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The title compound, [Ti(C14H15)2Cl2], belongs to a class of complexes that are potentially active as pre-catalysts in the stereospecific polymerization of olefins. In the crystal structure, mol­ecules lie on C2 axes with pseudo-tetrahedral coordination around the Ti atoms. Conformational features of the compound are discussed, in conjunction with calculations that demonstrate the existence of other energetically favorable conformations in addition to that found in the reported crystal structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104026344/fa1100sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104026344/fa1100Isup2.hkl
Contains datablock I

CCDC reference: 249727

Comment top

In view of possible applications in the area of polymerization of hydrocarbon monomers, we synthesized a new particularly fluxional titanocene, (CCP)2TiCl2 [CCP= cumylcyclopentadienyl, C6H5C(CH3)2C5H5], (I).

The synthesis, the 1H NMR spectrum and the X-ray structure are reported in this paper, together with some consideration of the conformations of the complex in solution.

The molecule (Fig. 1) possesses crystallographic twofold symmetry. This seems to be a fairly general feature for group IV metallocenes of formula (CpR)2MCl2 [CpR=C5H4C(Me)2R; R=alkyl or aryl, M=Ti, Zr and Hf] (Shan et al., 1994; Dorado et al., 1998; Grimmond et al., 1999), and several structural and conformational features look very similar across this class of complexes.

The metal centre adopts a pseudo-tetrahedral geometry with respect to the chloride ligands and cyclopentadienyl (Cp) ring centroids [Xa—Ti—Xb = 131.36 (5)°; Xa and Xb the Cp ring centroids]. The Cp rings are inclined [the dihedral angle between the mean planes is 53.71 (9)°] in a staggered conformation, while the ring substituents are mutually disposed in a pseudo-trans manner. The gem-dimethyl groups are oriented laterally, leaving the bulky phenyl rings in a distal disposition, that is, oriented away from the metal core and roughly perpendicular to the cyclopentadienyl ring [the dihedral angle between the mean planes is 81.1 (1)°]. As generally found in this class of complexes, the metal is not equidistant from the five Cp ring C atoms. In particular, the Ti—C1 and Ti—C5 distances are longer than the other Ti—C distances; this effect could be a consequence of the contact between gem-methyl groups and chloride ligands, each Cl atom lying, in projection, between two methyl groups [Cl1i···C8 = 3.687 (3) Å and Cl1i···C7 = 3.518 (4) Å; symmetry code as in Table 1]. Another possible consequence of this contact is the fact that atom C6 is slightly, but significantly, out of the plane of the Cp ring [0.266 (4) Å].

We have examined some basic conformational features of the complex, searching in particular for energetically feasible conformations having different steric encumbrances around the Cl atoms, which are possible polymerization sites. The analysis was carried out using the MOLDRAW software (Ugliengo et al., 1993) and taking into consideration only non-bonded interactions. The following conformational degrees of freedom were explored: (i) rotation of each Cp ring around the axis from Ti to the center of the Cp ring (ψ rotations); (ii) rotations around the C1—06 and C1i—C6i bonds (χ rotations).

Starting from the pseudo-trans crystallographic conformation (C1—Xa—Xb—C1i= −178°) we performed ψ rotations and then, in some of the energy minima found, the χ angles were varied so as to minimize the non-bonded energy. In this way, several conformational minima were found, with energies comparable to or even lower than that calculated for the crystallographic conformation (but within a few kcal mol−1) and corresponding to pseudo-gauche and pseudo-cis arrangements of the Cp groups. The interconversion between these conformations is always possible through the basic conformational degrees of freedom of the molecule (the torsion angles around the C6—C9 and C6i—C9i bonds in addition to the ψ and χ rotations). As an example, the two pseudo-cis conformers reported in Figs. 2 and 3 are characterized, respectively, by a low and a high steric encumbrance around the Cl atoms. Conformer A (Fig. 2) has a lower energy than the crystallographic conformer, while B (Fig. 3) has a higher energy, probably because in A there is less steric encumbrance around the Cl atoms, the two gem-methyl groups being oriented away from the Cl atoms. Clearly, in solution, a continuous interconversion among these (and other) conformers can be expected.

