Penta­carbonyl-2κ5C-chlorido-1κCl-bis­[1(η5)-cyclo­penta­dien­yl](μ-1-oxido­ethyl­ene-1:2κ2O:C)chromium(0)zirconium(IV)

Esterhuysen, C.; Retief, L.; Kruger, G.J.; Cronje, S.; Raubenheimer, H.G.

doi:10.1107/S1600536808042621

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page m125

doi:10.1107/S1600536808042621

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Pentacarbonyl-2κ⁵C-chlorido-1κCl-bis[1(η⁵)-cyclopentadienyl](μ-1-oxidoethylene-1:2κ²O:C)chromium(0)zirconium(IV)

Catharine Esterhuysen,^a ^* Lizette Retief,^a ‡ Gert J. Kruger,^b Stephanie Cronje ^a and Helgard G. Raubenheimer ^a

^aDepartment of Chemistry and Polymer Science, University of Stellenbosch, Private Bag X1, Matieland 7602, South Africa, and ^bDepartment of Chemistry and Biochemistry, University of Johannesburg, P O Box 524, Auckland Park, Johannesburg, 2006, South Africa
^*Correspondence e-mail: ce@sun.ac.za

(Received 8 December 2008; accepted 15 December 2008; online 8 January 2009)

The title compound, [CrZr(C₅H₅)₂(C₂H₃O)Cl(CO)₅], consists of two metal centres, with a (pentacarbonylchromium)oxymethylcarbene group coordinating as a monodentate ligand to the zirconocene chloride. π-Delocalization through the Zr—O—C=Cr unit is indicated by a short Zr—O distance [2.041 (3) Å] and a nearly linear Zr—O—C angle [170.5 (3)°]. Molecules are aligned with their molecular planes (through Zr, Cl, carbene and Cr) parallel to the ab plane. C—H⋯Cl interactions result in zigzag chains of molecules propagating parallel to the b axis.

Related literature

For related literature regarding catalytic data of the title compound, see: Sinn et al. (1980 ); Luruli et al. (2004 , 2006 ). For other cases of anionic Fischer-type carbenes being used as monodentate ligands, see: Barluenga & Fañanás (2000 ). For comparable structures, see: Esterhuysen, Nel & Cronje (2008 ); Esterhuysen, Neveling et al. (2008 ).

Experimental

Crystal data

[CrZr(C₅H₅)₂(C₂H₃O)Cl(CO)₅]
M_r = 491.94
Monoclinic, P 2₁ /c
a = 12.7395 (7) Å
b = 12.1117 (6) Å
c = 12.7859 (7) Å
β = 100.826 (5)°
V = 1937.71 (18) Å³
Z = 4
Mo Kα radiation
μ = 1.27 mm⁻¹
T = 173 (2) K
0.30 × 0.28 × 0.08 mm

Data collection

Philips PW1100 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.68, T_max = 0.88
3423 measured reflections
3423 independent reflections
2332 reflections with I > 2σ(I)
3 standard reflections every 50 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.109
S = 1.06
3423 reflections
235 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16⋯Cl1ⁱ	0.95	2.74	3.581 (8)	149
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: PWPC (Gomm, 1998 ); cell refinement: PWPC; data reduction: Xtal3.4 (Hall et al., 1995 ); 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, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808042621/at2691sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808042621/at2691Isup2.hkl

checkCIF report

Comment top

Since Cp₂TiCl₂ was shown to polymerize ethylene when activated by methylaluminoxane, MAO (Sinn et al., 1980), derivatives of this compound have been synthesized where a Cl ligand was replaced by a monodentate anionic Fischer-type carbene ligand (Barluenga and Fañanás, 2000). We have shown that zirconocene equivalents of this family of homogeneous catalysts, Cp₂Zr(Cl)OC(R)M(CO)₅ (where M = W or Cr), 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). Herein we report the crystal structure of the title zirconocene complex, (I).

In the molecular structure the Zr—O and O—C distances are similar to those found in the equivalent tungsten pentacarbonyl complex (Esterhuysen, Nel & Cronje, 2008). The Zr—O—C angle, on the other hand, is less linear than the previously published tungsten structure [177.4 (7)°], but similar to the hafnocene complex W(CO)₅C(C₆H₅)OHf(C₅H₅)₂Cl (Esterhuysen, Neveling et al., 2008), where the Hf—O—C angle deviates slightly more from linearity [171.4 (3)°]. These results are indicative of π delocalization through the Zr—O—C = W unit.

