Penta­carbonyl-2κ5C-chlorido-1κCl-bis­[1(η5)-cyclo­penta­dien­yl](μ-α-oxido­benzyl­idene-1:2κ2O:C)titanium(IV)tungsten(0)

Esterhuysen, C.; Nel, I.B.J.; Esterhuysen, M.W.; Cronje, S.

doi:10.1107/S1600536808036465

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page m1534

doi:10.1107/S1600536808036465

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Pentacarbonyl-2κ⁵C-chlorido-1κCl-bis[1(η⁵)-cyclopentadienyl](μ-α-oxidobenzylidene-1:2κ²O:C)titanium(IV)tungsten(0)

Catharine Esterhuysen,^a ^* I. B. Jacques Nel,^a ‡ Matthias W. Esterhuysen ^a § and Stephanie Cronje ^a

^aDepartment of Chemistry and Polymer Science, University of Stellenbosch, Private Bag X1, Matieland 7602, South Africa
^*Correspondence e-mail: ce@sun.ac.za

(Received 4 November 2008; accepted 6 November 2008; online 13 November 2008)

The title compound, [TiW(C₅H₅)₂(C₇H₅O)Cl(CO)₅], consists of two metal centres, with a (tungstenpentacarbonyl)oxyphenylcarbene unit coordinated by a titanocene chloride. The oxycarbene group is nearly planar, with the phenyl ring twisted by an angle of 39.1 (2)° with respect to this plane. One of the cyclopentadienyl rings undergoes an offset face-to-face π–π interaction [3.544 (6) Å] with the symmetry-related cyclopentadienyl ring of a neighbouring molecule.

Related literature

For related literature regarding anionic Fischer-type carbenes, see: Barluenga & Fañanás (2000 ). For information regarding the catalytic activity of similar complexes, see: Luruli et al. (2004 , 2006 ); Sinn et al. (1980 ). For comparable structures, see: Esterhuysen et al. (2008 ); Balzer et al. (1992 ). For related literature, see: Orpen et al. (1989 ).

Experimental

Crystal data

[TiW(C₅H₅)₂(C₇H₅O)Cl(CO)₅]
M_r = 642.54
Monoclinic, P 2₁ /c
a = 8.553 (1) Å
b = 12.268 (1) Å
c = 20.789 (3) Å
β = 95.903 (1)°
V = 2169.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 5.83 mm⁻¹
T = 173 (2) K
0.17 × 0.14 × 0.12 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997 ) T_min = 0.438, T_max = 0.542 (expected range = 0.402–0.497)
12664 measured reflections
4270 independent reflections
3701 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.062
S = 1.04
4270 reflections
280 parameters
H-atom parameters constrained
Δρ_max = 1.05 e Å⁻³
Δρ_min = −1.28 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

W—C1	2.204 (4)
Ti—O1	1.927 (2)
O1—C1	1.280 (4)

C1—O1—Ti	171.7 (2)

Data collection: COLLECT (Nonius, 1998 ); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ; Atwood & Barbour, 2003 ); software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808036465/at2672sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808036465/at2672Isup2.hkl

checkCIF report

Comment top

Anionic Fischer-type carbene ligands are known to act as monodentate ligands towards transition metals like Ti and Zr (Barluenga and Fañanás, 2000). We have shown that such zirconocene complexes, Cp₂Zr(Cl)OC(R)W(CO)₅, catalyze the oligomerization of 1-pentene, as well as the copolymerization of ethene and 1-pentene, in the presence of MAO (Luruli et al., 2004; Luruli et al., 2006). Since Cp₂TiCl₂ has been shown to polymerize ethylene when activated by methylaluminoxane, MAO (Sinn et al., 1980), the title complex (I) was synthesized as part of our investigation into improved Ziegler-Natta catalysts for polymerization of ethene.

