Dichlorido-1κCl,3κCl-hexa­kis­[1,1,2,2,3,3(η5)-cyclo­penta­dien­yl]di-μ2-oxido-1:2κ2O:O;2:3κ2O:O-trizirconium(IV)

Kraft, B.M.; Brennessel, W.W.

doi:10.1107/S1600536812024968

Volume 68
Part 7
Page m893
July 2012

Received 25 May 2012
Accepted 31 May 2012
Online 13 June 2012

Key indicators
Single-crystal X-ray study
T = 223 K
Mean (C-C) = 0.009 Å
R = 0.040
wR = 0.100
Data-to-parameter ratio = 24.0
Details

Dichlorido-1Cl,3Cl-hexakis[1,1,2,2,3,3(⁵)-cyclopentadienyl]di-₂-oxido-1:2²O:O;2:3²O:O-trizirconium(IV)

Bradley M. Kraft ^a ^* and William W. Brennessel ^b

^aDepartment of Chemistry, St. John Fisher College, Rochester, NY 14618, USA, and ^bDepartment of Chemistry, University of Rochester, Rochester, NY 14627, USA
Correspondence e-mail: bkraft@sjfc.edu

The title compound, [Zr₃(C₅H₅)₆Cl₂O₂], exists as discrete molecules possessing a series of three Cp₂Zr units (Cp is cyclopentadienyl) bridged by oxide ligands and end-capped by chloride ligands. The Cp planes in the central and terminal zirconocene units form dihedral angles of 53.3 (2) and 53.5 (2)°, respectively. The two Zr-O-Zr bridge angles are nearly linear and form a planar Zr₃O₂ core. The molecule bears C2 symmetry with the central Zr atom lying on a crystallographic twofold axis.

Related literature

For closely related Zr molecules with only one oxo bridge, see: Reid et al. (1965); Clarke & Drew (1974); Kuz'mina et al. (1988); Nieger et al. (1999); Spletstoser et al. (2007). For cyclic trimeric oxozirconocenes, see: Arnold et al. (2011); Boutonnet et al. (1995); Mikhailova et al. (1993). For similar structures with terminal Zr-Cl bonds, see: Corey et al. (1995); Reddy & Petersen (1989). For the Hf analog, but with methyl-substituted cyclopentadienyl rings, see: Wisniewska et al. (2008).

Experimental

Crystal data

[Zr₃(C₅H₅)₆Cl₂O₂]
M_r = 767.10
Orthorhombic, P b c n
a = 7.8809 (4) Å
b = 18.0518 (10) Å
c = 20.1883 (11) Å
V = 2872.1 (3) Å³
Z = 4
Mo K radiation
= 1.28 mm^-1
T = 223 K
0.20 × 0.18 × 0.04 mm

Data collection

Bruker SMART APEXII CCD Platform diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008b) T_min = 0.784, T_max = 0.951
34715 measured reflections
4032 independent reflections
2569 reflections with I > 2(I)
R_int = 0.099

Refinement

R[F² > 2(F²)] = 0.040
wR(F²) = 0.100
S = 1.01
4032 reflections
168 parameters
H-atom parameters constrained
_max = 0.52 e Å^-3
_min = -0.48 e Å^-3

Table 1
Selected geometric parameters (Å, °)

Zr1-O1	1.921 (3)
Zr1-Cl1	2.4857 (12)
Zr2-O1	1.980 (3)
Zr2-O1ⁱ	1.980 (2)

O1-Zr1-Cl1	97.23 (8)
O1-Zr2-O1ⁱ	102.43 (15)
Zr1-O1-Zr2	171.43 (15)
Symmetry code: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008a); molecular graphics: SHELXTL (Sheldrick, 2008a); software used to prepare material for publication: SHELXTL.

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PK2418 ).

References

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