Penta­carbonyl-2κ5C-chlorido-1κCl-bis­[1(η5)-cyclo­penta­dien­yl][μ-oxido(phenyl)methylene-1:2κ2O:C]hafnium(IV)tungsten(0)

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

doi:10.1107/S1600536808025245

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page m1150

doi:10.1107/S1600536808025245

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Pentacarbonyl-2κ⁵C-chlorido-1κCl-bis[1(η⁵)-cyclopentadienyl][μ-oxido(phenyl)methylene-1:2κ²O:C]hafnium(IV)tungsten(0)

Catharine Esterhuysen,^a ^* I. B. Jacques Nel ^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 August 2008; accepted 5 August 2008; online 9 August 2008)

The title compound, [HfW(C₅H₅)₂(C₇H₅O)Cl(CO)₅] or [W(CO)₅(C₇H₅O){Hf(C₅H₅)₂Cl}], contains two metal centres, with a (tungstenpentacarbonyl)oxyphenylcarbene unit coordinated to a hafnocene chloride. The Hf—O—C angle is nearly linear, and the C=O distance is slightly shorter than for equivalent alkoxycarbenes. One of the cyclopentadienyl (Cp) rings undergoes an offset face-to-face π–π interaction [3.495 (7) Å] with the symmetry-related Cp ring of a neighbouring molecule.

Related literature

For related literature regarding anionic Fischer-type carbenes, see: Barluenga & Fañanás (2000 ); Brüll et al. (2001 ). For comparable structures, see: Berlekamp et al. (1993 ); Erker et al. (1989 , 1991 ). For comparable bond lengths, see: Orpen et al. (1989 ).

Experimental

Crystal data

[HfW(C₅H₅)₂(C₇H₅O)Cl(CO)₅]
M_r = 773.13
Monoclinic, P 2₁ /c
a = 8.5422 (2) Å
b = 12.5546 (3) Å
c = 21.0237 (7) Å
β = 96.152 (1)°
V = 2241.68 (11) Å³
Z = 4
Mo Kα radiation
μ = 9.91 mm⁻¹
T = 173 (2) K
0.33 × 0.27 × 0.25 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997 ) T_min = 0.056, T_max = 0.089 (expected range = 0.053–0.084)
12410 measured reflections
5106 independent reflections
4234 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.079
S = 1.01
5106 reflections
280 parameters
H-atom parameters constrained
Δρ_max = 2.61 e Å⁻³
Δρ_min = −1.76 e Å⁻³

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/S1600536808025245/tk2291sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808025245/tk2291Isup2.hkl

checkCIF report

Comment top

Anionic Fischer-type carbene ligands, prepared by the standard addition of organolithium compounds to metal carbonyls, act as monodentate ligands towards transition metals like Ti and Zr (Barluenga and Fañanás, 2000). When the second metal unit is a zirconocene moiety, Cp₂ZrCl, then such complexes have been proven to catalyse the oligomerization of 1-pentene in the presence of methylaluminoxane, MAO (Brüll et al., 2001). Herein, we report the Hf equivalent of these zirconocene alkoxycarbene complexes.

In the title compound, (I, Fig. 1), the W=C_carbene and C_carbene—C distances are similar to those found in alkoxycarbene complexes, whereas the C—O distance is shorter [2.16 (1), 1.50 (3) and 1.47 (2) Å, respectively; Orpen et al., 1989]. The Hf—O distance is also shorter than those in the metallocyclic compounds C₂₆H₂₇HfO₅V [2.063 (3) Å; Erker et al., 1991] and C₂₈H₂₉HfO₅V [2.066 (3) Å; Berlekamp et al., 1993]. The Hf—O—C angle is nearly linear, with a larger value [171.4 (3)°] than the equivalent Hf—O—C angles of 163.6 (3) and 169.0 (3)° in C₂₆H₂₇HfO₅V (Erker et al., 1991) and C₂₈H₂₉HfO₅V (Berlekamp et al., 1993), respectively, as well as the Zr—O—C angle of 166.1 (5)° in W(CO)₅C(C₆H₅)OZr(C₅H₅)₂OC₆H₅ (Erker et al., 1989).

The C21/C22/C23/C24/C25 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 = 3.495 (7) Å; Symmetry code: (i) 1 - x, 2 - y, 1 - z)].

