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

Ogawa, T.; Kajita, Y.; Masuda, H.

doi:10.1107/S1600536809031882

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page m1129

doi:10.1107/S1600536809031882

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ADDENDA AND ERRATA

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

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

^aDepartment of Applied Chemistry, Nagoya Institute of Technology, Showa-ku, Nagoya 466-8555, Japan
^*Correspondence e-mail: masuda.hideki@nitech.ac.jp

(Received 10 August 2009; accepted 12 August 2009; online 22 August 2009)

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, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.045
wR(F²) = 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

Table 1
Selected bond lengths (Å)

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

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.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

For general background to the structure and coordination mode of (diphenylphosphino)diphenylphosphine (DPDP), see: Ferguson (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 top

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.

Computing details top

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); 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 (Rigaku, 2007).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Primed atoms are generated by the symmetry operator ((i) -x + 2, -y, -z + 2; (ii) -x + 1, -y + 1, -z + 1).
	Fig. 2. A partial packing diagram of the title compound.

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

Crystal data top

[ZrCl₄(C₂₄H₂₀OP₂)₂]·C₆H₆	Z = 1
M_r = 1083.81	F(000) = 554.00
Triclinic, P1	D_x = 1.401 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71070 Å
a = 9.6073 (3) Å	Cell parameters from 3589 reflections
b = 10.1521 (4) Å	θ = 3.2–27.5°
c = 14.0204 (10) Å	µ = 0.59 mm⁻¹
α = 79.027 (13)°	T = 173 K
β = 87.269 (13)°	Chip, colorless
γ = 73.096 (11)°	0.30 × 0.15 × 0.13 mm
V = 1284.42 (11) Å³

Data collection top

Rigaku Mercury diffractometer	4497 reflections with F² > 2σ(F²)
Detector resolution: 7.31 pixels mm^-1	R_int = 0.031
ω scans	θ_max = 27.5°
Absorption correction: multi-scan (Jacobson, 1998)	h = −12→12
T_min = 0.900, T_max = 0.927	k = −11→13
10324 measured reflections	l = −13→18
5669 independent reflections

Refinement top

Refinement on F²	0 restraints
R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.151	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
5669 reflections	Δρ_max = 1.04 e Å⁻³
296 parameters	Δρ_min = −0.81 e Å⁻³

Crystal data top

[ZrCl₄(C₂₄H₂₀OP₂)₂]·C₆H₆	γ = 73.096 (11)°
M_r = 1083.81	V = 1284.42 (11) Å³
Triclinic, P1	Z = 1
a = 9.6073 (3) Å	Mo Kα radiation
b = 10.1521 (4) Å	µ = 0.59 mm⁻¹
c = 14.0204 (10) Å	T = 173 K
α = 79.027 (13)°	0.30 × 0.15 × 0.13 mm
β = 87.269 (13)°