Experimental top

All experiments were carried out under nitrogen atmosphere using standard Schlenk techniques. Solvents were dried over sodium benzophenone (benzene) or calcium hydride (diethyl ether, dichloromethane). 6,6-Dimethyl-fulvene was synthesized according to Stone & Little (1984). Compound (I) was synthesized in two steps: (i) 6,6-Dimethyl-fulvene (36.8 × 10−3 mol) was added to a solution of phenyl lithium (36.8×10−3 mol) in diethyl ether (25 ml) precooled to 195 K, and left overnight to attain room temperature. The resutling precipitate [PhC(CH3)2CpLi] was filtered and dried under vacuum to give a white solid. Yield: 6 g, 85.7%. 1H NMR (400 MHz, 298 K, THF-d8): δ 1.61 (s, 6H, CH3), 5.57 (s, 4H, Cp), 6.94 (t, JHH=7.4 Hz, 1H, p-Ph), 7.08 (t, JHH=7.4 Hz, 2H, m-Ph), 7.30 (m, 2H, o-Ph). (ii) A benzene (45 ml) solution of TiCl4 (6×10−3 mol) was added to a suspension of PhC(CH3)2CpLi (13.1 × 10−3 mol) in benzene (100 ml) at room temperature. The reaction mixture was stirred overnight at 353 K and filtered through celite. The filtrate was concentrated until precipitation of a red material took place. The precipitate was filtered and dried under vacuum, and after slow crystallization from CH2Cl2 afforded dark red needles. 1H NMR (400 MHz, 298 K, CD2Cl2): δ 1.77 (s, 6H, CH3), 6.15 (t, JHH=2.5 Hz, 2H, Cp), 6.47 (t, JHH=2.5 Hz, 2H, Cp), 7.15–7.27 (unresolved multiplet, 5H, Ph). The molecular structure of this product was identified by comparison of the 1H NMR spectrum with that of cCpTiCl3 (Sassmannshausen et al., 1999) (same patterns and different chemical shifts). Crystals of CCP2TiCl2 suitable for structure determination were obtained by slow crystallization from dichloromethane solution at room temperature. The selected crystal was sealed in a Lindemann capillary in an inert atmosphere (N2).

Refinement top

Reflections corresponding to lattice centering were not collected. Methyl H atoms were positioned geometrically and treated as riding on their parent atoms (C—H = 0.96 Å). All other H atoms were located in difference maps and their coordinates were refined. For all H atoms, Uiso(H) was set at 1.2Ueq(carrier atom) [this does not correspond to values given in cif]..

Computing details top

Data collection: MACH3 Software (Enraf Nonius, 1996); cell refinement: CELLFIT (Centore, 2002); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON92 (Spek, 1992); software used to prepare material for publication: reference?.