Related literature top

For related literature regarding anionic Fischer-type carbenes, see: Barluenga & Fañanás (2000); Brüll et al. (2001). For comparable structures, see: Berlekamp et al. (1993); Erker et al. (1989, 1991). For comparable bond lengths, see: Orpen et al. (1989).

Experimental top

A solution of LiCH₃ (31 ml, 1.6M) in diethylether (50 ml) was added to a well stirred suspension of W(CO)₆ (17.802 g) in diethylether (100 ml). After solvent removal, dissolution of the residue in cold water (150 ml) and filtration, a solution of Et₄NCl (8.721 g) in cold water (50 ml) was added to the filtrate. Upon further filtration 0.740 g of the product {[W(CO)₅C(C₆H₅)O][NEt₄]} was dissolved in dichloromethane (70 ml) and added to a solution of Cp₂HfCl₂ (0.505 g) in dichloromethane (40 ml). After stirring for 30 min at -40°C AgBF₄ (0.261 g) was added. The solvent was removed and the residue extracted in 5 portions of 10 ml toluene. The extract was cooled to -40°C and filtered. The filtrate was dried over anhydrous MgSO₄, concentrated to saturation, and kept at -6°C, whereupon red crystals of the title compound suitable for X-ray diffraction analysis were obtained in 19% 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-oxido(phenyl)methylene- 1:2κ²O:C]hafnium(IV)tungsten(0) top

Crystal data top

[HfW(C₅H₅)₂(C₇H₅O)Cl(CO)₅]	F(000) = 1432
M_r = 773.13	D_x = 2.291 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 12410 reflections
a = 8.5422 (2) Å	θ = 1.9–27.5°
b = 12.5546 (3) Å	µ = 9.91 mm⁻¹
c = 21.0237 (7) Å	T = 173 K
β = 96.152 (1)°	Prism, red
V = 2241.68 (11) Å³	0.33 × 0.27 × 0.25 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	5106 independent reflections
Radiation source: fine-focus sealed tube	4234 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
ϕ and ω scans to fill Ewald sphere	θ_max = 27.5°, θ_min = 1.9°
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	h = −11→8
T_min = 0.056, T_max = 0.089	k = −16→15
12410 measured reflections	l = −26→27

Refinement top

Refinement on F²	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0436P)²] where P = (F_o² + 2F_c²)/3
5106 reflections	(Δ/σ)_max = 0.002
280 parameters	Δρ_max = 2.61 e Å⁻³
0 restraints	Δρ_min = −1.76 e Å⁻³

Crystal data top

[HfW(C₅H₅)₂(C₇H₅O)Cl(CO)₅]	V = 2241.68 (11) Å³
M_r = 773.13	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.5422 (2) Å	µ = 9.91 mm⁻¹
b = 12.5546 (3) Å	T = 173 K
c = 21.0237 (7) Å	0.33 × 0.27 × 0.25 mm
β = 96.152 (1)°