Molecules are linked by C—H···Cl interactions into zigzag chains along the b axis. All molecules in a chain point in the same direction, with their molecular planes parallel. Neighbouring chains in the a-direction have the same orientation, thus forming a layer parallel to the ab-plane. Molecules in neighbouring layers in the c-direction have alternating orientations.

Related literature top

For related literature regarding catalytic data of the title compound, see: Sinn et al. (1980); Luruli et al. (2004, 2006). For other cases of anionic Fischer-type carbenes being used as monodentate ligands, see: Barluenga & Fañanás (2000). For comparable structures, see: Esterhuysen, Nel & Cronje (2008); Esterhuysen, Neveling et al. (2008).

Experimental top

A solution of LiCH₃ (11 ml, 1.5M in diethylether, 16.5 mmol) in 10 ml diethylether was added to a well stirred suspension of Cr(CO)₆ (3.30 g, 15.0 mmol) in 100 ml of diethylether over the period of 1.5 h. The mixture was stripped of solvent in vacuo. The residue was dried for 3 h, extracted with cold (273 K), degassed water (1 × 40 ml, 2 × 20 ml) and the formed solution filtered. The aqueous solution was treated with a solution of [NEt₄]Cl (2.49 g, 15 mmol) in cold, degassed water (4 ml) and the formed precipitate was isolated and dried overnight in vacuo. The precipitate was dissolved in warm CH₂Cl₂ (5 ml) layered with penatne and cooled to 258 K to yield yellow crystals of (CO)₅Cr{=C(Me)O}[NEt₄]. A solution of 0.61 g (2.0 mmol) of the product in 30 ml of CH₂Cl₂ was added to a solution of Cp₂ZrCl₂ (0.58 g, 2.0 mmol) in 70 ml of diethylether at 233 K over a period of 40 min. AgBF₄ (0.39 g, 2.0 mmol) was then added to the mixture and stirred for an hour at 233 K. After reaching room temperature the solvent was removed in vacuo and the residue extracted in 5 portions of 10 ml of toluene. The extract was filtered, and the filtrate dried over anhydrous MgSO₄. The solution was layered with pentane and kept at 258 K to yield orange crystals suitable for X-ray diffraction analysis.

Computing details top

Data collection: PWPC (Gomm, 1998); cell refinement: PWPC (Gomm, 1998); data reduction: Xtal3.4 (Hall et al., 1995); 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, 2009).

Figures top

	Fig. 1. The molecular structure of (I) showing the atomic labelling scheme and displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A portion of the packing diagram showing zigzag chains of molecules forming a layer perpendicular to the c axis.

Pentacarbonyl-2κ⁵C-chlorido-1κCl-bis[1(η⁵)-cyclopentadienyl](µ-1- oxidoethylene-1:2κ²O:C)chromiumzirconium top

Crystal data top

[CrZr(C₅H₅)₂(C₂H₃O)Cl(CO)₅]	F(000) = 976
M_r = 491.94	D_x = 1.686 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 48 reflections
a = 12.7395 (7) Å	θ = 2–17°
b = 12.1117 (6) Å	µ = 1.27 mm⁻¹
c = 12.7859 (7) Å	T = 173 K
β = 100.826 (5)°	Plate, orange
V = 1937.71 (18) Å³	0.30 × 0.28 × 0.08 mm
Z = 4

Data collection top

Philips PW1100 diffractometer	2332 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.000
Graphite monochromator	θ_max = 25.0°, θ_min = 2.3°
ω–2θ scans	h = −15→14
Absorption correction: ψ scan (North et al., 1968)	k = 0→14
T_min = 0.68, T_max = 0.88	l = 0→15
3423 measured reflections	3 standard reflections every 50 reflections
3423 independent reflections	intensity decay: none

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.053P)²] where P = (F_o² + 2F_c²)/3
3423 reflections	(Δ/σ)_max < 0.001
235 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

[CrZr(C₅H₅)₂(C₂H₃O)Cl(CO)₅]	V = 1937.71 (18) Å³
M_r = 491.94	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.7395 (7) Å	µ = 1.27 mm⁻¹
b = 12.1117 (6) Å	T = 173 K
c = 12.7859 (7) Å	0.30 × 0.28 × 0.08 mm
β = 100.826 (5)°

