trans-Dichloridobis[tris­(4-methoxy­phen­yl)phosphine]palladium(II) benzene monosolvate

Blerk, C. van; Holzapfel, C.W.

doi:10.1107/S1600536809046261

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page m1536

doi:10.1107/S1600536809046261

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trans-Dichloridobis[tris(4-methoxyphenyl)phosphine]palladium(II) benzene monosolvate

Charmaine van Blerk ^a ^* and Cedric W. Holzapfel ^a

^aUniversity of Johannesburg, Department of Chemistry, PO Box 524, Auckland Park, Johannesburg 2006, South Africa
^*Correspondence e-mail: cvanblerk@uj.ac.za

(Received 23 September 2009; accepted 3 November 2009; online 7 November 2009)

The structure of the title compound, [PdCl₂(C₂₁H₂₁O₃P)₂]·C₆H₆, shows a square-planar geometry for the Pd^II atom within a Cl₂[P(PhOMe)₃]₂ ligand set. The crystal structure contains benzene as solvent. The Pd^II atom sits on a centre of inversion and therefore the asymmetric unit contains the Pd^II atom, one Cl atom, one tris(4-methoxyphenyl)phosphine ligand and one half of the benzene solvent molecule.

Related literature

For related structures and literature on similar palladium complexes, see: Robertson & Cole-Hamilton (2002 ); Van Leeuwen et al. (2003 ); Williams et al. (2008 ).

Experimental

Crystal data

[PdCl₂(C₂₁H₂₁O₃P)₂]·C₆H₆
M_r = 960.10
Triclinic, $[P \overline 1]$
a = 7.9338 (2) Å
b = 12.1886 (3) Å
c = 12.5268 (3) Å
α = 85.981 (3)°
β = 78.840 (2)°
γ = 76.155 (2)°
V = 1153.57 (5) Å³
Z = 1
Mo Kα radiation
μ = 0.63 mm⁻¹
T = 295 K
0.34 × 0.24 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (APEX2 AX-Scale; Bruker, 2008 ) T_min = 0.813, T_max = 0.939
31847 measured reflections
5781 independent reflections
4546 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.097
S = 1.08
5781 reflections
271 parameters
H-atom parameters constrained
Δρ_max = 1.26 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Data collection: SMART-NT (Bruker, 1999 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809046261/ez2192sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809046261/ez2192Isup2.hkl

checkCIF report

Comment top

The palladium-catalysed methoxycarbonylation (Robertson & Cole-Hamilton, 2002) of 1-alkenes is an active area of research. The palladium complexes (Ar₃P)₂PdX₂ (X = Cl, DMS, OTf etc.) are the preferred catalysts but most quantitative studies have been carried out with complexes where the phosphine ligand is limited to triphenylphosphine. The X-ray structures (Van Leeuwen et al., 2003 and Williams et al., 2008) of several of this class of palladium(II) complexes have been determined. Our studies (Williams et al., 2008) on the effect of substituents on the triarylphosphine ligands on regioselectivity and reaction rate showed trans-dichloro-bis[tris-(4-methoxy)phosphine] palladium(II) to be an exceptionally efficient catalyst for the production of linear esters from 1-alkenes at high rates.

The structure of the title compound (I), [PdCl₂(C₄₂H₄₂P₂O₆).C₆H₆] shows a square planar geometry for the Pd^II atom within the Cl₂(P(PhOMe)₃) ligand set. The crystal structure contains benzene as a solvate. The solvent molecule exhibits noticeable disorder but this disorder was not modelled. The palladium atom sits on a centre of inversion and therefore the asymmetric unit contains the palladium atom, one chlorine atom, one tris-(4-methoxyphenyl)phenylphosphine ligand and one half of the benzene solvent molecule.

Related literature top

For related structures and literature on similar palladium complexes, see: Robertson & Cole-Hamilton (2002); Van Leeuwen et al. (2003); Williams et al. (2008).