Data collection top

Nonius KappaCCD diffractometer	5106 independent reflections
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	4234 reflections with I > 2σ(I)
T_min = 0.056, T_max = 0.089	R_int = 0.049
12410 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.079	H-atom parameters constrained
S = 1.01	Δρ_max = 2.61 e Å⁻³
5106 reflections	Δρ_min = −1.76 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
Hf1	0.80934 (3)	0.779762 (17)	0.542399 (9)	0.01909 (8)
W1	0.46096 (3)	0.614746 (17)	0.676791 (9)	0.02237 (8)
Cl1	1.06982 (17)	0.83902 (12)	0.58304 (7)	0.0346 (3)
O1	0.3696 (5)	0.6436 (4)	0.52755 (18)	0.0401 (11)
O2	0.1151 (5)	0.5226 (4)	0.6774 (2)	0.0515 (12)
O3	0.4999 (6)	0.6018 (4)	0.82830 (19)	0.0530 (13)
O4	0.3679 (6)	0.8575 (4)	0.6959 (2)	0.0525 (13)
O5	0.5903 (7)	0.3811 (4)	0.6553 (2)	0.0590 (15)
O6	0.7432 (5)	0.7258 (3)	0.62527 (15)	0.0235 (8)
C1	0.4097 (6)	0.6334 (4)	0.5806 (3)	0.0250 (12)
C2	0.2402 (7)	0.5579 (5)	0.6782 (3)	0.0324 (13)
C3	0.4897 (7)	0.6036 (5)	0.7740 (3)	0.0328 (14)
C4	0.3955 (7)	0.7690 (5)	0.6888 (3)	0.0305 (14)
C5	0.5421 (7)	0.4640 (5)	0.6637 (3)	0.0321 (14)
C6	0.6979 (7)	0.6775 (4)	0.6743 (2)	0.0228 (11)
C7	0.8265 (6)	0.6792 (4)	0.7293 (2)	0.0218 (11)
C8	0.9276 (7)	0.7663 (5)	0.7384 (3)	0.0298 (13)
H8	0.9138	0.8259	0.7105	0.036*
C9	1.0477 (8)	0.7664 (5)	0.7879 (3)	0.0405 (16)
H9	1.1132	0.8273	0.7950	0.049*
C10	1.0734 (7)	0.6781 (6)	0.8273 (2)	0.0384 (16)
H10	1.1578	0.6776	0.8606	0.046*
C11	0.9740 (8)	0.5901 (5)	0.8175 (3)	0.0368 (15)
H11	0.9918	0.5289	0.8439	0.044*
C12	0.8507 (7)	0.5916 (5)	0.7701 (2)	0.0299 (13)
H12	0.7812	0.5324	0.7649	0.036*
C13	0.7818 (7)	0.9777 (4)	0.5270 (3)	0.0306 (13)
H13	0.8715	1.0229	0.5316	0.037*
C14	0.6886 (7)	0.9488 (5)	0.5760 (3)	0.0320 (13)
H14	0.7068	0.9681	0.6199	0.038*
C15	0.5638 (7)	0.8859 (4)	0.5475 (3)	0.0308 (13)
H15	0.4799	0.8578	0.5685	0.037*
C16	0.5844 (7)	0.8717 (5)	0.4830 (3)	0.0326 (14)
H16	0.5187	0.8310	0.4528	0.039*
C17	0.7188 (7)	0.9281 (5)	0.4710 (3)	0.0333 (14)
H17	0.7605	0.9320	0.4309	0.040*
C18	0.7079 (8)	0.6358 (5)	0.4693 (3)	0.0393 (16)
H18	0.5976	0.6332	0.4569	0.047*
C19	0.8207 (8)	0.6914 (5)	0.4373 (3)	0.0395 (16)
H19	0.8003	0.7322	0.3992	0.047*
C20	0.9681 (8)	0.6753 (6)	0.4722 (3)	0.0413 (16)
H20	1.0653	0.7037	0.4618	0.050*