Data collection top

Rigaku Mercury diffractometer	5669 independent reflections
Absorption correction: multi-scan (Jacobson, 1998)	4497 reflections with F² > 2σ(F²)
T_min = 0.900, T_max = 0.927	R_int = 0.031
10324 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.151	H-atom parameters constrained
S = 1.02	Δρ_max = 1.04 e Å⁻³
5669 reflections	Δρ_min = −0.81 e Å⁻³
296 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 was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zr1	1	0	1	0.01849 (13)
Cl1	1.14353 (9)	0.14927 (8)	1.03401 (6)	0.0305 (2)
Cl2	0.79704 (8)	0.12426 (8)	1.09344 (6)	0.02711 (18)
P1	0.79655 (8)	0.24267 (8)	0.80566 (5)	0.01964 (17)
P2	0.87015 (9)	0.33171 (9)	0.66302 (6)	0.0249 (2)
O1	0.9163 (2)	0.1442 (2)	0.87498 (15)	0.0212 (4)
C1	0.6603 (3)	0.1623 (3)	0.7861 (2)	0.0239 (6)
C2	0.6455 (4)	0.1237 (4)	0.6987 (2)	0.0404 (9)
C3	0.5388 (4)	0.0607 (5)	0.6859 (3)	0.0509 (11)
C4	0.4473 (4)	0.0343 (4)	0.7626 (2)	0.0377 (8)
C5	0.4620 (3)	0.0716 (3)	0.8512 (2)	0.0346 (7)
C6	0.5688 (3)	0.1353 (3)	0.8631 (2)	0.0301 (7)
C7	0.7107 (3)	0.3971 (3)	0.8540 (2)	0.0245 (6)
C8	0.5776 (3)	0.4851 (3)	0.8158 (2)	0.0339 (7)
C9	0.5195 (4)	0.6137 (4)	0.8442 (3)	0.0471 (10)
C10	0.5940 (4)	0.6522 (4)	0.9110 (3)	0.0482 (10)
C11	0.7256 (4)	0.5653 (3)	0.9496 (2)	0.0401 (9)
C12	0.7856 (3)	0.4366 (3)	0.9215 (2)	0.0288 (7)
C13	0.9801 (3)	0.4239 (3)	0.7122 (2)	0.0284 (7)
C14	0.9168 (4)	0.5667 (3)	0.7125 (2)	0.0375 (8)
C15	0.9878 (5)	0.6405 (4)	0.7568 (3)	0.0476 (10)
C16	1.1218 (5)	0.5752 (4)	0.7984 (3)	0.0513 (11)
C17	1.1876 (4)	0.4354 (4)	0.7969 (3)	0.0484 (10)
C18	1.1170 (4)	0.3584 (4)	0.7553 (2)	0.0358 (8)
C19	1.0058 (3)	0.1844 (3)	0.6233 (2)	0.0276 (6)
C20	1.0628 (5)	0.2151 (4)	0.5313 (3)	0.0552 (12)
C21	1.1635 (5)	0.1132 (5)	0.4917 (3)	0.0686 (15)
C22	1.2062 (4)	−0.0226 (4)	0.5424 (2)	0.0423 (9)
C23	1.1486 (4)	−0.0549 (4)	0.6320 (2)	0.0410 (9)
C24	1.0484 (4)	0.0476 (3)	0.6725 (2)	0.0358 (8)
C25	0.4088 (12)	0.5582 (15)	0.5682 (6)	0.165 (7)
C26	0.5127 (14)	0.6167 (11)	0.5268 (8)	0.167 (5)
C27	0.6047 (12)	0.5579 (14)	0.4560 (7)	0.171 (6)
H1	0.7090	0.1403	0.6467	0.049*
H2	0.5285	0.0358	0.6252	0.061*
H3	0.3746	−0.0093	0.7543	0.045*
H4	0.3994	0.0537	0.9034	0.041*
H5	0.5794	0.1603	0.9237	0.036*
H6	0.5267	0.4573	0.7704	0.041*
H7	0.4292	0.6746	0.8179	0.056*
H8	0.5540	0.7399	0.9307	0.058*
H9	0.7753	0.5936	0.9954	0.048*
H10	0.8763	0.3765	0.9477	0.035*
H11	0.8247	0.6134	0.6823	0.045*
H12	0.9430	0.7368	0.7582	0.057*
H13	1.1700	0.6262	0.8285	0.061*
H14	1.2819	0.3914	0.8245	0.058*
H15	1.1616	0.2615	0.7562	0.043*
H16	1.0318	0.3079	0.4953	0.066*
H17	1.2033	0.1364	0.4296	0.082*
H18	1.2752	−0.0933	0.5153	0.051*
H19	1.1776	−0.1486	0.6668	0.049*
H20	1.0088	0.0235	0.7345	0.043*
H21	0.3452	0.6006	0.6148	0.199*
H22	0.5231	0.6982	0.5461	0.200*
H23	0.6756	0.6003	0.4258	0.205*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zr1	0.0175 (2)	0.0156 (2)	0.0215 (2)	−0.00302 (15)	0.00179 (15)	−0.00429 (15)
Cl1	0.0292 (4)	0.0249 (3)	0.0416 (4)	−0.0116 (3)	−0.0023 (3)	−0.0096 (3)
Cl2	0.0237 (3)	0.0243 (3)	0.0309 (4)	−0.0023 (3)	0.0078 (3)	−0.0082 (3)
P1	0.0202 (3)	0.0174 (3)	0.0200 (3)	−0.0032 (2)	0.0018 (2)	−0.0041 (2)
P2	0.0277 (4)	0.0234 (4)	0.0211 (3)	−0.0051 (3)	0.0007 (3)	−0.0013 (3)
O1	0.0228 (10)	0.0185 (9)	0.0204 (10)	−0.0038 (8)	−0.0003 (8)	−0.0020 (8)
C1	0.0240 (14)	0.0194 (14)	0.0268 (15)	−0.0042 (12)	0.0027 (12)	−0.0045 (12)
C2	0.043 (2)	0.063 (2)	0.0286 (17)	−0.032 (2)	0.0102 (15)	−0.0183 (17)
C3	0.057 (2)	0.075 (3)	0.042 (2)	−0.042 (2)	0.0090 (19)	−0.029 (2)
C4	0.0338 (18)	0.044 (2)	0.042 (2)	−0.0189 (17)	−0.0023 (15)	−0.0118 (17)
C5	0.0272 (16)	0.0403 (19)	0.0376 (19)	−0.0138 (15)	0.0068 (14)	−0.0054 (15)
C6	0.0313 (17)	0.0321 (17)	0.0274 (16)	−0.0106 (14)	0.0035 (13)	−0.0057 (13)
C7	0.0252 (15)	0.0184 (14)	0.0291 (15)	−0.0046 (12)	0.0053 (12)	−0.0064 (12)
C8	0.0274 (16)	0.0271 (16)	0.045 (2)	−0.0015 (14)	−0.0034 (15)	−0.0106 (15)
C9	0.036 (2)	0.033 (2)	0.063 (2)	0.0057 (16)	0.0071 (19)	−0.0124 (19)
C10	0.060 (2)	0.0254 (18)	0.055 (2)	−0.0007 (18)	0.014 (2)	−0.0178 (17)
C11	0.063 (2)	0.0270 (17)	0.0353 (19)	−0.0181 (18)	0.0053 (17)	−0.0107 (15)
C12	0.0389 (18)	0.0210 (15)	0.0262 (15)	−0.0097 (14)	0.0031 (13)	−0.0026 (12)
C13	0.0317 (16)	0.0284 (16)	0.0237 (15)	−0.0091 (14)	0.0075 (13)	−0.0025 (12)
C14	0.049 (2)	0.0249 (17)	0.0371 (19)	−0.0130 (16)	0.0107 (16)	0.0007 (14)
C15	0.072 (3)	0.0304 (19)	0.047 (2)	−0.026 (2)	0.019 (2)	−0.0107 (17)
C16	0.070 (3)	0.053 (2)	0.049 (2)	−0.041 (2)	0.012 (2)	−0.019 (2)
C17	0.046 (2)	0.060 (2)	0.049 (2)	−0.028 (2)	−0.0003 (19)	−0.015 (2)
C18	0.0355 (18)	0.0371 (19)	0.0354 (18)	−0.0113 (16)	0.0031 (15)	−0.0074 (15)
C19	0.0296 (16)	0.0298 (16)	0.0247 (15)	−0.0089 (13)	0.0026 (12)	−0.0080 (13)
C20	0.077 (3)	0.036 (2)	0.045 (2)	−0.008 (2)	0.030 (2)	−0.0062 (18)
C21	0.085 (3)	0.056 (2)	0.046 (2)	0.003 (2)	0.039 (2)	−0.009 (2)
C22	0.050 (2)	0.041 (2)	0.0311 (18)	−0.0035 (18)	0.0114 (16)	−0.0136 (16)
C23	0.051 (2)	0.0328 (18)	0.0328 (18)	−0.0020 (17)	0.0065 (17)	−0.0076 (15)
C24	0.047 (2)	0.0298 (17)	0.0247 (16)	−0.0032 (15)	0.0104 (15)	−0.0053 (13)
C25	0.142 (9)	0.180 (11)	0.057 (4)	0.105 (9)	0.007 (4)	0.026 (6)
C26	0.168 (10)	0.152 (9)	0.091 (6)	0.074 (8)	−0.027 (6)	0.014 (6)
C27	0.146 (8)	0.169 (10)	0.084 (6)	0.082 (8)	0.016 (5)	0.048 (6)