Data collection top

Philips PW1100 diffractometer	2332 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.000
T_min = 0.68, T_max = 0.88	3 standard reflections every 50 reflections
3423 measured reflections	intensity decay: none
3423 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.06	Δρ_max = 0.55 e Å⁻³
3423 reflections	Δρ_min = −0.58 e Å⁻³
235 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
Zr1	0.67690 (3)	0.45977 (3)	0.79870 (3)	0.03838 (16)
Cr2	0.82371 (6)	0.82936 (6)	0.79664 (6)	0.0441 (2)
Cl1	0.51592 (14)	0.56328 (16)	0.80604 (18)	0.1054 (7)
O1	0.6062 (3)	0.7896 (4)	0.6561 (3)	0.0785 (12)
O2	0.7878 (4)	1.0760 (3)	0.7936 (4)	0.1005 (16)
O3	0.7167 (4)	0.7914 (4)	0.9852 (4)	0.1065 (17)
O4	0.9358 (4)	0.8437 (4)	0.6086 (4)	0.0886 (14)
O5	1.0309 (4)	0.8682 (5)	0.9517 (4)	0.1162 (19)
O6	0.7769 (3)	0.5916 (3)	0.8006 (3)	0.0532 (9)
C1	0.6880 (4)	0.8052 (4)	0.7069 (4)	0.0492 (12)
C2	0.8007 (5)	0.9823 (5)	0.7944 (4)	0.0631 (15)
C3	0.7572 (5)	0.8072 (5)	0.9152 (5)	0.0627 (15)
C4	0.8933 (4)	0.8394 (4)	0.6786 (5)	0.0566 (13)
C5	0.9534 (5)	0.8515 (5)	0.8931 (5)	0.0689 (16)
C6	0.8496 (4)	0.6625 (4)	0.7962 (4)	0.0449 (11)
C7	0.9547 (4)	0.6101 (5)	0.7899 (6)	0.086 (2)
H7A	1.0080	0.6678	0.7871	0.129*
H7B	0.9469	0.5645	0.7256	0.129*
H7C	0.9780	0.5639	0.8528	0.129*
C8	0.8066 (5)	0.4232 (6)	0.9667 (5)	0.0733 (18)
H8	0.8737	0.4599	0.9772	0.088*
C9	0.7144 (6)	0.4611 (5)	0.9977 (4)	0.0769 (19)
H9	0.7065	0.5287	1.0332	0.092*
C10	0.6349 (5)	0.3814 (6)	0.9672 (4)	0.0758 (18)
H10	0.5635	0.3850	0.9787	0.091*
C11	0.6779 (6)	0.2982 (5)	0.9184 (5)	0.0762 (19)
H11	0.6414	0.2335	0.8893	0.091*
C12	0.7831 (6)	0.3228 (5)	0.9179 (5)	0.0711 (17)
H12	0.8315	0.2779	0.8887	0.085*
C13	0.7269 (6)	0.4442 (6)	0.6179 (5)	0.081 (2)
H13	0.7843	0.4867	0.6012	0.097*
C14	0.6228 (6)	0.4758 (6)	0.6006 (5)	0.084 (2)
H14	0.5943	0.5445	0.5727	0.100*
C15	0.5653 (7)	0.3857 (10)	0.6326 (6)	0.119 (3)
H15	0.4901	0.3814	0.6282	0.142*
C16	0.6386 (11)	0.3060 (7)	0.6711 (6)	0.124 (4)
H16	0.6228	0.2365	0.6989	0.149*
C17	0.7361 (9)	0.3420 (7)	0.6632 (5)	0.106 (3)
H17	0.8011	0.3027	0.6854	0.127*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zr1	0.0412 (3)	0.0306 (2)	0.0410 (3)	−0.0002 (2)	0.00175 (18)	0.0023 (2)
Cr2	0.0464 (5)	0.0299 (4)	0.0544 (5)	0.0011 (3)	0.0054 (4)	0.0004 (3)
Cl1	0.0717 (11)	0.0871 (13)	0.1666 (19)	0.0361 (10)	0.0464 (12)	0.0408 (12)
O1	0.048 (2)	0.097 (3)	0.084 (3)	0.002 (2)	−0.005 (2)	0.002 (2)
O2	0.121 (4)	0.035 (2)	0.140 (4)	0.013 (2)	0.013 (3)	−0.005 (2)
O3	0.134 (5)	0.122 (4)	0.076 (3)	0.023 (4)	0.053 (3)	0.009 (3)
O4	0.086 (3)	0.096 (3)	0.094 (3)	−0.016 (3)	0.042 (3)	−0.007 (3)
O5	0.077 (3)	0.118 (4)	0.132 (4)	−0.015 (3)	−0.033 (3)	−0.002 (4)
O6	0.052 (2)	0.0333 (18)	0.073 (2)	−0.0062 (16)	0.0079 (17)	−0.0001 (16)
C1	0.058 (3)	0.039 (3)	0.054 (3)	0.008 (2)	0.018 (3)	0.005 (2)
C2	0.074 (4)	0.041 (3)	0.071 (4)	0.004 (3)	0.007 (3)	−0.003 (3)
C3	0.076 (4)	0.055 (3)	0.057 (3)	0.008 (3)	0.010 (3)	−0.005 (3)
C4	0.054 (3)	0.045 (3)	0.071 (4)	−0.008 (3)	0.014 (3)	0.000 (3)
C5	0.061 (4)	0.052 (3)	0.088 (4)	−0.007 (3)	−0.002 (3)	−0.003 (3)
C6	0.044 (3)	0.036 (3)	0.052 (3)	0.000 (2)	0.003 (2)	0.002 (2)
C7	0.048 (3)	0.049 (3)	0.160 (7)	0.008 (3)	0.016 (4)	0.004 (4)
C8	0.073 (4)	0.076 (4)	0.058 (4)	−0.007 (4)	−0.020 (3)	0.016 (3)
C9	0.115 (6)	0.071 (4)	0.041 (3)	0.015 (4)	0.004 (3)	−0.011 (3)
C10	0.083 (5)	0.099 (5)	0.047 (3)	−0.006 (4)	0.019 (3)	0.015 (3)
C11	0.124 (6)	0.049 (3)	0.050 (4)	−0.013 (4)	0.002 (4)	0.014 (3)
C12	0.084 (5)	0.065 (4)	0.061 (4)	0.026 (4)	0.005 (3)	0.020 (3)
C13	0.104 (6)	0.093 (5)	0.048 (3)	−0.021 (4)	0.019 (4)	−0.003 (3)
C14	0.100 (5)	0.094 (5)	0.048 (3)	−0.010 (5)	−0.007 (3)	0.023 (3)
C15	0.104 (6)	0.185 (10)	0.053 (4)	−0.072 (7)	−0.021 (4)	−0.008 (5)
C16	0.232 (12)	0.088 (6)	0.047 (4)	−0.088 (8)	0.009 (6)	−0.022 (4)
C17	0.188 (10)	0.076 (5)	0.058 (4)	0.042 (6)	0.032 (5)	−0.012 (4)

