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Acta Cryst. (2009). E65, m611    [ doi:10.1107/S1600536809015839 ]

The ansa-bridged cyclopentadienyl titanium complex [{[eta]5-C5Me4CH2-C(NMe2)=N}TiCl2]

D. Guo, H.-B. Tong and M. Zhou

Abstract top

The title complex, dichlorido[N,N-dimethyl-2-([eta]5-tetramethylcyclopentadienyl)acetamidinido-[kappa]N']titanium(IV), [Ti(C13H20N2)Cl2], exhibits an unusual ansa-bridged conformation. The cyclopentadienyl ring and the mean plane of the Ti-N=C-C-C fragment form a dihedral angle of 88.08 (11)°.

Comment top

The homogeneous coordination polymerization catalysts, especially group IV metallocene catalysts, have created new opportunities for the production of ethylene α-olefin copolymers and received extensive attention in recent years (Mahanthappa et al., 2004). The constrained geometry catalysts with a pendant nitrogen or oxygen donor on the cyclopentadienyl ligand, such as Me2Si-(η5-Me4C5)(t-BuN)TiCl2 (Hughes et al., 1993) and 2-tetramethylcyclopentadienyl-4-methylphenoxytitaniumdibenzyl (Zhang et al., 2004) have been developed due to their structural features and good catalytic activities (Chen et al., 1997). Here we present the synthesis and crystal structure of a new ansa-bridged cyclopentadienyl titanium complex (I)

In (I) (Fig. 1), the distance from the central metal atom Ti to the centroid of Cp* is 2.024 (2) Å. The bond lengths Ti—N1, Ti—Cl1 and Ti—Cl2 are 1.823 (3), 2.3104 (12) and 2.3036 (12) Å, respectively. The bond angle Cl1—Ti—Cl2 is 105.40 (5) °. Atoms C1, C6, C7, N1 and Ti are exactly co-planar with a highest deviation of 0.0191 Å. The two planes - Cp* and C1/C6/C7/N1/Ti are almost perpendicular making a dihedral angle of 88.08 (11)°. The bond angles C1—C6—C7, C6—C7—N1 and C7—N1—Ti are 106.7 (3),116.7 (3) and 129.5 (2) °, respectively.

Related literature top

For related crystal structures, see: Hughes et al. (1993); Zhang et al. (2004). For general background, see: Chen et al. (1997); Mahanthappa et al. (2004).

Experimental top

(CH3)2NCN (0.36 ml, 4.52 mmol) was added to a solution of PhN(Li)SiMe3(0.386 g, 2.26 mmol) in THF (30 cm3) at -78 °C. The resulting mixture was warmed to ca.25°C and stirred for overnight. CpTiCl3 (0.99 g, 4.52 mmol) was added at -78°C. The resulting mixture was warmed to ca.25°C and stirred for 24 h. The volatiles were removed in vacuo, and there residue was extracted with dichloromethane and filtered. The filtrate was concentrated to give red crystals of (I)(0.14 g, 13%).

Anal. calcd. for C13H20Cl2N2Ti(%): C, 48.33; H, 6.24; N, 8.67. Found: C, 48.25; H, 6.25; N, 8.73. A l l manipulations were performed under argonusing standard Schlenk and vacuum line techniques. THF was dried and distilled over Na underargon prior to use. Elemental analysis and NMR spectra are completely in agreement with the structure of (I). Spectroscopic analysis, 1HNMR (CDCl3): d 2.11~2.18 (d, 12 H, Cp—CH3), d 2.80, 3.10 (d, 6 H, N(CH3)2), d 4.09 (s, 2 H, CH2). 13CNMR (CDCl3): d 10.0, 10.8 (Cp-CH3), d 28.9 (CH2), d 33.3, 35.9 (N(CH3)2), d 118.5, 123.2, 127.4,128.6, 129.0 (Cp), 171.6 (CH2-C(NMe2)-N).