Geometric parameters (Å, º) top

Zr1—Cl1	2.4450 (9)	C19—C24	1.380 (4)
Zr1—Cl1ⁱ	2.4450 (9)	C20—C21	1.379 (6)
Zr1—Cl2	2.4627 (7)	C21—C22	1.377 (5)
Zr1—Cl2ⁱ	2.4627 (7)	C22—C23	1.369 (5)
Zr1—O1	2.0820 (18)	C23—C24	1.386 (5)
Zr1—O1ⁱ	2.0820 (18)	C25—C26	1.358 (19)
P1—P2	2.2057 (10)	C25—C27ⁱⁱ	1.33 (2)
P1—O1	1.5281 (19)	C26—C27	1.399 (16)
P1—C1	1.787 (3)	C2—H1	0.950
P1—C7)	1.788 (3)	C3—H2	0.950
P2—C13	1.833 (4)	C4—H3	0.950
P2—C19	1.833 (3)	C5—H4	0.950
C1—C2	1.382 (5)	C6—H5	0.950
C1—C6	1.397 (4)	C8—H6	0.950
C2—C3	1.391 (7)	C9—H7	0.950
C3—C4	1.392 (6)	C10—H8	0.950
C4—C5	1.390 (6)	C11—H9	0.950
C5—C6	1.394 (6)	C12—H10	0.950
C7—C8	1.393 (4)	C14—H11	0.950
C7—C12	1.397 (5)	C15—H12	0.950
C8—C9	1.387 (5)	C16—H13	0.950
C9—C10	1.382 (7)	C17—H14	0.950
C10—C11	1.379 (5)	C18—H15	0.950
C11—C12	1.389 (5)	C20—H16	0.950
C13—C14	1.400 (4)	C21—H17	0.950
C13—C18	1.397 (4)	C22—H18	0.950
C14—C15	1.388 (7)	C23—H19	0.950
C15—C16	1.366 (6)	C24—H20	0.950
C16—C17	1.379 (6)	C25—H21	0.950
C17—C18	1.390 (7)	C26—H22	0.950
C19—C20	1.392 (5)	C27—H23	0.950