C21	0.9484 (9)	0.6108 (5)	0.5246 (3)	0.0459 (18)
H21	1.0292	0.5881	0.5563	0.055*
C22	0.7886 (9)	0.5853 (5)	0.5224 (3)	0.0439 (17)
H22	0.7425	0.5411	0.5520	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hf1	0.01979 (13)	0.02021 (13)	0.01715 (11)	0.00217 (9)	0.00150 (8)	0.00140 (8)
W1	0.02045 (13)	0.02513 (14)	0.02122 (12)	−0.00133 (9)	0.00071 (9)	0.00187 (8)
Cl1	0.0253 (8)	0.0370 (8)	0.0403 (7)	−0.0042 (7)	−0.0014 (6)	0.0026 (6)
O1	0.040 (3)	0.053 (3)	0.025 (2)	−0.007 (2)	−0.0049 (18)	0.0019 (19)
O2	0.025 (2)	0.066 (3)	0.065 (3)	−0.013 (2)	0.012 (2)	−0.007 (3)
O3	0.053 (3)	0.084 (4)	0.024 (2)	0.002 (3)	0.008 (2)	0.013 (2)
O4	0.067 (4)	0.036 (3)	0.052 (3)	0.016 (3)	−0.003 (2)	−0.011 (2)
O5	0.074 (4)	0.040 (3)	0.057 (3)	0.024 (3)	−0.020 (3)	−0.009 (2)
O6	0.028 (2)	0.024 (2)	0.0179 (16)	−0.0010 (17)	0.0020 (15)	0.0039 (14)
C1	0.017 (3)	0.023 (3)	0.034 (3)	−0.007 (2)	0.002 (2)	0.000 (2)
C2	0.033 (4)	0.033 (3)	0.031 (3)	0.000 (3)	0.006 (2)	−0.002 (3)
C3	0.028 (3)	0.040 (4)	0.030 (3)	−0.007 (3)	0.003 (2)	0.004 (3)
C4	0.028 (3)	0.038 (4)	0.025 (3)	0.001 (3)	0.001 (2)	−0.005 (3)
C5	0.026 (3)	0.039 (4)	0.029 (3)	0.003 (3)	−0.010 (2)	−0.001 (3)
C6	0.031 (3)	0.016 (3)	0.021 (2)	0.003 (2)	0.003 (2)	0.005 (2)
C7	0.017 (3)	0.027 (3)	0.022 (2)	0.005 (2)	0.002 (2)	−0.001 (2)
C8	0.023 (3)	0.034 (3)	0.032 (3)	−0.007 (3)	0.004 (2)	0.004 (3)
C9	0.036 (4)	0.051 (4)	0.034 (3)	−0.013 (3)	0.000 (3)	−0.005 (3)
C10	0.027 (3)	0.065 (5)	0.021 (3)	0.011 (3)	−0.004 (2)	−0.005 (3)
C11	0.032 (3)	0.050 (4)	0.027 (3)	0.007 (3)	0.000 (2)	0.005 (3)
C12	0.035 (3)	0.030 (3)	0.025 (3)	0.001 (3)	0.005 (2)	0.008 (2)
C13	0.028 (3)	0.014 (3)	0.051 (3)	−0.002 (2)	0.008 (3)	0.010 (2)
C14	0.037 (4)	0.026 (3)	0.033 (3)	0.005 (3)	0.005 (3)	0.003 (3)
C15	0.021 (3)	0.028 (3)	0.045 (3)	0.010 (2)	0.010 (3)	0.014 (3)
C16	0.029 (3)	0.030 (3)	0.036 (3)	0.006 (3)	−0.011 (3)	0.005 (2)
C17	0.029 (3)	0.038 (3)	0.033 (3)	0.006 (3)	0.005 (2)	0.019 (3)
C18	0.037 (4)	0.047 (4)	0.033 (3)	−0.009 (3)	0.004 (3)	−0.021 (3)
C19	0.047 (4)	0.049 (4)	0.023 (3)	0.004 (3)	0.005 (3)	−0.006 (3)
C20	0.030 (4)	0.050 (4)	0.046 (3)	0.010 (3)	0.012 (3)	−0.011 (3)
C21	0.055 (5)	0.038 (4)	0.043 (4)	0.018 (4)	0.002 (3)	−0.007 (3)
C22	0.071 (5)	0.022 (3)	0.041 (3)	−0.007 (3)	0.017 (3)	−0.013 (3)