Figures top
[Figure 1] Fig. 1. An ORTEP-3 (Farrugia, 1997) view of the molecular structure of CCP2TiCl2. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A model of the calculated A conformer of CCP2TiCl2.
[Figure 3] Fig. 3. A model of the calculated B conformer of CCP2TiCl2.
Bis(cumylcyclopentadienyl) dichlorotitanium(IV) top
Crystal data top
(C14H15)2[TiCl2]F(000) = 1016
Mr = 485.29Dx = 1.378 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2ycCell parameters from 25 reflections
a = 18.816 (5) Åθ = 13.9–14.8°
b = 6.645 (3) ŵ = 0.61 mm1
c = 19.12 (2) ÅT = 298 K
β = 101.77 (3)°Prism, red
V = 2340 (3) Å30.5 × 0.2 × 0.13 mm
Z = 4
Data collection top
Nonius MACH3
diffractometer
2233 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.045
Graphite monochromatorθmax = 27.9°, θmin = 2.2°
non–profiled ω scansh = 2424
Absorption correction: ψ scan
(North et al., 1968). Number of ψ scan sets used was 1. Theta correction was applied.
k = 08
Tmin = 0.859, Tmax = 0.923l = 025
2877 measured reflections1 standard reflections every 120 min
2792 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: difference Fourier map
wR(F2) = 0.128H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0819P)2 + 0.4482P]
where P = (Fo2 + 2Fc2)/3
2792 reflections(Δ/σ)max < 0.001
170 parametersΔρmax = 0.61 e Å3
0 restraintsΔρmin = 0.78 e Å3
Crystal data top
(C14H15)2[TiCl2]V = 2340 (3) Å3
Mr = 485.29Z = 4
Monoclinic, C2/cMo Kα radiation
a = 18.816 (5) ŵ = 0.61 mm1
b = 6.645 (3) ÅT = 298 K
c = 19.12 (2) Å0.5 × 0.2 × 0.13 mm
β = 101.77 (3)°
Data collection top
Nonius MACH3
diffractometer
2233 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968). Number of ψ scan sets used was 1. Theta correction was applied.
Rint = 0.045
Tmin = 0.859, Tmax = 0.9231 standard reflections every 120 min
2877 measured reflections intensity decay: none
2792 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.128H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.61 e Å3
2792 reflectionsΔρmin = 0.78 e Å3
170 parameters
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
C10.06286 (12)0.0907 (3)0.15592 (11)0.0289 (4)
C20.02153 (12)0.2437 (3)0.17943 (11)0.0314 (4)
H20.0421 (13)0.363 (4)0.2008 (13)0.031*
C30.05246 (13)0.1901 (4)0.16214 (12)0.0372 (5)
H30.0909 (14)0.267 (4)0.1692 (14)0.037*
C40.05733 (13)0.0035 (4)0.12736 (12)0.0386 (5)
H40.0981 (14)0.069 (4)0.1120 (14)0.039*
C50.01326 (13)0.0615 (4)0.12536 (12)0.0352 (5)
H50.0269 (13)0.188 (4)0.1074 (14)0.035*
C60.14266 (12)0.1075 (3)0.15258 (11)0.0321 (5)
C70.17176 (14)0.0925 (4)0.12944 (15)0.0459 (6)
H7A0.14600.12660.08220.046*
H7B0.16490.19680.16220.046*