Cl(1)···C(11)ⁱⁱⁱ	3.525 (4)	H(7)···H(3)^xi	3.057
Cl(2)···C(4)^iv	3.562 (4)	H(7)···H(13)^ix	2.668
Cl(2)···C(5)^iv	3.585 (4)	H(7)···H(14)^ix	3.540
C(4)···Cl(2)^iv	3.562 (4)	H(7)···H(19)^xiii	3.174
C(5)···Cl(2)^iv	3.585 (4)	H(7)···H(21)	3.273
C(11)···Cl(1)ⁱⁱⁱ	3.525 (4)	H(8)···Cl(1)ⁱⁱⁱ	3.494
Cl(1)···H(4)^v	3.032	H(8)···Cl(2)^vi	3.258
Cl(1)···H(8)ⁱⁱⁱ	3.494	H(8)···C(4)^xi	3.362
Cl(1)···H(9)ⁱⁱⁱ	2.887	H(8)···C(5)^xi	3.208
Cl(1)···H(12)ⁱⁱⁱ	3.318	H(8)···C(6)^vi	3.398
Cl(2)···H(3)^iv	2.911	H(8)···H(3)^xi	3.321
Cl(2)···H(4)^iv	2.961	H(8)···H(4)^xi	3.055
Cl(2)···H(7)^vi	2.927	H(8)···H(4)^vi	3.535
Cl(2)···H(8)^vi	3.258	H(8)···H(5)^vi	2.572
Cl(2)···H(13)ⁱⁱⁱ	3.045	H(9)···Cl(1)ⁱⁱⁱ	2.887
C(2)···H(17)^vii	3.413	H(9)···C(16)ⁱⁱⁱ	3.110
C(2)···H(18)^vii	3.110	H(9)···C(17)ⁱⁱⁱ	2.899
C(3)···H(17)^vii	3.277	H(9)···H(10)ⁱⁱⁱ	3.588
C(3)···H(18)^vii	3.282	H(9)···H(13)ⁱⁱⁱ	2.949
C(3)···H(23)ⁱⁱ	3.560	H(9)···H(14)ⁱⁱⁱ	2.582
C(4)···H(8)^viii	3.362	H(10)···H(9)ⁱⁱⁱ	3.588
C(4)···H(15)^ix	3.020	H(10)···H(13)ⁱⁱⁱ	3.143
C(5)···H(8)^viii	3.208	H(11)···C(20)^x	3.460
C(5)···H(14)^ix	3.164	H(11)···C(21)^x	3.354
C(5)···H(15)^ix	3.157	H(11)···H(16)^x	2.879
C(6)···H(4)^iv	3.442	H(11)···H(17)^x	2.667
C(6)···H(8)^vi	3.398	H(11)···H(22)	3.352
C(6)···H(14)^ix	3.176	H(12)···Cl(1)ⁱⁱⁱ	3.318
C(8)···H(14)^ix	3.237	H(12)···C(23)^xi	3.490
C(8)···H(21)	3.481	H(12)···C(24)^xi	3.568
C(9)···H(13)^ix	3.339	H(12)···H(17)^x	2.930
C(10)···H(5)^vi	3.352	H(12)···H(19)^xi	2.960
C(11)···H(13)ⁱⁱⁱ	3.366	H(12)···H(20)^xi	3.109
C(11)···H(14)ⁱⁱⁱ	3.275	H(13)···Cl(2)ⁱⁱⁱ	3.045
C(12)···H(13)ⁱⁱⁱ	3.465	H(13)···C(9)^v	3.339
C(13)···H(16)^x	3.566	H(13)···C(11)ⁱⁱⁱ	3.366
C(14)···H(16)^x	3.027	H(13)···C(12)ⁱⁱⁱ	3.465
C(14)···H(17)^x	3.209	H(13)···H(6)^v	3.492
C(15)···H(16)^x	3.479	H(13)···H(7)^v	2.668
C(15)···H(17)^x	3.335	H(13)···H(9)ⁱⁱⁱ	2.949
C(15)···H(19)^xi	3.244	H(13)···H(10)ⁱⁱⁱ	3.143
C(16)···H(7)^v	3.426	H(13)···H(19)^xi	2.912
C(16)···H(9)ⁱⁱⁱ	3.110	H(13)···H(21)^v	3.382
C(16)···H(19)^xi	3.220	H(14)···C(5)^v	3.164
C(16)···H(21)^v	3.293	H(14)···C(6)^v	3.176
C(17)···H(6)^v	3.327	H(14)···C(8)^v	3.237
C(17)···H(9)ⁱⁱⁱ	2.899	H(14)···C(11)ⁱⁱⁱ	3.275
C(17)···H(21)^v	3.332	H(14)···H(4)^v	3.268
C(17)···H(23)^x	3.371	H(14)···H(5)^v	3.293
C(18)···H(23)^x	3.192	H(14)···H(6)^v	2.665
C(20)···H(11)^x	3.460	H(14)···H(7)^v	3.540
C(21)···H(1)^vii	3.425	H(14)···H(9)ⁱⁱⁱ	2.582
C(21)···H(2)^vii	3.408	H(14)···H(21)^v	3.424
C(21)···H(11)^x	3.354	H(14)···H(23)^x	3.500
C(22)···H(1)^vii	3.091	H(15)···C(4)^v	3.020
C(22)···H(2)^v	3.600	H(15)···C(5)^v	3.157
C(22)···H(2)^vii	3.375	H(15)···H(3)^v	2.914