In the title compound (Fig. 1), the W=C_carbene and C_carbene—C distances are similar to those found in the equivalent hafnocene complex [2.177 (6) and 1.291 (6) Å, respectively; Esterhuysen et al., 2008], while the Ti—O distance is similar to the related compound Cp₂Ti(Cl)OC(C₆H₅)Mn(CO)₂(C₅H₄CH₃) (Balzer et al., 1992). The Ti—O—C angle deviates slightly from linearity, which is similar to the related hafnocene complex [171.4 (3)°], but more linear than the manganese complex [160.8 (5)°]. These results are indicative of π delocalization through the Ti—O—C=W unit. As a result, the Cl/Ti/O1/C1/W/C3/O3 moiety is approximately planar, with the phenyl ring (C21/C22/C23/C24/C25/C26) twisted at an angle of 39.1 (2)° with respect to this plane.

The C31/C32/C33/C34/C35 Cp ring [with centroid Cg(1)] undergoes offset face-to-face π–π interactions with the symmetry related Cp ring on a neighbouring molecule [Cg(1)···Cg(1)ⁱ = 3.544 (6) Å; Symmetry code: (i) - x, 2 - y, 1 - z)].

Related literature top

For related literature regarding anionic Fischer-type carbenes, see: Barluenga & Fañanás (2000). For information regarding the catalytic activity of similar complexes, see: Luruli et al. (2004, 2006); Sinn et al. (1980). For comparable structures, see: Esterhuysen et al. (2008); Balzer et al. (1992). For related literature, see: Orpen et al. (1989).

Experimental top

A solution of LiCH₃ (31.0 ml, 1.6M, 50.2 mmol) in 50 ml of diethylether was added to a well stirred suspension of W(CO)₆ (17.80 g, 50.6 mmol) in 100 ml of diethylether. After solvent removal in vacuo, dissolution of the residue in 150 ml of cold water and filtration, a solution of Et₄NCl (8.72 g, 52.6 mmol) in 50 ml of cold water was added to the filtrate. Upon further filtration 1.13 g (2.0 mmol) of the product {[W(CO)₅C(C₆H₅)O][NEt₄]} was dissolved in 70 ml of dichloromethane and added to a solution of Cp₂TiCl₂ (0.51 g, 2.0 mmol) in 40 ml of dichloromethane. After stirring for 30 min at -40°C AgBF₄ (0.39 g, 2.0 mmol) was added. The red concentrate, stripped of solvent, was purified by chromatography at -20°C on silica with 400 ml of dichloromethane-pentane (2:1) followed by 200 ml of diethyl ether-hexane (2:1) (column 15 × 2 cm). The eluent was dried in vacuo, and the residue dissolved in toluene, layered with pentane and kept at -6°C, whereupon brown crystals of the title compound suitable for X-ray diffraction analysis were obtained in 38% yield.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN(Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001; Atwood & Barbour, 2003); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

Fig. 1. The molecular structure of (I) showing the atomic labelling scheme and displacement ellipsoids drawn at the 50% probability level.

Pentacarbonyl-2κ⁵C-chlorido-1κCl-bis[1(η⁵)-cyclopentadienyl](µ- α-oxidobenzylidene-1:2κ²O:C)titaniumtungsten top

Crystal data top

[TiW(C₅H₅)₂(C₇H₅O)Cl(CO)₅]	F(000) = 1232
M_r = 642.54	D_x = 1.967 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3701 reflections
a = 8.553 (1) Å	θ = 1.9–26.0°
b = 12.268 (1) Å	µ = 5.83 mm⁻¹
c = 20.789 (3) Å	T = 173 K
β = 95.903 (1)°	Prism, brown
V = 2169.8 (3) Å³	0.17 × 0.14 × 0.12 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	4270 independent reflections
Radiation source: fine-focus sealed tube	3701 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
ϕ and ω scans to fill Ewald sphere	θ_max = 26.0°, θ_min = 1.9°
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	h = −10→10
T_min = 0.438, T_max = 0.542	k = −12→15
12664 measured reflections	l = −25→25

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.062	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0268P)² + 1.3791P] where P = (F_o² + 2F_c²)/3
4270 reflections	(Δ/σ)_max = 0.001
280 parameters	Δρ_max = 1.05 e Å⁻³
0 restraints	Δρ_min = −1.28 e Å⁻³

