—N4	101.77 (13)	H9A—C9—H9B	109.5
N3—Ti1—N4	74.68 (14)	Si1—C9—H9C	109.5
N2—Ti1—N4	169.84 (13)	H9A—C9—H9C	109.5
N1—Ti1—Cl1	111.41 (10)	H9B—C9—H9C	109.5
N3—Ti1—Cl1	113.23 (10)	Si1—C10—H10A	109.5
N2—Ti1—Cl1	95.13 (9)	Si1—C10—H10B	109.5
N4—Ti1—Cl1	95.00 (10)	H10A—C10—H10B	109.5
N3—Ti1—Si1	134.19 (11)	Si1—C10—H10C	109.5
N4—Ti1—Si1	138.01 (9)	H10A—C10—H10C	109.5
Cl1—Ti1—Si1	97.07 (5)	H10B—C10—H10C	109.5
N1—Ti1—Si2	130.26 (10)	N2—C11—H11A	109.5
N2—Ti1—Si2	138.34 (9)	N2—C11—H11B	109.5
Cl1—Ti1—Si2	102.91 (4)	H11A—C11—H11B	109.5
Si1—Ti1—Si2	159.95 (4)	N2—C11—H11C	109.5
N1—Si1—N2	94.26 (16)	H11A—C11—H11C	109.5
N1—Si1—C10	117.3 (2)	H11B—C11—H11C	109.5
N2—Si1—C10	108.0 (2)	N2—C12—H12A	109.5
N1—Si1—C9	114.0 (2)	N2—C12—H12B	109.5
N2—Si1—C9	114.5 (2)	H12A—C12—H12B	109.5
C10—Si1—C9	108.3 (2)	N2—C12—H12C	109.5
C10—Si1—Ti1	110.52 (18)	H12A—C12—H12C	109.5
C9—Si1—Ti1	141.20 (18)	H12B—C12—H12C	109.5
N3—Si2—N4	96.25 (16)	C18—C13—C14	119.1 (4)
N3—Si2—C21	116.0 (2)	C18—C13—N3	121.0 (4)
N4—Si2—C21	109.9 (2)	C14—C13—N3	119.9 (4)
N3—Si2—C22	114.6 (2)	C15—C14—C13	119.4 (5)
N4—Si2—C22	112.7 (2)	C15—C14—C19	118.8 (4)
C21—Si2—C22	107.2 (2)	C13—C14—C19	121.9 (4)
C21—Si2—Ti1	118.36 (18)	C16—C15—C14	121.3 (5)
C22—Si2—Ti1	134.44 (18)	C16—C15—H15A	119.3
C1—N1—Si1	124.5 (3)	C14—C15—H15A	119.3
C1—N1—Ti1	135.6 (3)	C17—C16—C15	118.9 (5)
Si1—N1—Ti1	99.43 (16)	C17—C16—H16A	120.6
C12—N2—C11	108.9 (4)	C15—C16—H16A	120.6
C12—N2—Si1	117.9 (3)	C16—C17—C18	121.9 (5)
C11—N2—Si1	112.8 (3)	C16—C17—H17A	119.1
C12—N2—Ti1	119.6 (3)	C18—C17—H17A	119.1
C11—N2—Ti1	109.2 (3)	C17—C18—C13	119.4 (5)
Si1—N2—Ti1	87.02 (14)	C17—C18—C20	119.1 (4)
C13—N3—Si2	122.5 (3)	C13—C18—C20	121.6 (4)
C13—N3—Ti1	136.5 (3)	C14—C19—H19A	109.5
Si2—N3—Ti1	99.94 (17)	C14—C19—H19B	109.5
C24—N4—C23	108.3 (4)	H19A—C19—H19B	109.5
C24—N4—Si2	113.1 (3)	C14—C19—H19C	109.5
C23—N4—Si2	117.5 (3)	H19A—C19—H19C	109.5
C24—N4—Ti1	112.7 (3)	H19B—C19—H19C	109.5
C23—N4—Ti1	116.6 (3)	C18—C20—H20A	109.5
Si2—N4—Ti1	87.61 (15)	C18—C20—H20B	109.5
C2—C1—C6	119.2 (4)	H20A—C20—H20B	109.5
C2—C1—N1	121.0 (4)	C18—C20—H20C	109.5
C6—C1—N1	119.8 (4)	H20A—C20—H20C	109.5
C3—C2—C1	119.0 (4)	H20B—C20—H20C	109.5
C3—C2—C7	119.8 (4)	Si2—C21—H21A	109.5
C1—C2—C7	121.2 (4)	Si2—C21—H21B	109.5
C4—C3—C2	121.4 (5)	H21A—C21—H21B	109.5
C4—C3—H3A	119.3	Si2—C21—H21C	109.5
C2—C3—H3A	119.3	H21A—C21—H21C	109.5
C5—C4—C3	119.5 (5)	H21B—C21—H21C	109.5
C5—C4—H4A	120.2	Si2—C22—H22A	109.5
C3—C4—H4A	120.2	Si2—C22—H22B	109.5
C4—C5—C6	121.4 (5)	H22A—C22—H22B	109.5
C4—C5—H5A	119.3	Si2—C22—H22C	109.5
C6—C5—H5A	119.3	H22A—C22—H22C	109.5
C5—C6—C1	119.4 (5)	H22B—C22—H22C	109.5
C5—C6—C8	119.5 (4)	N4—C23—H23A	109.5
C1—C6—C8	121.0 (4)	N4—C23—H23B	109.5
C2—C7—H7A	109.5	H23A—C23—H23B	109.5
C2—C7—H7B	109.5	N4—C23—H23C	109.5
H7A—C7—H7B	109.5	H23A—C23—H23C	109.5
C2—C7—H7C	109.5	H23B—C23—H23C	109.5
H7A—C7—H7C	109.5	N4—C24—H24A	109.5
H7B—C7—H7C	109.5	N4—C24—H24B	109.5
C6—C8—H8A	109.5	H24A—C24—H24B	109.5
C6—C8—H8B	109.5	N4—C24—H24C	109.5
H8A—C8—H8B	109.5	H24A—C24—H24C	109.5
C6—C8—H8C	109.5	H24B—C24—H24C	109.5
H8A—C8—H8C	109.5

Experimental details

Crystal data
Chemical formula	[Ti(C₁₂H₂₁N₂Si)₂Cl]
M_r	526.12
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	213
a, b, c (Å)	34.145 (5), 9.2718 (15), 20.909 (3)
β (°)	122.894 (2)
V (Å³)	5558.2 (15)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.51
Crystal size (mm)	0.40 × 0.30 × 0.15

Data collection
Diffractometer	Bruker SMART area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.814, 0.928
No. of measured, independent and observed [I > 2σ(I)] reflections	10981, 4866, 4473
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.072, 0.168, 1.17
No. of reflections	4866
No. of parameters	289
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.062P)² + 21.4919P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.48

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Ti1—N1	1.989 (3)	Ti1—N4	2.291 (4)
Ti1—N3	1.995 (3)	Ti1—Cl1	2.3374 (13)
Ti1—N2	2.282 (4)

Acknowledgements

This work was carried out under the sponsorship of the Natural Science Foundation of Shanxi Province (2008011024).

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