C(22)···H(3)^v	3.494	H(15)···H(4)^v	3.149
C(22)···H(22)^xii	3.500	H(15)···H(23)^x	3.233
C(23)···H(3)^v	3.020	H(16)···C(13)^x	3.566
C(23)···H(12)^viii	3.490	H(16)···C(14)^x	3.027
C(23)···H(21)^xii	3.506	H(16)···C(15)^x	3.479
C(24)···H(3)^v	3.242	H(16)···H(11)^x	2.879
C(24)···H(12)^viii	3.568	H(16)···H(23)^x	3.494
C(25)···H(6)	2.983	H(17)···C(2)^vii	3.413
C(25)···H(18)^xiii	3.342	H(17)···C(3)^vii	3.277
C(26)···H(1)ⁱⁱ	3.419	H(17)···C(14)^x	3.209
C(26)···H(6)	3.481	H(17)···C(15)^x	3.335
C(26)···H(18)^xiii	3.138	H(17)···H(1)^vii	3.071
C(27)···H(6)ⁱⁱ	3.518	H(17)···H(2)^vii	2.827
H(1)···C(21)^vii	3.425	H(17)···H(11)^x	2.667
H(1)···C(22)^vii	3.091	H(17)···H(12)^x	2.930
H(1)···C(26)ⁱⁱ	3.419	H(17)···H(22)^x	3.566
H(1)···H(17)^vii	3.071	H(18)···C(2)^vii	3.110
H(1)···H(18)^vii	2.397	H(18)···C(3)^vii	3.282
H(1)···H(22)ⁱⁱ	3.424	H(18)···C(25)^xii	3.342
H(2)···C(21)^vii	3.408	H(18)···C(26)^xii	3.138
H(2)···C(22)^ix	3.600	H(18)···H(1)^vii	2.397
H(2)···C(22)^vii	3.375	H(18)···H(2)^vii	2.762
H(2)···H(17)^vii	2.827	H(18)···H(21)^xii	3.046
H(2)···H(18)^vii	2.762	H(18)···H(22)^xii	2.675
H(2)···H(22)ⁱⁱ	3.190	H(19)···C(15)^viii	3.244
H(2)···H(23)ⁱⁱ	3.595	H(19)···C(16)^viii	3.220
H(3)···Cl(2)^iv	2.911	H(19)···H(3)^v	3.088
H(3)···C(22)^ix	3.494	H(19)···H(7)^xii	3.174
H(3)···C(23)^ix	3.020	H(19)···H(12)^viii	2.960
H(3)···C(24)^ix	3.242	H(19)···H(13)^viii	2.912
H(3)···H(7)^viii	3.057	H(19)···H(21)^xii	2.796
H(3)···H(8)^viii	3.321	H(20)···H(3)^v	3.452
H(3)···H(15)^ix	2.914	H(20)···H(12)^viii	3.109
H(3)···H(19)^ix	3.088	H(21)···C(8)	3.481
H(3)···H(20)^ix	3.452	H(21)···C(16)^ix	3.293
H(4)···Cl(1)^ix	3.032	H(21)···C(17)^ix	3.332
H(4)···Cl(2)^iv	2.961	H(21)···C(23)^xiii	3.506
H(4)···C(6)^iv	3.442	H(21)···H(6)	2.756
H(4)···H(4)^iv	3.226	H(21)···H(7)	3.273
H(4)···H(5)^iv	2.901	H(21)···H(13)^ix	3.382
H(4)···H(8)^viii	3.055	H(21)···H(14)^ix	3.424
H(4)···H(8)^vi	3.535	H(21)···H(18)^xiii	3.046
H(4)···H(14)^ix	3.268	H(21)···H(19)^xiii	2.796
H(4)···H(15)^ix	3.149	H(22)···C(22)^xiii	3.500
H(5)···C(10)^vi	3.352	H(22)···H(1)ⁱⁱ	3.424
H(5)···H(4)^iv	2.901	H(22)···H(2)ⁱⁱ	3.190
H(5)···H(8)^vi	2.572	H(22)···H(6)	3.593
H(5)···H(14)^ix	3.293	H(22)···H(11)	3.352
H(6)···C(17)^ix	3.327	H(22)···H(17)^x	3.566
H(6)···C(25)	2.983	H(22)···H(18)^xiii	2.675
H(6)···C(26)	3.481	H(23)···C(3)ⁱⁱ	3.560
H(6)···C(27)ⁱⁱ	3.518	H(23)···C(17)^x	3.371
H(6)···H(13)^ix	3.492	H(23)···C(18)^x	3.192
H(6)···H(14)^ix	2.665	H(23)···H(2)ⁱⁱ	3.595
H(6)···H(21)	2.756	H(23)···H(14)^x	3.500
H(6)···H(22)	3.593	H(23)···H(15)^x	3.233
H(7)···Cl(2)^vi	2.927	H(23)···H(16)^x	3.494
H(7)···C(16)^ix	3.426