Refinement top

The H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93-0.97 Å, and Uiso = 1.2-1.5 Ueq(parent atom).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are omitted for clarity.
dichlorido[N,N-dimethyl-2-(η5- tetramethylcyclopentadienyl)acetamidinido-κN']titanium(IV) top
Crystal data top
[Ti(C13H20N2)Cl2]Dx = 1.411 Mg m−3
Mr = 323.11Mo Kα radiation
λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 4409 reflections
a = 12.600 (5) Åθ = 2.5–27.0º
b = 15.498 (6) ŵ = 0.90 mm−1
c = 15.574 (5) ÅT = 213 K
V = 3041.1 (19) Å3Block, orange
Z = 80.30 × 0.20 × 0.20 mm
F000 = 1344
Data collection top
Siemens SMART
diffractometer		2677 independent reflections
Radiation source: fine-focus sealed tube2554 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.037
T = 213 Kθmax = 25.0º
ω scansθmin = 2.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997)		h = −14→14
Tmin = 0.774, Tmax = 0.841k = −18→12
11691 measured reflectionsl = −18→18
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.056H-atom parameters constrained
wR(F2) = 0.117  w = 1/[σ2(Fo2) + (0.036P)2 + 4.3005P]
where P = (Fo2 + 2Fc2)/3
S = 1.27(Δ/σ)max = 0.001
2677 reflectionsΔρmax = 0.38 e Å−3
169 parametersΔρmin = −0.30 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Ti(C13H20N2)Cl2]V = 3041.1 (19) Å3
Mr = 323.11Z = 8
Orthorhombic, PbcaMo Kα
a = 12.600 (5) ŵ = 0.90 mm−1
b = 15.498 (6) ÅT = 213 K
c = 15.574 (5) Å0.30 × 0.20 × 0.20 mm
Data collection top
Siemens SMART
diffractometer		2677 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997)		2554 reflections with I > 2σ(I)
Tmin = 0.774, Tmax = 0.841Rint = 0.037
11691 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.056169 parameters
wR(F2) = 0.117H-atom parameters constrained
S = 1.27Δρmax = 0.38 e Å−3
2677 reflectionsΔρmin = −0.30 e Å−3
Special details top