Crystal data top

[TiW(C₅H₅)₂(C₇H₅O)Cl(CO)₅]	V = 2169.8 (3) Å³
M_r = 642.54	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.553 (1) Å	µ = 5.83 mm⁻¹
b = 12.268 (1) Å	T = 173 K
c = 20.789 (3) Å	0.17 × 0.14 × 0.12 mm
β = 95.903 (1)°

Data collection top

Nonius KappaCCD diffractometer	4270 independent reflections
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	3701 reflections with I > 2σ(I)
T_min = 0.438, T_max = 0.542	R_int = 0.048
12664 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.062	H-atom parameters constrained
S = 1.04	Δρ_max = 1.05 e Å⁻³
4270 reflections	Δρ_min = −1.28 e Å⁻³
280 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

	x	y	z	U_iso*/U_eq
W	−0.040028 (18)	0.614346 (12)	0.673068 (7)	0.02272 (7)
Ti	0.30368 (8)	0.78191 (5)	0.53935 (3)	0.02177 (16)
Cl	0.55600 (14)	0.83949 (10)	0.58007 (5)	0.0410 (3)
O1	0.2431 (3)	0.7285 (2)	0.62039 (11)	0.0245 (6)
O2	−0.1363 (4)	0.6408 (3)	0.52255 (14)	0.0404 (8)
O3	−0.3832 (4)	0.5174 (3)	0.67496 (16)	0.0509 (9)
O4	−0.0034 (5)	0.6032 (3)	0.82667 (14)	0.0521 (10)
O5	0.0917 (5)	0.3753 (3)	0.65428 (18)	0.0569 (10)
O6	−0.1413 (5)	0.8615 (3)	0.69147 (17)	0.0505 (9)
C1	0.1989 (4)	0.6800 (3)	0.66995 (16)	0.0207 (8)
C2	−0.0937 (5)	0.6307 (3)	0.5758 (2)	0.0282 (9)
C3	−0.2601 (5)	0.5542 (3)	0.67555 (19)	0.0326 (10)
C4	−0.0115 (5)	0.6062 (3)	0.7719 (2)	0.0331 (10)
C5	0.0453 (5)	0.4607 (4)	0.66182 (19)	0.0340 (10)
C6	−0.1093 (5)	0.7727 (4)	0.68423 (19)	0.0332 (10)
C21	0.3261 (4)	0.6812 (3)	0.72524 (16)	0.0227 (8)
C22	0.3483 (5)	0.5921 (3)	0.76655 (17)	0.0261 (9)
H22	0.2780	0.5321	0.7615	0.031*
C23	0.4726 (5)	0.5901 (4)	0.81522 (19)	0.0337 (10)
H23	0.4888	0.5281	0.8424	0.040*
C24	0.5731 (5)	0.6791 (4)	0.82394 (18)	0.0359 (11)
H24	0.6580	0.6779	0.8572	0.043*
C25	0.5499 (5)	0.7688 (4)	0.7844 (2)	0.0378 (10)
H25	0.6173	0.8302	0.7912	0.045*
C26	0.4280 (5)	0.7699 (3)	0.73471 (17)	0.0300 (9)
H26	0.4141	0.8314	0.7070	0.036*
C31	0.0676 (5)	0.8817 (3)	0.5469 (2)	0.0321 (10)
H31	−0.0155	0.8518	0.5683	0.039*
C32	0.0882 (5)	0.8697 (3)	0.4812 (2)	0.0337 (10)
H32	0.0225	0.8290	0.4503	0.040*
C33	0.2228 (5)	0.9284 (4)	0.4690 (2)	0.0362 (10)
H33	0.2646	0.9343	0.4285	0.043*
C34	0.2847 (5)	0.9768 (3)	0.5274 (2)	0.0335 (10)
H34	0.3745	1.0227	0.5330	0.040*
C35	0.1924 (5)	0.9463 (3)	0.57560 (19)	0.0319 (10)
H35	0.2101	0.9654	0.6200	0.038*
C41	0.2059 (6)	0.6425 (4)	0.4682 (2)	0.0424 (12)
H41	0.0960	0.6397	0.4555	0.051*
C42	0.2865 (7)	0.5904 (4)	0.5223 (2)	0.0439 (12)
H42	0.2405	0.5442	0.5519	0.053*