Cl(1)—Zr(1)—Cl(1)ⁱ	180	C(20)—C(21)—C(22)	119.9 (4)
Cl(1)—Zr(1)—Cl(2)	89.73 (2)	C(21)—C(22)—C(23)	119.6 (3)
Cl(1)—Zr(1)—Cl(2)ⁱ	90.27 (2)	C(22)—C(23)—C(24)	120.7 (3)
Cl(1)—Zr(1)—O(1)	90.01 (7)	C(19)—C(24)—C(23)	120.5 (3)
Cl(1)—Zr(1)—O(1)ⁱ	89.99 (7)	C(26)—C(25)—C(27)ⁱⁱ	120.6 (10)
Cl(1)ⁱ—Zr(1)—Cl(2)	90.27 (2)	C(25)—C(26)—C(27)	120.5 (13)
Cl(1)ⁱ—Zr(1)—Cl(2)ⁱ	89.73 (2)	C(25)ⁱⁱ—C(27)—C(26)	118.9 (12)
Cl(1)ⁱ—Zr(1)—O(1)	89.99 (7)	C(1)—C(2)—H(1)	119.6
Cl(1)ⁱ—Zr(1)—O(1)ⁱ	90.01 (7)	C(3)—C(2)—H(1)	119.6
Cl(2)—Zr(1)—Cl(2)ⁱ	180	C(2)—C(3)—H(2)	120.2
Cl(2)—Zr(1)—O(1)	89.43 (5)	C(4)—C(3)—H(2)	120.2
Cl(2)—Zr(1)—O(1)ⁱ	90.57 (5)	C(3)—C(4)—H(3)	119.9
Cl(2)ⁱ—Zr(1)—O(1)	90.57 (5)	C(5)—C(4)—H(3)	119.9
Cl(2)ⁱ—Zr(1)—O(1)ⁱ	89.43 (5)	C(4)—C(5)—H(4)	120.1
O(1)—Zr(1)—O(1)ⁱ	180	C(6)—C(5)—H(4)	120.1
P(2)—P(1)—O(1)	115.79 (9)	C(1)—C(6)—H(5)	120.0
P(2)—P(1)—C(1)	108.46 (10)	C(5)—C(6)—H(5)	120.0
P(2)—P(1)—C(7)	101.63 (10)	C(7)—C(8)—H(6)	120.1
O(1)—P(1)—C(1)	111.99 (13)	C(9)—C(8)—H(6)	120.1
O(1)—P(1)—C(7)	109.97 (14)	C(8)—C(9)—H(7)	120.3
C(1)—P(1)—C(7)	108.32 (15)	C(10)—C(9)—H(7)	120.3
P(1)—P(2)—C(13)	95.26 (11)	C(9)—C(10)—H(8)	119.4
P(1)—P(2)—C(19)	105.04 (10)	C(11)—C(10)—H(8)	119.5
C(13)—P(2)—C(19)	103.65 (16)	C(10)—C(11)—H(9)	119.9
Zr(1)—O(1)—P(1)	155.63 (13)	C(12)—C(11)—H(9)	119.9
P(1)—C(1)—C(2)	122.1 (2)	C(7)—C(12)—H(10)	120.5
P(1)—C(1)—C(6)	118.3 (2)	C(11)—C(12)—H(10)	120.5
C(2)—C(1)—C(6)	119.6 (3)	C(13)—C(14)—H(11)	119.8
C(1)—C(2)—C(3)	120.7 (3)	C(15)—C(14)—H(11)	119.8
C(2)—C(3)—C(4)	119.7 (4)	C(14)—C(15)—H(12)	119.9
C(3)—C(4)—C(5)	120.1 (4)	C(16)—C(15)—H(12)	119.9
C(4)—C(5)—C(6)	119.8 (3)	C(15)—C(16)—H(13)	119.8
C(1)—C(6)—C(5)	120.1 (3)	C(17)—C(16)—H(13)	119.8
P(1)—C(7)—C(8)	119.6 (2)	C(16)—C(17)—H(14)	119.8
P(1)—C(7)—C(12)	119.5 (2)	C(18)—C(17)—H(14)	119.8
C(8)—C(7)—C(12)	120.4 (3)	C(13)—C(18)—H(15)	120.1
C(7)—C(8)—C(9)	119.8 (3)	C(17)—C(18)—H(15)	120.1
C(8)—C(9)—C(10)	119.4 (3)	C(19)—C(20)—H(16)	119.4
C(9)—C(10)—C(11)	121.1 (3)	C(21)—C(20)—H(16)	119.4
C(10)—C(11)—C(12)	120.2 (4)	C(20)—C(21)—H(17)	120.1
C(7)—C(12)—C(11)	119.0 (3)	C(22)—C(21)—H(17)	120.1
P(2)—C(13)—C(14)	117.1 (2)	C(21)—C(22)—H(18)	120.2
P(2)—C(13)—C(18)	124.0 (2)	C(23)—C(22)—H(18)	120.2
C(14)—C(13)—C(18)	118.8 (3)	C(22)—C(23)—H(19)	119.6
C(13)—C(14)—C(15)	120.4 (3)	C(24)—C(23)—H(19)	119.6
C(14)—C(15)—C(16)	120.2 (3)	C(19)—C(24)—H(20)	119.8
C(15)—C(16)—C(17)	120.3 (5)	C(23)—C(24)—H(20)	119.8
C(16)—C(17)—C(18)	120.5 (4)	C(26)—C(25)—H(21)	119.7
C(13)—C(18)—C(17)	119.8 (3)	C(27)ⁱⁱ—C(25)—H(21)	119.7
P(2)—C(19)—C(20)	115.2 (2)	C(25)—C(26)—H(22)	119.7
P(2)—C(19)—C(24)	126.5 (2)	C(27)—C(26)—H(22)	119.8
C(20)—C(19)—C(24)	118.2 (3)	C(25)ⁱⁱ—C(27)—H(23)	120.6
C(19)—C(20)—C(21)	121.1 (3)	C(26)—C(27)—H(23)	120.6

