Chloridobis{N-[(dimethyl-amino)-dimethyl-sil-yl]-2,6-dimethyl-anilido-κN,N'}titanium(III).

In the monomeric title titanium(III) compound, [Ti(C(12)H(21)N(2)Si)(2)Cl], 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 mol-ecule 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 = 526.12

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.072

wR(F 2) = 0.168

S = 1.17

4866 reflections

289 parameters

H-atom parameters constrained

Δρmax = 0.47 e Å−3

Δρmin = −0.48 e Å−3

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.

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810025092/rk2217Isup2.hkl

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

[Ti(C12H21N2Si)2Cl]	F(000) = 2248
Mr = 526.12	Dx = 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

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

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(Fo2) + (0.062P)2 + 21.4919P] where P = (Fo2 + 2Fc2)/3
4866 reflections	(Δ/σ)max = 0.001
289 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.48 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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

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)