Geometric parameters (Å, º) top

Zr1—O6	2.041 (3)	C6—C7	1.498 (7)
Zr1—Cl1	2.4205 (16)	C7—H7A	0.9800
Zr1—C16	2.463 (7)	C7—H7B	0.9800
Zr1—C17	2.470 (6)	C7—H7C	0.9800
Zr1—C12	2.476 (5)	C8—C12	1.373 (8)
Zr1—C11	2.483 (5)	C8—C9	1.387 (9)
Zr1—C15	2.490 (6)	C8—H8	0.9500
Zr1—C8	2.492 (5)	C9—C10	1.400 (9)
Zr1—C9	2.500 (5)	C9—H9	0.9500
Zr1—C10	2.503 (5)	C10—C11	1.354 (9)
Zr1—C14	2.504 (6)	C10—H10	0.9500
Zr1—C13	2.517 (6)	C11—C12	1.374 (9)
Cr2—C2	1.875 (6)	C11—H11	0.9500
Cr2—C5	1.885 (6)	C12—H12	0.9500
Cr2—C3	1.889 (6)	C13—C14	1.358 (9)
Cr2—C4	1.892 (6)	C13—C17	1.362 (9)
Cr2—C1	1.910 (6)	C13—H13	0.9500
Cr2—C6	2.048 (5)	C14—C15	1.417 (10)
O1—C1	1.135 (6)	C14—H14	0.9500
O2—C2	1.146 (6)	C15—C16	1.368 (13)
O3—C3	1.130 (6)	C15—H15	0.9500
O4—C4	1.131 (6)	C16—C17	1.338 (12)
O5—C5	1.141 (7)	C16—H16	0.9500
O6—C6	1.271 (5)	C17—H17	0.9500