Cl(1)—Zr(1)—O(1)—P(1)	−126.6 (3)	C(19)—P(2)—C(13)—C(18)	−30.0 (3)
Cl(1)—Zr(1)—O(1)ⁱ—P(1)ⁱ	−53.4 (3)	P(1)—C(1)—C(2)—C(3)	179.7 (2)
Cl(1)ⁱ—Zr(1)—O(1)—P(1)	53.4 (3)	P(1)—C(1)—C(6)—C(5)	−179.4 (2)
Cl(1)ⁱ—Zr(1)—O(1)ⁱ—P(1)ⁱ	126.6 (3)	C(2)—C(1)—C(6)—C(5)	−1.0 (4)
Cl(2)—Zr(1)—O(1)—P(1)	−36.8 (3)	C(6)—C(1)—C(2)—C(3)	1.3 (5)
Cl(2)—Zr(1)—O(1)ⁱ—P(1)ⁱ	−143.2 (3)	C(1)—C(2)—C(3)—C(4)	−1.0 (5)
Cl(2)ⁱ—Zr(1)—O(1)—P(1)	143.2 (3)	C(2)—C(3)—C(4)—C(5)	0.4 (5)
Cl(2)ⁱ—Zr(1)—O(1)ⁱ—P(1)ⁱ	36.8 (3)	C(3)—C(4)—C(5)—C(6)	−0.1 (4)
P(2)—P(1)—O(1)—Zr(1)	−171.5 (3)	C(4)—C(5)—C(6)—C(1)	0.4 (4)
O(1)—P(1)—P(2)—C(13)	−61.58 (14)	P(1)—C(7)—C(8)—C(9)	−171.8 (3)
O(1)—P(1)—P(2)—C(19)	44.08 (17)	P(1)—C(7)—C(12)—C(11)	172.2 (2)
P(2)—P(1)—C(1)—C(2)	19.8 (2)	C(8)—C(7)—C(12)—C(11)	−0.2 (5)
P(2)—P(1)—C(1)—C(6)	−161.7 (2)	C(12)—C(7)—C(8)—C(9)	0.6 (5)
C(1)—P(1)—P(2)—C(13)	171.56 (13)	C(7)—C(8)—C(9)—C(10)	−0.7 (6)
C(1)—P(1)—P(2)—C(19)	−82.77 (16)	C(8)—C(9)—C(10)—C(11)	0.4 (6)
P(2)—P(1)—C(7)—C(8)	72.2 (2)	C(9)—C(10)—C(11)—C(12)	−0.0 (6)
P(2)—P(1)—C(7)—C(12)	−100.3 (2)	C(10)—C(11)—C(12)—C(7)	−0.1 (4)
C(7)—P(1)—P(2)—C(13)	57.55 (15)	P(2)—C(13)—C(14)—C(15)	173.9 (3)
C(7)—P(1)—P(2)—C(19)	163.22 (17)	P(2)—C(13)—C(18)—C(17)	−175.3 (2)
O(1)—P(1)—C(1)—C(2)	−109.2 (2)	C(14)—C(13)—C(18)—C(17)	−0.4 (5)
O(1)—P(1)—C(1)—C(6)	69.2 (2)	C(18)—C(13)—C(14)—C(15)	−1.4 (5)
C(1)—P(1)—O(1)—Zr(1)	−46.5 (4)	C(13)—C(14)—C(15)—C(16)	1.6 (6)
O(1)—P(1)—C(7)—C(8)	−164.6 (2)	C(14)—C(15)—C(16)—C(17)	−0.1 (5)
O(1)—P(1)—C(7)—C(12)	22.9 (3)	C(15)—C(16)—C(17)—C(18)	−1.6 (6)
C(7)—P(1)—O(1)—Zr(1)	74.0 (3)	C(16)—C(17)—C(18)—C(13)	1.9 (6)
C(1)—P(1)—C(7)—C(8)	−41.9 (3)	P(2)—C(19)—C(20)—C(21)	−178.6 (4)
C(1)—P(1)—C(7)—C(12)	145.6 (2)	P(2)—C(19)—C(24)—C(23)	177.4 (3)
C(7)—P(1)—C(1)—C(2)	129.4 (2)	C(20)—C(19)—C(24)—C(23)	1.9 (6)
C(7)—P(1)—C(1)—C(6)	−52.2 (2)	C(24)—C(19)—C(20)—C(21)	−2.5 (7)
P(1)—P(2)—C(13)—C(14)	−98.1 (2)	C(19)—C(20)—C(21)—C(22)	1.8 (8)
P(1)—P(2)—C(13)—C(18)	76.9 (2)	C(20)—C(21)—C(22)—C(23)	−0.3 (7)
P(1)—P(2)—C(19)—C(20)	177.0 (3)	C(21)—C(22)—C(23)—C(24)	−0.4 (7)
P(1)—P(2)—C(19)—C(24)	1.3 (3)	C(22)—C(23)—C(24)—C(19)	−0.5 (6)
C(13)—P(2)—C(19)—C(20)	−83.7 (3)	C(26)—C(25)—C(27)ⁱⁱ—C(26)ⁱⁱ	−1.8 (15)
C(13)—P(2)—C(19)—C(24)	100.6 (3)	C(27)ⁱⁱ—C(25)—C(26)—C(27)	1.8 (16)
C(19)—P(2)—C(13)—C(14)	155.0 (2)	C(25)—C(26)—C(27)—C(25)ⁱⁱ	−1.8 (15)

Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+1, −y+1, −z+1; (iii) −x+2, −y+1, −z+2; (iv) −x+1, −y, −z+2; (v) x+1, y, z; (vi) −x+1, −y+1, −z+2; (vii) −x+2, −y, −z+1; (viii) x, y−1, z; (ix) x−1, y, z; (x) −x+2, −y+1, −z+1; (xi) x, y+1, z; (xii) x+1, y−1, z; (xiii) x−1, y+1, z.

Experimental details

Crystal data
Chemical formula	[ZrCl₄(C₂₄H₂₀OP₂)₂]·C₆H₆
M_r	1083.81
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	9.6073 (3), 10.1521 (4), 14.0204 (10)
α, β, γ (°)	79.027 (13), 87.269 (13), 73.096 (11)
V (Å³)	1284.42 (11)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.59
Crystal size (mm)	0.30 × 0.15 × 0.13

Data collection
Diffractometer	Rigaku Mercury diffractometer
Absorption correction	Multi-scan (Jacobson, 1998)
T_min, T_max	0.900, 0.927
No. of measured, independent and observed [F² > 2σ(F²)] reflections	10324, 5669, 4497
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.151, 1.02
No. of reflections	5669
No. of parameters	296
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.04, −0.81

Computer programs: CrystalClear (Rigaku, 2007), CrystalStructure (Rigaku, 2007), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Selected bond lengths (Å) top

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

Acknowledgements

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.

References

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