Tetra­chlorido[(diphenyl­phosphino)diphenyl­phosphine oxide-κO]zirconium(IV) benzene monosolvate

Takahiko Ogawa; Yuji Kajita; Hideki Masuda

doi:10.1107/S1600536809031882

. 2009 Aug 22;65(Pt 9):m1129. doi: 10.1107/S1600536809031882

Tetrachlorido[(diphenylphosphino)diphenylphosphine oxide-κO]zirconium(IV) benzene monosolvate

Takahiko Ogawa ^a, Yuji Kajita ^a, Hideki Masuda ^a,^*

PMCID: PMC2969906 PMID: 21577468

Abstract

In the title centrosymmetric mononuclear Zr^IV compound, [ZrCl₄{P(O)(C₆H₅)₂P(C₆H₅)₂}₂]·C₆H₆, the central Zr^IV ion is coordinated by two O atoms from two symmetry-related (diphenylphosphino)diphenylphosphine ligands and four Cl atoms in a distorted octahedral geometry with the four Cl atoms in the equatorial positions. The molecule lies about a center of inversion and the benzene solvent molecule about another center of inversion. The P=O bond [1.528 (2) Å] is slightly longer than a typical P=O double bond (average 1.500 ).

Related literature

For general background to the structure and coordination mode of (diphenylphosphino)diphenylphosphine (DPDP), see: Ferguson et al. (1990 ▶); Kuramshin & Khramov (1983 ▶). For a Zr^IVcomplex with a DPDP ligand, see: Muratova et al. (1980 ▶). For comparison P–O bond distances, see: Berners-Price et al. (2009 ▶).

Experimental

Crystal data

[ZrCl₄(C₂₄H₂₀OP₂)₂]·C₆H₆
M _r = 1083.81
Triclinic,
a = 9.6073 (3) Å
b = 10.1521 (4) Å
c = 14.0204 (10) Å
α = 79.027 (13)°
β = 87.269 (13)°
γ = 73.096 (11)°
V = 1284.42 (11) Å³
Z = 1
Mo Kα radiation
μ = 0.59 mm⁻¹
T = 173 K
0.30 × 0.15 × 0.13 mm

Data collection

Rigaku Mercury diffractometer
Absorption correction: multi-scan (Jacobson, 1998 ▶) T _min = 0.900, T _max = 0.927
10324 measured reflections
5669 independent reflections
4497 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.151
S = 1.02
5669 reflections
296 parameters
H-atom parameters constrained
Δρ_max = 1.04 e Å⁻³
Δρ_min = −0.81 e Å⁻³

Data collection: CrystalClear (Rigaku, 2007 ▶); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku, 2007 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: CrystalStructure.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809031882/ng2624sup1.cif

e-65-m1129-sup1.cif^{(31.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809031882/ng2624Isup2.hkl

e-65-m1129-Isup2.hkl^{(277.5KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Zr1—Cl1	2.4450 (9)
Zr1—Cl2	2.4627 (7)
Zr1—O1	2.0820 (18)

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Acknowledgments

We gratefully acknowledge the support of this work by a Grant-in-Aid for Scientific Research from the Ministry of Education, Science, Sports and Culture.

supplementary crystallographic information

Comment

The phosphinoyl derivative, (diphenylphosphino)diphenylphosphine (DPDP), has a unique structure and coordination mode (Ferguson 1990 and Muratova et al., 1980). The complex which contains DPDP ligands is very rare and is a novel Zr^IVcomplex with DPDP ligand (Kuramshin & Khramov et al., 1983). The centrosymmetric unit of the title compound, [ZrCl₄(C₂₄H₂₀P₂O)₂] C₆H₆, contains a neutral Zr^IV complex and a solvent benzene molecule (Fig. 1). The compound crystallized in the triclinic space group P1. In the complex, the Zr^IV ion is six-coordinated in a slightly distorted octahedral environment by two O atoms of DPDP ligand and four Cl ions. The P atoms do not coordinate to the Zr^IV atom. The Zr—Cl(1) [2.4450 (9) Å] and Zr—Cl(2) [2.4627 (9) Å] bond lengths are slightly different each other (Table 1). The P—O bond length [1.5281 (19) Å] is slightly longer compared with a typical double bond (Berners-Price et al., 2009). The P—P bond length [2.2057 (10) Å] is similar to several P^III—P^V derivatives.

Experimental

The title compound was prepared by the reaction of ZrCl₄ (0.03 g, 0.13 mmol) and (diphenylphosphino)diphenylphosphine (0.10 g, 0.26 mmol) in benzene (5 ml). The mixture was filtered and set aside to crystallize at ambient temperature for several days, giving colorless single crystals.