H7C0.22260.07920.12950.046*
C80.18787 (13)0.1706 (4)0.22559 (13)0.0436 (6)
H8A0.23840.17250.22340.044*
H8B0.18020.07630.26140.044*
H8C0.17320.30240.23760.044*
C90.15024 (12)0.2640 (3)0.09483 (12)0.0338 (5)
C100.09289 (14)0.3160 (4)0.04037 (13)0.0441 (6)
H100.0478 (15)0.265 (5)0.0396 (15)0.044*
C110.10198 (16)0.4453 (5)0.01404 (15)0.0503 (6)
H110.0627 (16)0.461 (5)0.0544 (16)0.050*
C120.16934 (16)0.5249 (4)0.01488 (15)0.0484 (6)
H120.1755 (15)0.618 (5)0.0533 (16)0.048*
C130.22667 (16)0.4757 (5)0.03841 (17)0.0536 (7)
H130.2727 (16)0.521 (5)0.0373 (16)0.054*
C140.21794 (14)0.3461 (4)0.09295 (15)0.0458 (6)
H140.2563 (16)0.306 (4)0.1295 (16)0.046*
Cl10.09241 (3)0.28492 (8)0.23306 (3)0.03997 (18)
Ti10.00000.03735 (7)0.25000.02553 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0353 (10)0.0239 (10)0.0275 (9)0.0007 (8)0.0066 (8)0.0019 (8)
C20.0420 (12)0.0209 (9)0.0324 (10)0.0016 (8)0.0100 (9)0.0034 (8)
C30.0402 (12)0.0366 (12)0.0350 (11)0.0108 (10)0.0083 (9)0.0114 (10)
C40.0363 (11)0.0443 (14)0.0319 (11)0.0067 (10)0.0007 (9)0.0026 (10)
C50.0438 (12)0.0294 (11)0.0313 (10)0.0046 (9)0.0049 (9)0.0080 (9)
C60.0332 (10)0.0294 (11)0.0342 (10)0.0002 (8)0.0082 (8)0.0007 (9)
C70.0486 (14)0.0366 (13)0.0570 (15)0.0091 (11)0.0215 (12)0.0009 (11)
C80.0385 (12)0.0515 (15)0.0390 (12)0.0056 (11)0.0032 (10)0.0013 (11)
C90.0393 (11)0.0287 (10)0.0348 (11)0.0011 (9)0.0112 (9)0.0040 (9)
C100.0407 (12)0.0498 (15)0.0408 (13)0.0085 (11)0.0059 (10)0.0044 (11)
C110.0543 (15)0.0530 (17)0.0417 (13)0.0033 (13)0.0051 (11)0.0082 (12)
C120.0618 (16)0.0369 (13)0.0507 (15)0.0041 (12)0.0211 (13)0.0064 (12)
C130.0468 (15)0.0482 (16)0.0695 (19)0.0094 (12)0.0208 (14)0.0090 (14)
C140.0380 (12)0.0444 (15)0.0541 (15)0.0036 (11)0.0073 (11)0.0060 (12)
Cl10.0411 (3)0.0230 (3)0.0548 (4)0.0075 (2)0.0075 (2)0.0015 (2)
Ti10.0300 (3)0.0155 (3)0.0302 (3)0.0000.00406 (19)0.000
Geometric parameters (Å, º) top
C1—C21.408 (3)C7—H7A0.9600
C1—C51.419 (3)C7—H7B0.9600
C1—C61.520 (3)C7—H7C0.9600
C1—Ti12.495 (3)C8—H8A0.9600
C2—C31.409 (3)C8—H8B0.9600
C2—Ti12.386 (2)C8—H8C0.9600
C2—H20.94 (3)C9—C101.382 (3)
C3—C41.401 (4)C9—C141.393 (3)
C3—Ti12.325 (3)C10—C111.386 (4)
C3—H30.92 (3)C10—H100.91 (3)
C4—C51.404 (3)C11—C121.377 (4)
C4—Ti12.388 (3)C11—H110.96 (3)
C4—H40.90 (3)C12—C131.364 (4)
C5—Ti12.452 (3)C12—H120.99 (3)
C5—H50.96 (3)C13—C141.388 (4)
C6—C71.536 (3)C13—H130.92 (3)
C6—C81.538 (3)C14—H140.94 (3)
C6—C91.544 (3)Cl1—Ti12.368 (3)
C2—C1—C5106.6 (2)C9—C10—C11121.6 (2)
C2—C1—C6125.11 (19)C9—C10—H10120.1 (18)
C5—C1—C6127.40 (19)C11—C10—H10118.4 (19)
C2—C1—Ti169.04 (12)C12—C11—C10120.1 (3)
C5—C1—Ti171.65 (13)C12—C11—H11120.6 (19)