C43	0.4452 (7)	0.6184 (3)	0.5251 (2)	0.0458 (13)
H43	0.5260	0.5968	0.5573	0.055*
C44	0.4629 (6)	0.6842 (4)	0.4713 (2)	0.0432 (12)
H44	0.5593	0.7138	0.4604	0.052*
C45	0.3183 (6)	0.6991 (4)	0.43667 (19)	0.0399 (11)
H45	0.2983	0.7406	0.3981	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
W	0.02340 (10)	0.02525 (10)	0.01927 (9)	−0.00116 (7)	0.00104 (7)	0.00126 (6)
Ti	0.0253 (4)	0.0243 (4)	0.0157 (3)	0.0017 (3)	0.0022 (3)	0.0023 (3)
Cl	0.0411 (7)	0.0424 (6)	0.0388 (6)	−0.0064 (5)	0.0013 (5)	0.0034 (5)
O1	0.0297 (16)	0.0257 (14)	0.0179 (12)	−0.0016 (12)	0.0008 (11)	0.0041 (11)
O2	0.045 (2)	0.0505 (19)	0.0231 (15)	−0.0082 (16)	−0.0072 (14)	0.0014 (13)
O3	0.0308 (19)	0.066 (2)	0.057 (2)	−0.0159 (18)	0.0105 (16)	−0.0051 (18)
O4	0.060 (2)	0.075 (3)	0.0213 (17)	0.0082 (19)	0.0064 (15)	0.0073 (15)
O5	0.072 (3)	0.037 (2)	0.056 (2)	0.0205 (18)	−0.018 (2)	−0.0063 (16)
O6	0.065 (2)	0.0354 (19)	0.051 (2)	0.0102 (17)	0.0045 (18)	−0.0071 (16)
C1	0.024 (2)	0.0187 (19)	0.0199 (17)	0.0039 (16)	0.0048 (15)	0.0006 (15)
C2	0.026 (2)	0.028 (2)	0.030 (2)	−0.0050 (17)	0.0034 (18)	−0.0016 (17)
C3	0.033 (3)	0.034 (3)	0.030 (2)	0.000 (2)	0.0032 (19)	0.0010 (19)
C4	0.034 (3)	0.039 (3)	0.028 (2)	−0.0027 (19)	0.0086 (19)	0.0048 (18)
C5	0.035 (3)	0.036 (3)	0.028 (2)	0.001 (2)	−0.0089 (18)	0.0017 (19)
C6	0.036 (3)	0.037 (3)	0.026 (2)	0.000 (2)	0.0020 (18)	−0.0027 (19)
C21	0.024 (2)	0.027 (2)	0.0166 (16)	0.0010 (17)	0.0020 (15)	0.0004 (15)
C22	0.028 (2)	0.028 (2)	0.0224 (18)	0.0026 (17)	0.0045 (16)	0.0019 (16)
C23	0.033 (2)	0.044 (3)	0.024 (2)	0.008 (2)	0.0022 (18)	0.0088 (19)
C24	0.027 (2)	0.058 (3)	0.022 (2)	0.007 (2)	−0.0016 (17)	−0.004 (2)
C25	0.031 (2)	0.047 (3)	0.034 (2)	−0.011 (2)	−0.0023 (19)	0.001 (2)
C26	0.032 (2)	0.038 (2)	0.0194 (18)	−0.0063 (19)	0.0004 (17)	0.0061 (17)
C31	0.029 (2)	0.031 (2)	0.038 (2)	0.0088 (19)	0.0072 (19)	0.0127 (18)
C32	0.035 (3)	0.036 (3)	0.027 (2)	0.010 (2)	−0.0108 (19)	0.0062 (17)
C33	0.041 (3)	0.040 (3)	0.029 (2)	0.006 (2)	0.0071 (19)	0.0161 (19)
C34	0.037 (3)	0.021 (2)	0.043 (2)	−0.0007 (19)	0.004 (2)	0.0065 (18)
C35	0.041 (3)	0.024 (2)	0.031 (2)	0.0067 (19)	0.0072 (19)	−0.0009 (17)
C41	0.049 (3)	0.044 (3)	0.035 (2)	−0.003 (2)	0.004 (2)	−0.022 (2)
C42	0.070 (4)	0.027 (2)	0.038 (2)	−0.003 (2)	0.018 (2)	−0.010 (2)
C43	0.063 (4)	0.034 (3)	0.041 (3)	0.021 (2)	0.007 (2)	−0.005 (2)
C44	0.046 (3)	0.049 (3)	0.038 (2)	0.012 (2)	0.018 (2)	−0.007 (2)
C45	0.055 (3)	0.043 (3)	0.023 (2)	0.010 (2)	0.010 (2)	−0.0064 (19)