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 (Å2) top
xyzUiso*/Ueq
Ti0.21528 (5)0.56734 (4)0.10562 (4)0.02449 (19)
Cl10.10277 (7)0.66810 (6)0.04506 (6)0.0396 (3)
Cl20.11570 (8)0.49802 (7)0.20873 (6)0.0416 (3)
N10.3122 (2)0.63161 (19)0.16445 (18)0.0302 (7)
N20.4755 (2)0.69295 (19)0.19627 (19)0.0326 (7)
C10.3752 (3)0.5272 (2)0.0479 (2)0.0289 (8)
C20.3304 (3)0.4522 (2)0.0835 (2)0.0285 (8)
C30.2387 (3)0.4307 (2)0.0348 (2)0.0314 (8)
C40.2270 (3)0.4933 (2)−0.0298 (2)0.0313 (8)
C50.3117 (3)0.5534 (2)−0.0221 (2)0.0299 (8)
C60.4650 (3)0.5788 (2)0.0867 (2)0.0347 (9)
H6A0.50140.61230.04230.042*
H6B0.51660.54030.11410.042*
C70.4158 (3)0.6384 (2)0.1528 (2)0.0282 (8)
C80.4285 (3)0.7477 (3)0.2621 (3)0.0458 (10)
H8A0.35290.73620.26580.069*
H8B0.43960.80780.24730.069*
H8C0.46150.73560.31710.069*
C90.5892 (3)0.7047 (3)0.1806 (3)0.0447 (10)
H9A0.61760.65360.15310.067*
H9B0.62530.71410.23480.067*
H9C0.59990.75440.14370.067*
C100.3711 (3)0.4014 (3)0.1590 (2)0.0421 (10)
H10A0.40400.34860.13870.063*
H10B0.31250.38720.19680.063*
H10C0.42290.43550.19000.063*
C110.1708 (3)0.3522 (2)0.0475 (3)0.0442 (10)
H11A0.09670.36780.04120.066*
H11B0.18260.32900.10460.066*
H11C0.18920.30900.00500.066*
C120.1436 (3)0.4946 (3)−0.0985 (3)0.0448 (10)
H12A0.17330.4725−0.15160.067*
H12B0.11940.5534−0.10730.067*
H12C0.08420.4588−0.08120.067*
C130.3304 (3)0.6293 (3)−0.0800 (2)0.0438 (10)
H13A0.38360.6667−0.05470.066*
H13B0.26470.6611−0.08720.066*
H13C0.35500.6091−0.13550.066*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ti0.0217 (3)0.0269 (3)0.0249 (3)0.0006 (3)0.0008 (2)−0.0016 (3)
Cl10.0328 (5)0.0388 (5)0.0471 (6)0.0091 (4)−0.0028 (4)0.0043 (4)
Cl20.0404 (5)0.0474 (6)0.0370 (5)−0.0053 (5)0.0098 (4)0.0072 (4)
N10.0284 (16)0.0325 (16)0.0296 (15)0.0011 (13)0.0017 (13)−0.0100 (13)
N20.0275 (16)0.0341 (17)0.0362 (17)−0.0027 (13)−0.0056 (13)−0.0058 (14)
C10.0254 (18)0.0333 (19)0.0281 (18)0.0029 (15)0.0048 (14)−0.0097 (16)
C20.0273 (18)0.0292 (18)0.0292 (18)0.0055 (15)0.0010 (15)−0.0057 (15)
C30.0316 (19)0.0304 (19)0.0322 (19)0.0039 (16)−0.0029 (16)−0.0050 (16)
C40.034 (2)0.0330 (19)0.0270 (18)0.0037 (16)−0.0009 (15)−0.0057 (16)
C50.0337 (19)0.0284 (18)0.0275 (18)0.0008 (16)0.0073 (15)−0.0039 (15)
C60.0242 (18)0.040 (2)0.040 (2)−0.0016 (16)0.0036 (16)−0.0100 (17)
C70.0259 (18)0.0284 (18)0.0302 (19)0.0013 (15)−0.0026 (15)−0.0004 (15)
C80.049 (2)0.041 (2)0.047 (2)−0.002 (2)−0.010 (2)−0.018 (2)
C90.035 (2)0.045 (2)0.054 (3)−0.0144 (19)−0.0090 (19)0.000 (2)
C100.044 (2)0.041 (2)0.041 (2)0.0107 (19)−0.0116 (19)0.0001 (19)
C110.045 (2)0.034 (2)0.054 (3)−0.0069 (19)−0.009 (2)−0.0018 (19)
C120.052 (3)0.049 (2)0.034 (2)−0.003 (2)−0.0164 (19)−0.0002 (19)
C130.053 (3)0.042 (2)0.036 (2)−0.001 (2)0.0120 (19)0.0009 (18)
Geometric parameters (Å, °) top
Ti—N11.823 (3)C6—C71.515 (5)