C6—C1—Ti1132.29 (14)C10—C11—H11118.6 (19)
C1—C2—C3109.0 (2)C13—C12—C11119.3 (3)
C1—C2—Ti177.53 (13)C13—C12—H12120.8 (17)
C3—C2—Ti170.21 (13)C11—C12—H12119.9 (17)
C1—C2—H2122.9 (15)C12—C13—C14120.9 (3)
C3—C2—H2128.0 (15)C12—C13—H13121 (2)
Ti1—C2—H2121.2 (15)C14—C13—H13118 (2)
C4—C3—C2107.5 (2)C13—C14—C9120.8 (3)
C4—C3—Ti175.21 (15)C13—C14—H14123.2 (18)
C2—C3—Ti175.01 (13)C9—C14—H14116.0 (18)
C4—C3—H3126.0 (17)C3i—Ti1—C398.90 (14)
C2—C3—H3126.4 (17)C3—Ti1—Cl1i137.93 (7)
Ti1—C3—H3119.2 (17)C3—Ti1—Cl199.28 (7)
C3—C4—C5108.3 (2)Cl1i—Ti1—Cl191.96 (5)
C3—C4—Ti170.23 (13)C3—Ti1—C2i78.69 (11)
C5—C4—Ti175.62 (14)Cl1—Ti1—C2i114.61 (6)
C3—C4—H4126.5 (18)C3—Ti1—C234.78 (8)
C5—C4—H4125.0 (18)Cl1—Ti1—C2132.15 (7)
Ti1—C4—H4116.2 (17)C2i—Ti1—C277.01 (12)
C4—C5—C1108.4 (2)C3—Ti1—C4i132.52 (10)
C4—C5—Ti170.68 (13)Cl1—Ti1—C4i112.66 (7)
C1—C5—Ti175.03 (13)C2—Ti1—C4i111.80 (10)
C4—C5—H5126.9 (15)C3—Ti1—C434.55 (9)
C1—C5—H5124.7 (15)Cl1—Ti1—C476.86 (7)
Ti1—C5—H5119.3 (16)C2—Ti1—C456.68 (9)
C1—C6—C7111.21 (18)C4i—Ti1—C4166.95 (13)
C1—C6—C8110.50 (18)C3—Ti1—C556.80 (9)
C7—C6—C8109.5 (2)Cl1—Ti1—C592.24 (6)
C1—C6—C9108.39 (18)C2—Ti1—C555.87 (8)
C7—C6—C9106.65 (19)C4—Ti1—C533.71 (9)
C8—C6—C9110.5 (2)C3—Ti1—C5i129.25 (9)
C6—C7—H7A109.5Cl1—Ti1—C5i82.53 (7)
C6—C7—H7B109.5C2—Ti1—C5i131.57 (8)
H7A—C7—H7B109.5C4—Ti1—C5i147.86 (9)
C6—C7—H7C109.5C5—Ti1—C5i172.49 (11)
H7A—C7—H7C109.5C3i—Ti1—C196.05 (10)
H7B—C7—H7C109.5C3—Ti1—C156.71 (8)
C6—C8—H8A109.5Cl1i—Ti1—C183.84 (6)
C6—C8—H8B109.5Cl1—Ti1—C1125.54 (6)
H8A—C8—H8B109.5C2—Ti1—C133.44 (7)
C6—C8—H8C109.5C4—Ti1—C155.88 (9)
H8A—C8—H8C109.5C5—Ti1—C133.32 (7)
H8B—C8—H8C109.5C2—Ti1—C1i107.51 (9)
C10—C9—C14117.4 (2)C4—Ti1—C1i118.91 (9)
C10—C9—C6122.4 (2)C5—Ti1—C1i151.67 (8)
C14—C9—C6120.0 (2)C1—Ti1—C1i140.12 (10)
C5—C1—C2—C31.5 (2)C3—C2—Ti1—C579.41 (15)
C6—C1—C2—C3168.60 (19)C1—C2—Ti1—C5i142.38 (13)
Ti1—C1—C2—C363.70 (16)C3—C2—Ti1—C5i101.86 (16)
C5—C1—C2—Ti162.20 (16)C3—C2—Ti1—C1115.8 (2)
C6—C1—C2—Ti1127.7 (2)C1—C2—Ti1—C1i169.33 (8)
C1—C2—C3—C40.3 (2)C3—C2—Ti1—C1i74.91 (15)
Ti1—C2—C3—C468.81 (17)C3—C4—Ti1—C3i16.0 (2)
C1—C2—C3—Ti168.48 (17)C5—C4—Ti1—C3i99.92 (16)
C2—C3—C4—C52.1 (3)C5—C4—Ti1—C3115.9 (2)
Ti1—C3—C4—C566.60 (17)C3—C4—Ti1—Cl1i144.29 (13)
C2—C3—C4—Ti168.67 (15)C5—C4—Ti1—Cl1i28.38 (15)
C3—C4—C5—C13.0 (3)C3—C4—Ti1—Cl1129.11 (15)
Ti1—C4—C5—C166.10 (16)C5—C4—Ti1—Cl1114.97 (15)
C3—C4—C5—Ti163.08 (16)C3—C4—Ti1—C2i17.56 (16)
C2—C1—C5—C42.8 (3)C5—C4—Ti1—C2i133.48 (14)
C6—C1—C5—C4167.0 (2)C3—C4—Ti1—C238.89 (14)
Ti1—C1—C5—C463.26 (16)C5—C4—Ti1—C277.03 (15)
C2—C1—C5—Ti160.49 (15)C3—C4—Ti1—C4i9.1 (4)
C6—C1—C5—Ti1129.7 (2)C5—C4—Ti1—C4i106.9 (4)