Geometric parameters (Å, º) top

W—C3	2.028 (5)	C22—H22	0.9500
W—C2	2.038 (4)	C23—C24	1.389 (7)
W—C5	2.043 (5)	C23—H23	0.9500
W—C4	2.047 (4)	C24—C25	1.375 (6)
W—C6	2.051 (5)	C24—H24	0.9500
W—C1	2.204 (4)	C25—C26	1.391 (5)
Ti—O1	1.927 (2)	C25—H25	0.9500
Ti—Cl	2.3446 (14)	C26—H26	0.9500
Ti—C41	2.358 (4)	C31—C32	1.404 (6)
Ti—C32	2.358 (4)	C31—C35	1.411 (6)
Ti—C33	2.374 (4)	C31—H31	0.9500
Ti—C43	2.377 (4)	C32—C33	1.402 (6)
Ti—C42	2.378 (4)	C32—H32	0.9500
Ti—C45	2.379 (4)	C33—C34	1.406 (6)
Ti—C31	2.381 (4)	C33—H33	0.9500
Ti—C35	2.385 (4)	C34—C35	1.389 (5)
Ti—C44	2.385 (4)	C34—H34	0.9500
Ti—C34	2.408 (4)	C35—H35	0.9500
O1—C1	1.280 (4)	C41—C45	1.403 (6)
O2—C2	1.135 (5)	C41—C42	1.410 (7)
O3—C3	1.144 (5)	C41—H41	0.9500
O4—C4	1.134 (5)	C42—C43	1.395 (7)
O5—C5	1.138 (5)	C42—H42	0.9500
O6—C6	1.137 (5)	C43—C44	1.399 (6)
C1—C21	1.499 (5)	C43—H43	0.9500
C21—C22	1.391 (5)	C44—C45	1.377 (7)
C21—C26	1.396 (5)	C44—H44	0.9500
C22—C23	1.390 (6)	C45—H45	0.9500