Geometric parameters (Å, º) top

Hf1—O6	2.006 (3)	C8—H8	0.9500
Hf1—Cl1	2.4139 (14)	C9—C10	1.387 (9)
Hf1—C16	2.464 (5)	C9—H9	0.9500
Hf1—C17	2.465 (5)	C10—C11	1.395 (9)
Hf1—C18	2.469 (6)	C10—H10	0.9500
Hf1—C21	2.479 (6)	C11—C12	1.371 (8)
Hf1—C22	2.480 (6)	C11—H11	0.9500
Hf1—C20	2.483 (6)	C12—H12	0.9500
Hf1—C19	2.484 (5)	C13—C17	1.389 (8)
Hf1—C14	2.494 (6)	C13—C14	1.415 (8)
Hf1—C15	2.496 (5)	C13—H13	0.9500
Hf1—C13	2.514 (5)	C14—C15	1.408 (8)
W1—C2	2.019 (6)	C14—H14	0.9500
W1—C1	2.037 (6)	C15—C16	1.397 (8)
W1—C3	2.038 (6)	C15—H15	0.9500
W1—C4	2.040 (6)	C16—C17	1.395 (8)
W1—C5	2.044 (6)	C16—H16	0.9500
W1—C6	2.177 (6)	C17—H17	0.9500
O1—C1	1.137 (6)	C18—C22	1.401 (9)
O2—C2	1.156 (7)	C18—C19	1.417 (9)
O3—C3	1.135 (7)	C18—H18	0.9500
O4—C4	1.149 (7)	C19—C20	1.403 (9)
O5—C5	1.139 (7)	C19—H19	0.9500
O6—C6	1.291 (6)	C20—C21	1.393 (9)
C6—C7	1.508 (7)	C20—H20	0.9500
C7—C8	1.394 (8)	C21—C22	1.398 (10)
C7—C12	1.397 (7)	C21—H21	0.9500
C8—C9	1.381 (8)	C22—H22	0.9500