C2—C1—C6—C7176.0 (2)C3—C4—Ti1—C5115.9 (2)
C5—C1—C6—C716.0 (3)C3—C4—Ti1—C5i77.6 (2)
Ti1—C1—C6—C783.2 (2)C5—C4—Ti1—C5i166.5 (2)
C2—C1—C6—C854.1 (3)C3—C4—Ti1—C179.34 (15)
C5—C1—C6—C8137.8 (2)C5—C4—Ti1—C136.57 (13)
Ti1—C1—C6—C838.6 (3)C3—C4—Ti1—C1i53.87 (16)
C2—C1—C6—C967.1 (3)C5—C4—Ti1—C1i169.79 (13)
C5—C1—C6—C9100.9 (3)C4—C5—Ti1—C3i110.36 (16)
Ti1—C1—C6—C9159.88 (15)C1—C5—Ti1—C3i5.76 (18)
C1—C6—C9—C1021.6 (3)C4—C5—Ti1—C337.56 (15)
C7—C6—C9—C1098.2 (3)C1—C5—Ti1—C378.55 (15)
C8—C6—C9—C10142.9 (2)C4—C5—Ti1—Cl1i153.75 (15)
C1—C6—C9—C14163.7 (2)C1—C5—Ti1—Cl1i90.14 (13)
C7—C6—C9—C1476.5 (3)C4—C5—Ti1—Cl162.06 (14)
C8—C6—C9—C1442.4 (3)C1—C5—Ti1—Cl1178.17 (13)
C14—C9—C10—C110.2 (4)C4—C5—Ti1—C2i64.22 (18)
C6—C9—C10—C11175.0 (2)C1—C5—Ti1—C2i51.89 (17)
C9—C10—C11—C120.2 (5)C4—C5—Ti1—C279.64 (16)
C10—C11—C12—C130.2 (5)C1—C5—Ti1—C236.47 (13)
C11—C12—C13—C140.3 (5)C4—C5—Ti1—C4i156.0 (2)
C12—C13—C14—C90.4 (5)C1—C5—Ti1—C4i39.9 (2)
C10—C9—C14—C130.3 (4)C1—C5—Ti1—C4116.1 (2)
C6—C9—C14—C13175.3 (3)C4—C5—Ti1—C1116.1 (2)
C4—C3—Ti1—C3i168.14 (17)C4—C5—Ti1—C1i19.1 (2)
C2—C3—Ti1—C3i55.00 (12)C1—C5—Ti1—C1i97.0 (2)
C4—C3—Ti1—Cl1i53.49 (18)C2—C1—Ti1—C3i58.77 (15)
C2—C3—Ti1—Cl1i59.64 (17)C5—C1—Ti1—C3i175.52 (14)
C4—C3—Ti1—Cl149.96 (14)C6—C1—Ti1—C3i60.2 (2)
C2—C3—Ti1—Cl1163.10 (12)C2—C1—Ti1—C337.93 (14)
C4—C3—Ti1—C2i163.40 (16)C5—C1—Ti1—C378.83 (15)
C2—C3—Ti1—C2i83.47 (16)C6—C1—Ti1—C3156.9 (2)
C4—C3—Ti1—C2113.1 (2)C2—C1—Ti1—Cl1i157.48 (13)
C4—C3—Ti1—C4i177.24 (14)C5—C1—Ti1—Cl1i85.76 (13)
C2—C3—Ti1—C4i64.10 (17)C6—C1—Ti1—Cl1i38.52 (18)
C2—C3—Ti1—C4113.1 (2)C2—C1—Ti1—Cl1114.51 (12)
C4—C3—Ti1—C536.62 (14)C5—C1—Ti1—Cl12.24 (15)
C2—C3—Ti1—C576.51 (14)C6—C1—Ti1—Cl1126.53 (17)
C4—C3—Ti1—C5i137.86 (14)C2—C1—Ti1—C2i25.13 (18)
C2—C3—Ti1—C5i109.01 (15)C5—C1—Ti1—C2i141.88 (14)
C4—C3—Ti1—C176.72 (15)C6—C1—Ti1—C2i93.83 (19)
C2—C3—Ti1—C136.42 (12)C5—C1—Ti1—C2116.8 (2)
C4—C3—Ti1—C1i134.68 (14)C6—C1—Ti1—C2119.0 (2)
C2—C3—Ti1—C1i112.18 (14)C2—C1—Ti1—C4i86.20 (15)
C1—C2—Ti1—C3i119.87 (15)C5—C1—Ti1—C4i157.05 (14)
C3—C2—Ti1—C3i124.38 (15)C6—C1—Ti1—C4i32.8 (2)
C1—C2—Ti1—C3115.8 (2)C2—C1—Ti1—C479.75 (15)
C1—C2—Ti1—Cl1i24.76 (14)C5—C1—Ti1—C437.01 (14)
C3—C2—Ti1—Cl1i140.51 (13)C6—C1—Ti1—C4161.3 (2)
C1—C2—Ti1—Cl192.98 (14)C2—C1—Ti1—C5116.8 (2)
C3—C2—Ti1—Cl122.77 (16)C6—C1—Ti1—C5124.3 (3)
C1—C2—Ti1—C2i155.44 (18)C2—C1—Ti1—C5i74.2 (2)
C3—C2—Ti1—C2i88.81 (15)C5—C1—Ti1—C5i169.02 (17)
C1—C2—Ti1—C4i109.82 (14)C6—C1—Ti1—C5i44.7 (3)
C3—C2—Ti1—C4i134.43 (14)C2—C1—Ti1—C1i15.98 (12)
C1—C2—Ti1—C477.13 (15)C5—C1—Ti1—C1i132.73 (14)
C3—C2—Ti1—C438.62 (14)C6—C1—Ti1—C1i102.98 (19)
C1—C2—Ti1—C536.34 (12)
Symmetry code: (i) x, y, z+1/2.