C3—W—C2	86.90 (16)	C21—C1—W	125.7 (2)
C3—W—C5	90.63 (17)	O2—C2—W	174.3 (4)
C2—W—C5	91.35 (16)	O3—C3—W	177.2 (4)
C3—W—C4	88.38 (17)	O4—C4—W	176.6 (4)
C2—W—C4	173.19 (17)	O5—C5—W	178.6 (4)
C5—W—C4	93.62 (16)	O6—C6—W	177.1 (4)
C3—W—C6	93.55 (17)	C22—C21—C26	118.8 (4)
C2—W—C6	88.91 (16)	C22—C21—C1	120.5 (3)
C5—W—C6	175.82 (17)	C26—C21—C1	120.6 (3)
C4—W—C6	86.47 (16)	C23—C22—C21	120.6 (4)
C3—W—C1	179.75 (15)	C23—C22—H22	119.7
C2—W—C1	92.86 (14)	C21—C22—H22	119.7
C5—W—C1	89.45 (15)	C24—C23—C22	119.8 (4)
C4—W—C1	91.85 (15)	C24—C23—H23	120.1
C6—W—C1	86.37 (15)	C22—C23—H23	120.1
O1—Ti—Cl	96.14 (8)	C25—C24—C23	120.1 (4)
O1—Ti—C41	101.07 (14)	C25—C24—H24	120.0
Cl—Ti—C41	134.35 (14)	C23—C24—H24	120.0
O1—Ti—C32	109.71 (14)	C24—C25—C26	120.2 (4)
Cl—Ti—C32	133.57 (12)	C24—C25—H25	119.9
C41—Ti—C32	78.56 (17)	C26—C25—H25	119.9
O1—Ti—C33	135.06 (13)	C25—C26—C21	120.5 (4)
Cl—Ti—C33	101.17 (12)	C25—C26—H26	119.8
C41—Ti—C33	95.76 (17)	C21—C26—H26	119.8
C32—Ti—C33	34.46 (15)	C32—C31—C35	107.7 (4)
O1—Ti—C43	90.49 (14)	C32—C31—Ti	71.9 (2)
Cl—Ti—C43	80.67 (15)	C35—C31—Ti	72.9 (2)
C41—Ti—C43	57.43 (19)	C32—C31—H31	126.1
C32—Ti—C43	134.63 (17)	C35—C31—H31	126.1
C33—Ti—C43	132.96 (16)	Ti—C31—H31	120.8
O1—Ti—C42	77.09 (13)	C33—C32—C31	108.0 (4)
Cl—Ti—C42	113.08 (15)	C33—C32—Ti	73.4 (2)
C41—Ti—C42	34.65 (17)	C31—C32—Ti	73.6 (2)
C32—Ti—C42	109.99 (18)	C33—C32—H32	126.0
C33—Ti—C42	130.25 (17)	C31—C32—H32	126.0
C43—Ti—C42	34.13 (18)	Ti—C32—H32	118.9
O1—Ti—C45	133.08 (14)	C32—C33—C34	107.7 (4)
Cl—Ti—C45	108.73 (13)	C32—C33—Ti	72.1 (2)
C41—Ti—C45	34.45 (16)	C34—C33—Ti	74.2 (2)
C32—Ti—C45	81.11 (16)	C32—C33—H33	126.2
C33—Ti—C45	79.00 (16)	C34—C33—H33	126.2
C43—Ti—C45	56.85 (17)	Ti—C33—H33	119.4
C42—Ti—C45	56.82 (16)	C35—C34—C33	108.5 (4)
O1—Ti—C31	79.09 (13)	C35—C34—Ti	72.3 (2)
Cl—Ti—C31	125.21 (12)	C33—C34—Ti	71.6 (2)
C41—Ti—C31	99.57 (17)	C35—C34—H34	125.8
C32—Ti—C31	34.47 (14)	C33—C34—H34	125.8
C33—Ti—C31	57.05 (14)	Ti—C34—H34	122.1
C43—Ti—C31	152.69 (18)	C34—C35—C31	108.0 (4)
C42—Ti—C31	118.56 (17)	C34—C35—Ti	74.1 (2)
C45—Ti—C31	113.73 (16)	C31—C35—Ti	72.6 (2)
O1—Ti—C35	81.89 (12)	C34—C35—H35	126.0
Cl—Ti—C35	90.79 (11)	C31—C35—H35	126.0
C41—Ti—C35	133.17 (17)	Ti—C35—H35	119.2
C32—Ti—C35	57.28 (15)	C45—C41—C42	107.1 (5)
C33—Ti—C35	56.94 (15)	C45—C41—Ti	73.6 (3)
C43—Ti—C35	167.92 (17)	C42—C41—Ti	73.5 (3)
C42—Ti—C35	149.50 (17)	C45—C41—H41	126.4
C45—Ti—C35	134.76 (15)	C42—C41—H41	126.4
C31—Ti—C35	34.43 (14)	Ti—C41—H41	118.5
O1—Ti—C44	124.66 (14)	C43—C42—C41	108.4 (4)
Cl—Ti—C44	78.77 (13)	C43—C42—Ti	72.9 (2)
C41—Ti—C44	56.67 (18)	C41—C42—Ti	71.9 (3)
C32—Ti—C44	112.91 (16)	C43—C42—H42	125.8
C33—Ti—C44	99.40 (16)	C41—C42—H42	125.8
C43—Ti—C44	34.17 (16)	Ti—C42—H42	121.1
C42—Ti—C44	56.31 (17)	C42—C43—C44	107.1 (5)
C45—Ti—C44	33.62 (16)	C42—C43—Ti	73.0 (3)
C31—Ti—C44	146.91 (16)	C44—C43—Ti	73.2 (2)
C35—Ti—C44	152.05 (16)	C42—C43—H43	126.5
O1—Ti—C34	113.94 (12)	C44—C43—H43	126.5
Cl—Ti—C34	77.75 (11)	Ti—C43—H43	119.3
C41—Ti—C34	129.81 (17)	C45—C44—C43	109.2 (5)
C32—Ti—C34	56.81 (15)	C45—C44—Ti	72.9 (2)
C33—Ti—C34	34.20 (15)	C43—C44—Ti	72.6 (2)
C43—Ti—C34	148.78 (17)	C45—C44—H44	125.4
C42—Ti—C34	164.43 (16)	C43—C44—H44	125.4
C45—Ti—C34	109.94 (15)	Ti—C44—H44	120.7
C31—Ti—C34	56.44 (14)	C44—C45—C41	108.1 (4)
C35—Ti—C34	33.69 (13)	C44—C45—Ti	73.4 (2)
C44—Ti—C34	118.36 (16)	C41—C45—Ti	72.0 (2)
C1—O1—Ti	171.7 (2)	C44—C45—H45	125.9
O1—C1—C21	111.2 (3)	C41—C45—H45	125.9
O1—C1—W	123.0 (3)	Ti—C45—H45	120.4