O6—Zr1—Cl1	97.24 (10)	C3—Cr2—C6	87.6 (2)
O6—Zr1—C16	130.2 (3)	C4—Cr2—C6	87.8 (2)
Cl1—Zr1—C16	110.7 (3)	C1—Cr2—C6	88.58 (19)
O6—Zr1—C17	100.8 (3)	C6—O6—Zr1	170.5 (3)
Cl1—Zr1—C17	134.4 (2)	O1—C1—Cr2	178.0 (5)
C16—Zr1—C17	31.5 (3)	O2—C2—Cr2	179.2 (6)
O6—Zr1—C12	104.4 (2)	O3—C3—Cr2	178.3 (6)
Cl1—Zr1—C12	133.79 (17)	O4—C4—Cr2	178.7 (5)
C16—Zr1—C12	85.4 (3)	O5—C5—Cr2	177.9 (6)
C17—Zr1—C12	80.9 (2)	O6—C6—C7	112.5 (4)
O6—Zr1—C11	132.73 (19)	O6—C6—Cr2	123.2 (3)
Cl1—Zr1—C11	106.9 (2)	C7—C6—Cr2	124.3 (4)
C16—Zr1—C11	77.9 (3)	C6—C7—H7A	109.5
C17—Zr1—C11	90.6 (3)	C6—C7—H7B	109.5
C12—Zr1—C11	32.2 (2)	H7A—C7—H7B	109.5
O6—Zr1—C15	123.2 (2)	C6—C7—H7C	109.5
Cl1—Zr1—C15	82.4 (3)	H7A—C7—H7C	109.5
C16—Zr1—C15	32.1 (3)	H7B—C7—H7C	109.5
C17—Zr1—C15	52.7 (3)	C12—C8—C9	107.3 (6)
C12—Zr1—C15	116.3 (3)	C12—C8—Zr1	73.3 (3)
C11—Zr1—C15	100.2 (3)	C9—C8—Zr1	74.2 (3)
O6—Zr1—C8	79.46 (18)	C12—C8—H8	126.3
Cl1—Zr1—C8	119.22 (18)	C9—C8—H8	126.3
C16—Zr1—C8	117.0 (3)	Zr1—C8—H8	118.2
C17—Zr1—C8	105.2 (3)	C8—C9—C10	107.4 (6)
C12—Zr1—C8	32.1 (2)	C8—C9—Zr1	73.5 (3)
C11—Zr1—C8	53.3 (2)	C10—C9—Zr1	73.9 (3)
C15—Zr1—C8	148.3 (3)	C8—C9—H9	126.3
O6—Zr1—C9	89.1 (2)	C10—C9—H9	126.3
Cl1—Zr1—C9	87.62 (17)	Zr1—C9—H9	118.3
C16—Zr1—C9	130.9 (3)	C11—C10—C9	107.9 (6)
C17—Zr1—C9	133.9 (2)	C11—C10—Zr1	73.4 (3)
C12—Zr1—C9	53.1 (2)	C9—C10—Zr1	73.6 (3)
C11—Zr1—C9	53.1 (2)	C11—C10—H10	126.0
C15—Zr1—C9	147.1 (3)	C9—C10—H10	126.0
C8—Zr1—C9	32.3 (2)	Zr1—C10—H10	118.8
O6—Zr1—C10	121.38 (19)	C10—C11—C12	108.6 (6)
Cl1—Zr1—C10	81.00 (17)	C10—C11—Zr1	75.1 (3)
C16—Zr1—C10	103.6 (3)	C12—C11—Zr1	73.6 (3)
C17—Zr1—C10	121.9 (3)	C10—C11—H11	125.7
C12—Zr1—C10	52.9 (2)	C12—C11—H11	125.7
C11—Zr1—C10	31.5 (2)	Zr1—C11—H11	117.6
C15—Zr1—C10	114.7 (3)	C8—C12—C11	108.7 (6)
C8—Zr1—C10	53.5 (2)	C8—C12—Zr1	74.6 (3)
C9—Zr1—C10	32.5 (2)	C11—C12—Zr1	74.2 (3)
O6—Zr1—C14	90.23 (19)	C8—C12—H12	125.7
Cl1—Zr1—C14	85.7 (2)	C11—C12—H12	125.7
C16—Zr1—C14	53.6 (3)	Zr1—C12—H12	117.5
C17—Zr1—C14	52.9 (3)	C14—C13—C17	109.2 (7)
C12—Zr1—C14	133.6 (2)	C14—C13—Zr1	73.8 (4)
C11—Zr1—C14	130.8 (2)	C17—C13—Zr1	72.2 (4)
C15—Zr1—C14	33.0 (2)	C14—C13—H13	125.4
C8—Zr1—C14	153.9 (3)	C17—C13—H13	125.4
C9—Zr1—C14	173.1 (2)	Zr1—C13—H13	120.3
C10—Zr1—C14	146.9 (2)	C13—C14—C15	106.2 (7)
O6—Zr1—C13	78.71 (18)	C13—C14—Zr1	74.9 (3)