Ti—C12.292 (3)C6—H6A0.9800
Ti—Cl22.3036 (12)C6—H6B0.9800
Ti—Cl12.3104 (12)C8—H8A0.9700
Ti—C22.325 (3)C8—H8B0.9700
Ti—C52.341 (3)C8—H8C0.9700
Ti—C42.405 (3)C9—H9A0.9700
Ti—C32.406 (4)C9—H9B0.9700
N1—C71.322 (4)C9—H9C0.9700
N2—C71.319 (4)C10—H10A0.9700
N2—C81.457 (5)C10—H10B0.9700
N2—C91.464 (5)C10—H10C0.9700
C1—C21.406 (5)C11—H11A0.9700
C1—C51.412 (5)C11—H11B0.9700
C1—C61.512 (5)C11—H11C0.9700
C2—C31.422 (5)C12—H12A0.9700
C2—C101.504 (5)C12—H12B0.9700
C3—C41.405 (5)C12—H12C0.9700
C3—C111.500 (5)C13—H13A0.9700
C4—C51.422 (5)C13—H13B0.9700
C4—C121.500 (5)C13—H13C0.9700
C5—C131.500 (5)
N1—Ti—C175.92 (13)C5—C4—Ti70.10 (19)
N1—Ti—Cl2105.63 (10)C12—C4—Ti125.2 (3)
C1—Ti—Cl2128.71 (10)C1—C5—C4107.5 (3)
N1—Ti—Cl1104.29 (10)C1—C5—C13126.9 (3)
C1—Ti—Cl1124.25 (10)C4—C5—C13125.5 (3)
Cl2—Ti—Cl1105.40 (5)C1—C5—Ti70.40 (19)
N1—Ti—C294.34 (13)C4—C5—Ti75.1 (2)
C1—Ti—C235.44 (13)C13—C5—Ti121.3 (2)
Cl2—Ti—C294.88 (10)C1—C6—C7106.7 (3)
Cl1—Ti—C2147.26 (9)C1—C6—H6A110.4
N1—Ti—C597.46 (13)C7—C6—H6A110.4
C1—Ti—C535.48 (12)C1—C6—H6B110.4
Cl2—Ti—C5146.31 (9)C7—C6—H6B110.4
Cl1—Ti—C591.94 (10)H6A—C6—H6B108.6
C2—Ti—C558.66 (12)N2—C7—N1122.9 (3)
N1—Ti—C4131.33 (13)N2—C7—C6120.4 (3)
C1—Ti—C458.19 (12)N1—C7—C6116.7 (3)
Cl2—Ti—C4114.96 (10)N2—C8—H8A109.5
Cl1—Ti—C490.13 (9)N2—C8—H8B109.5
C2—Ti—C457.72 (12)H8A—C8—H8B109.5
C5—Ti—C434.83 (12)N2—C8—H8C109.5
N1—Ti—C3128.99 (13)H8A—C8—H8C109.5
C1—Ti—C358.23 (12)H8B—C8—H8C109.5
Cl2—Ti—C388.61 (10)N2—C9—H9A109.5
Cl1—Ti—C3118.89 (9)N2—C9—H9B109.5
C2—Ti—C334.93 (12)H9A—C9—H9B109.5
C5—Ti—C357.70 (12)N2—C9—H9C109.5
C4—Ti—C333.97 (12)H9A—C9—H9C109.5
C7—N1—Ti129.5 (2)H9B—C9—H9C109.5
C7—N2—C8120.2 (3)C2—C10—H10A109.5
C7—N2—C9123.5 (3)C2—C10—H10B109.5
C8—N2—C9116.3 (3)H10A—C10—H10B109.5
C2—C1—C5108.4 (3)C2—C10—H10C109.5
C2—C1—C6125.4 (3)H10A—C10—H10C109.5
C5—C1—C6125.5 (3)H10B—C10—H10C109.5
C2—C1—Ti73.55 (19)C3—C11—H11A109.5
C5—C1—Ti74.12 (19)C3—C11—H11B109.5
C6—C1—Ti110.9 (2)H11A—C11—H11B109.5
C1—C2—C3108.0 (3)C3—C11—H11C109.5
C1—C2—C10127.2 (3)H11A—C11—H11C109.5
C3—C2—C10124.8 (3)H11B—C11—H11C109.5
C1—C2—Ti71.01 (19)C4—C12—H12A109.5
C3—C2—Ti75.7 (2)C4—C12—H12B109.5
C10—C2—Ti119.9 (2)H12A—C12—H12B109.5
C4—C3—C2107.8 (3)C4—C12—H12C109.5
C4—C3—C11126.4 (3)H12A—C12—H12C109.5
C2—C3—C11125.7 (3)H12B—C12—H12C109.5
C4—C3—Ti73.0 (2)C5—C13—H13A109.5
C2—C3—Ti69.41 (19)C5—C13—H13B109.5
C11—C3—Ti125.7 (3)H13A—C13—H13B109.5
C3—C4—C5108.3 (3)C5—C13—H13C109.5
C3—C4—C12126.4 (3)H13A—C13—H13C109.5
C5—C4—C12125.2 (3)H13B—C13—H13C109.5
C3—C4—Ti73.1 (2)
Acknowledgements top

The authors thank the Natural Science Foundation of China (grant No. 20672070 to MZ), the Natural Science Foundation of Shanxi (grant No. 2007011020) and the Foundation for Returned Overseas Chinese Scholars of Shanxi Province.

references
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