Experimental details

Crystal data
Chemical formula	[TiW(C₅H₅)₂(C₇H₅O)Cl(CO)₅]
M_r	642.54
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	8.553 (1), 12.268 (1), 20.789 (3)
β (°)	95.903 (1)
V (Å³)	2169.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.83
Crystal size (mm)	0.17 × 0.14 × 0.12

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)
T_min, T_max	0.438, 0.542
No. of measured, independent and observed [I > 2σ(I)] reflections	12664, 4270, 3701
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.062, 1.04
No. of reflections	4270
No. of parameters	280
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.05, −1.28

Computer programs: COLLECT (Nonius, 1998), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN(Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001; Atwood & Barbour, 2003), publCIF (Westrip, 2008).

Selected geometric parameters (Å, º) top

W—C1	2.204 (4)	O1—C1	1.280 (4)
Ti—O1	1.927 (2)

C1—O1—Ti	171.7 (2)

Footnotes

‡Currently at: Indus Consulting, PO Box 67283, Centurion 0169, South Africa.

§Currently at: Puris Natural Aroma Chemicals, PO Box 12127, Die Boord 7613, South Africa.

Acknowledgements

We thank the NRF and the University of Stellenbosch for financial support.

References

Atwood, J. L. & Barbour, L. J. (2003). Cryst. Growth Des. 3, 3–8. Web of Science CrossRef CAS Google Scholar
Balzer, B. L., Cazanoue, M., Sabat, M. & Finn, M. G. (1992). Organometallics, 11, 1759–1761. CSD CrossRef CAS Web of Science Google Scholar
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Barluenga, J. & Fañanás, F. J. (2000). Tetrahedron, 56, 4597–4628. Web of Science CrossRef CAS Google Scholar
Esterhuysen, C., Nel, I. B. J. & Cronje, S. (2008). Acta Cryst. E64, m1150. Web of Science CSD CrossRef IUCr Journals Google Scholar
Luruli, N., Grumel, V., Brüll, R., Du Toit, A., Pasch, H., Van Reenen, A. J. & Raubenheimer, H. G. (2004). J. Polym. Sci. A1, 5121–5133. CrossRef Google Scholar
Luruli, N., Heinz, L. C., Grumel, V., Brüll, R., Pasch, H. & Raubenheimer, H. G. (2006). Polymer, 47, 56–66. Web of Science CrossRef CAS Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Orpen, A. G., Brammer, L., Allen, F. H., Kennard, O., Watson, D. G. & Taylor, R. (1989). J. Chem. Soc. Dalton Trans. pp. S1–83. CrossRef Web of Science Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sinn, H., Kaminsky, W., Vollmer, H. J. & Woldt, R. (1980). Angew. Chem. Int. Ed. Engl. 19, 390–392. CrossRef Web of Science Google Scholar
Westrip, S. P. (2008). publCIF. In preparation. Google Scholar

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