Cl1—Zr1—C13	115.91 (19)	C15—C14—Zr1	73.0 (3)
C16—Zr1—C13	52.3 (3)	C13—C14—H14	126.9
C17—Zr1—C13	31.7 (2)	C15—C14—H14	126.9
C12—Zr1—C13	108.2 (2)	Zr1—C14—H14	117.5
C11—Zr1—C13	122.3 (2)	C16—C15—C14	107.0 (8)
C15—Zr1—C13	52.6 (3)	C16—C15—Zr1	72.9 (4)
C8—Zr1—C13	122.5 (3)	C14—C15—Zr1	74.1 (4)
C9—Zr1—C13	154.5 (3)	C16—C15—H15	126.5
C10—Zr1—C13	153.4 (2)	C14—C15—H15	126.5
C14—Zr1—C13	31.4 (2)	Zr1—C15—H15	118.6
C2—Cr2—C5	89.1 (2)	C17—C16—C15	108.9 (8)
C2—Cr2—C3	93.4 (2)	C17—C16—Zr1	74.5 (4)
C5—Cr2—C3	88.0 (3)	C15—C16—Zr1	75.0 (5)
C2—Cr2—C4	91.1 (2)	C17—C16—H16	125.5
C5—Cr2—C4	91.6 (3)	C15—C16—H16	125.5
C3—Cr2—C4	175.4 (2)	Zr1—C16—H16	116.8
C2—Cr2—C1	91.2 (2)	C16—C17—C13	108.7 (9)
C5—Cr2—C1	176.2 (2)	C16—C17—Zr1	74.0 (5)
C3—Cr2—C1	88.2 (2)	C13—C17—Zr1	76.1 (4)
C4—Cr2—C1	92.2 (2)	C16—C17—H17	125.7
C2—Cr2—C6	178.9 (2)	C13—C17—H17	125.6
C5—Cr2—C6	91.2 (2)	Zr1—C17—H17	116.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···Cl1ⁱ	0.95	2.74	3.581 (8)	149

Symmetry code: (i) −x+1, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	[CrZr(C₅H₅)₂(C₂H₃O)Cl(CO)₅]
M_r	491.94
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	12.7395 (7), 12.1117 (6), 12.7859 (7)
β (°)	100.826 (5)
V (Å³)	1937.71 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.27
Crystal size (mm)	0.30 × 0.28 × 0.08

Data collection
Diffractometer	Philips PW1100 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.68, 0.88
No. of measured, independent and observed [I > 2σ(I)] reflections	3423, 3423, 2332
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.109, 1.06
No. of reflections	3423
No. of parameters	235
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.58

Computer programs: PWPC (Gomm, 1998), Xtal3.4 (Hall et al., 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001; Atwood & Barbour, 2003), publCIF (Westrip, 2009).

Selected geometric parameters (Å, º) top

Zr1—O6	2.041 (3)	O6—C6	1.271 (5)

C6—O6—Zr1	170.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···Cl1ⁱ	0.95	2.74	3.581 (8)	148.5

Symmetry code: (i) −x+1, y−1/2, −z+3/2.

Footnotes

‡Currently at The Coaching Café, 6 Bright Str, Somerset West, 7130, South Africa.

Acknowledgements

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

References

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