O6—Hf1—Cl1	97.55 (11)	O3—C3—W1	176.2 (6)
O6—Hf1—C16	108.77 (18)	O4—C4—W1	175.9 (6)
Cl1—Hf1—C16	132.40 (15)	O5—C5—W1	178.1 (6)
O6—Hf1—C17	133.27 (18)	O6—C6—C7	110.4 (5)
Cl1—Hf1—C17	101.53 (15)	O6—C6—W1	123.3 (4)
C16—Hf1—C17	32.89 (19)	C7—C6—W1	126.1 (4)
O6—Hf1—C18	100.41 (18)	C8—C7—C12	119.0 (5)
Cl1—Hf1—C18	134.01 (16)	C8—C7—C6	120.5 (5)
C16—Hf1—C18	79.9 (2)	C12—C7—C6	120.5 (5)
C17—Hf1—C18	96.2 (2)	C9—C8—C7	120.3 (6)
O6—Hf1—C21	91.47 (19)	C9—C8—H8	119.9
Cl1—Hf1—C21	83.03 (18)	C7—C8—H8	119.9
C16—Hf1—C21	133.2 (2)	C8—C9—C10	120.4 (6)
C17—Hf1—C21	132.8 (2)	C8—C9—H9	119.8
C18—Hf1—C21	54.7 (2)	C10—C9—H9	119.8
O6—Hf1—C22	78.04 (18)	C9—C10—C11	119.4 (5)
Cl1—Hf1—C22	114.19 (19)	C9—C10—H10	120.3
C16—Hf1—C22	109.7 (2)	C11—C10—H10	120.3
C17—Hf1—C22	129.0 (2)	C12—C11—C10	120.3 (6)
C18—Hf1—C22	32.9 (2)	C12—C11—H11	119.9
C21—Hf1—C22	32.7 (2)	C10—C11—H11	119.9
O6—Hf1—C20	124.08 (19)	C11—C12—C7	120.6 (6)
Cl1—Hf1—C20	80.31 (16)	C11—C12—H12	119.7
C16—Hf1—C20	113.1 (2)	C7—C12—H12	119.7
C17—Hf1—C20	101.1 (2)	C17—C13—C14	107.8 (5)
C18—Hf1—C20	54.6 (2)	C17—C13—Hf1	71.9 (3)
C21—Hf1—C20	32.6 (2)	C14—C13—Hf1	72.8 (3)
C22—Hf1—C20	54.1 (2)	C17—C13—H13	126.1
O6—Hf1—C19	131.56 (19)	C14—C13—H13	126.1
Cl1—Hf1—C19	109.27 (17)	Hf1—C13—H13	121.0
C16—Hf1—C19	82.0 (2)	C15—C14—C13	107.0 (5)
C17—Hf1—C19	80.5 (2)	C15—C14—Hf1	73.7 (3)
C18—Hf1—C19	33.3 (2)	C13—C14—Hf1	74.3 (3)
C21—Hf1—C19	54.5 (2)	C15—C14—H14	126.5
C22—Hf1—C19	54.5 (2)	C13—C14—H14	126.5
C20—Hf1—C19	32.8 (2)	Hf1—C14—H14	117.6
O6—Hf1—C14	82.99 (16)	C16—C15—C14	108.5 (5)
Cl1—Hf1—C14	91.77 (15)	C16—C15—Hf1	72.4 (3)
C16—Hf1—C14	54.65 (19)	C14—C15—Hf1	73.5 (3)
C17—Hf1—C14	54.37 (19)	C16—C15—H15	125.8
C18—Hf1—C14	132.1 (2)	C14—C15—H15	125.8
C21—Hf1—C14	171.9 (2)	Hf1—C15—H15	120.1
C22—Hf1—C14	149.4 (2)	C17—C16—C15	107.6 (5)
C20—Hf1—C14	152.4 (2)	C17—C16—Hf1	73.6 (3)
C19—Hf1—C14	133.5 (2)	C15—C16—Hf1	74.9 (3)
O6—Hf1—C15	80.05 (17)	C17—C16—H16	126.2
Cl1—Hf1—C15	124.55 (15)	C15—C16—H16	126.2
C16—Hf1—C15	32.70 (19)	Hf1—C16—H16	117.3
C17—Hf1—C15	54.02 (19)	C13—C17—C16	109.0 (5)
C18—Hf1—C15	100.2 (2)	C13—C17—Hf1	75.7 (3)
C21—Hf1—C15	151.8 (2)	C16—C17—Hf1	73.5 (3)
C22—Hf1—C15	119.2 (2)	C13—C17—H17	125.5
C20—Hf1—C15	145.3 (2)	C16—C17—H17	125.5
C19—Hf1—C15	112.9 (2)	Hf1—C17—H17	117.1
C14—Hf1—C15	32.78 (19)	C22—C18—C19	107.5 (6)
O6—Hf1—C13	114.49 (16)	C22—C18—Hf1	74.0 (3)
Cl1—Hf1—C13	79.09 (14)	C19—C18—Hf1	73.9 (3)
C16—Hf1—C13	54.2 (2)	C22—C18—H18	126.3
C17—Hf1—C13	32.39 (19)	C19—C18—H18	126.3
C18—Hf1—C13	128.5 (2)	Hf1—C18—H18	117.8
C21—Hf1—C13	150.0 (2)	C20—C19—C18	107.4 (6)
C22—Hf1—C13	161.3 (2)	C20—C19—Hf1	73.6 (3)
C20—Hf1—C13	119.7 (2)	C18—C19—Hf1	72.8 (3)
C19—Hf1—C13	109.8 (2)	C20—C19—H19	126.3
C14—Hf1—C13	32.82 (18)	C18—C19—H19	126.3
C15—Hf1—C13	53.89 (19)	Hf1—C19—H19	119.2
C2—W1—C1	87.3 (2)	C21—C20—C19	108.7 (6)
C2—W1—C3	88.5 (2)	C21—C20—Hf1	73.5 (4)
C1—W1—C3	173.9 (2)	C19—C20—Hf1	73.6 (3)
C2—W1—C4	93.7 (2)	C21—C20—H20	125.7
C1—W1—C4	88.9 (2)	C19—C20—H20	125.7
C3—W1—C4	86.9 (2)	Hf1—C20—H20	119.0
C2—W1—C5	90.3 (2)	C20—C21—C22	107.9 (6)
C1—W1—C5	90.7 (2)	C20—C21—Hf1	73.9 (4)
C3—W1—C5	93.8 (2)	C22—C21—Hf1	73.7 (4)
C4—W1—C5	175.9 (2)	C20—C21—H21	126.1
C2—W1—C6	179.2 (2)	C22—C21—H21	126.1
C1—W1—C6	92.1 (2)	Hf1—C21—H21	118.4
C3—W1—C6	92.1 (2)	C21—C22—C18	108.6 (6)
C4—W1—C6	85.8 (2)	C21—C22—Hf1	73.6 (4)
C5—W1—C6	90.1 (2)	C18—C22—Hf1	73.1 (4)
C6—O6—Hf1	171.4 (3)	C21—C22—H22	125.7
O1—C1—W1	174.9 (5)	C18—C22—H22	125.7
O2—C2—W1	177.5 (5)	Hf1—C22—H22	119.4

Experimental details

Crystal data
Chemical formula	[HfW(C₅H₅)₂(C₇H₅O)Cl(CO)₅]
M_r	773.13
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	8.5422 (2), 12.5546 (3), 21.0237 (7)
β (°)	96.152 (1)
V (Å³)	2241.68 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	9.91
Crystal size (mm)	0.33 × 0.27 × 0.25

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)
T_min, T_max	0.056, 0.089
No. of measured, independent and observed [I > 2σ(I)] reflections	12410, 5106, 4234
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.079, 1.01
No. of reflections	5106
No. of parameters	280
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.61, −1.76

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

Footnotes

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

Acknowledgements

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

References

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