Experimental details

Crystal data
Chemical formula(C14H15)2[TiCl2]
Mr485.29
Crystal system, space groupMonoclinic, C2/c
Temperature (K)298
a, b, c (Å)18.816 (5), 6.645 (3), 19.12 (2)
β (°) 101.77 (3)
V3)2340 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.61
Crystal size (mm)0.5 × 0.2 × 0.13
Data collection
DiffractometerNonius MACH3
diffractometer
Absorption correctionψ scan
(North et al., 1968). Number of ψ scan sets used was 1. Theta correction was applied.
Tmin, Tmax0.859, 0.923
No. of measured, independent and
observed [I > 2σ(I)] reflections
2877, 2792, 2233
Rint0.045
(sin θ/λ)max1)0.659
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.128, 1.07
No. of reflections2792
No. of parameters170
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.61, 0.78

Computer programs: MACH3 Software (Enraf Nonius, 1996), CELLFIT (Centore, 2002), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and PLATON92 (Spek, 1992), reference?.

Selected geometric parameters (Å, º) top
C1—C21.408 (3)C3—C41.401 (4)
C1—C51.419 (3)C3—Ti12.325 (3)
C1—Ti12.495 (3)C4—C51.404 (3)
C2—C31.409 (3)C4—Ti12.388 (3)
C2—Ti12.386 (2)C5—Ti12.452 (3)
C7—C6—C8109.5 (2)Cl1i—Ti1—Cl191.96 (5)
C6—C1—C5—C4167.0 (2)C1—C6—C9—C14163.7 (2)
C2—C1—C6—C854.1 (3)
Symmetry code: (i) x, y, z+1/2.
 

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