Experimental top

Tris-(4-methoxyphenyl)phosphine (704 mg, 0.2 mmol) was added to a solution of lithium chloride (85 mg, 0.2 mmol) and palladium(II) chloride (177 mg, 0.1 mmol) in 15 ml me thanol. The mixture was heated under reflux in an atmosphere of nitrogen for 1 h resulting in the formation of the product as a yellow precipitate. The solution was allowed to cool to room temperature and the product (710 mg) was collected by filtration, washed with fresh methanol and dried under vacuum. The product was recrystallized from 1:1 ethyl acetate:benzene to furnish yellow plates (m. p. > 250°C, decomp.) A suitable single-crystal was selected for the single-crystal X-ray diffraction analysis.

Computing details top

Data collection: SMART-NT (Bruker, 1999); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001) and Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

Fig. 1. : Molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level. Atoms labelled with (i) are at symmetry position (– x, – y, – z) and atoms labelled with (ii) are at symmetry position (– x + 1, – y + 1, – z + 1)

trans-Dichloridobis[tris(4-methoxyphenyl)phosphine]palladium(II) benzene monosolvate top

Crystal data top

[PdCl₂(C₂₁H₂₁O₃P)₂]·C₆H₆	Z = 1
M_r = 960.10	F(000) = 494
Triclinic, P1	D_x = 1.382 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9338 (2) Å	Cell parameters from 9954 reflections
b = 12.1886 (3) Å	θ = 1.7–28.3°
c = 12.5268 (3) Å	µ = 0.63 mm⁻¹
α = 85.981 (3)°	T = 295 K
β = 78.840 (2)°	Flat, yellow
γ = 76.155 (2)°	0.34 × 0.24 × 0.10 mm
V = 1153.57 (5) Å³

Data collection top

Bruker SMART CCD diffractometer	5781 independent reflections
Radiation source: fine-focus sealed tube	4546 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ϕ and ω scans	θ_max = 28.4°, θ_min = 1.7°
Absorption correction: multi-scan (APEX2 Ax-Scale; Bruker, 2008)	h = −10→10
T_min = 0.813, T_max = 0.939	k = −16→16
31847 measured reflections	l = −16→16

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.04P)² + 0.8985P] where P = (F_o² + 2F_c²)/3
5781 reflections	(Δ/σ)_max < 0.001
271 parameters	Δρ_max = 1.26 e Å⁻³
0 restraints	Δρ_min = −0.53 e Å⁻³

Crystal data top

[PdCl₂(C₂₁H₂₁O₃P)₂]·C₆H₆	γ = 76.155 (2)°
M_r = 960.10	V = 1153.57 (5) Å³
Triclinic, P1	Z = 1
a = 7.9338 (2) Å	Mo Kα radiation
b = 12.1886 (3) Å	µ = 0.63 mm⁻¹
c = 12.5268 (3) Å	T = 295 K
α = 85.981 (3)°	0.34 × 0.24 × 0.10 mm
β = 78.840 (2)°

Data collection top

Bruker SMART CCD diffractometer	5781 independent reflections
Absorption correction: multi-scan (APEX2 Ax-Scale; Bruker, 2008)	4546 reflections with I > 2σ(I)
T_min = 0.813, T_max = 0.939	R_int = 0.046
31847 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.08	Δρ_max = 1.26 e Å⁻³
5781 reflections	Δρ_min = −0.53 e Å⁻³
271 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
C1	0.4425 (16)	0.4281 (7)	0.5761 (6)	0.155 (3)
H1	0.4046	0.3780	0.6295	0.186*
C2	0.5827 (15)	0.4708 (8)	0.5889 (6)	0.157 (3)
H2	0.6361	0.4503	0.6495	0.188*
C3	0.3558 (14)	0.4537 (7)	0.4915 (8)	0.164 (3)
H3	0.2608	0.4232	0.4866	0.197*
C11	0.0548 (3)	0.1003 (2)	−0.2660 (2)	0.0322 (5)
C12	−0.0842 (4)	0.0505 (3)	−0.2715 (2)	0.0394 (6)
H12	−0.1180	0.0008	−0.2162	0.047*
C13	−0.1725 (4)	0.0744 (3)	−0.3587 (2)	0.0457 (7)
H13	−0.2650	0.0406	−0.3614	0.055*
C14	−0.1248 (4)	0.1475 (3)	−0.4413 (2)	0.0415 (6)
C15	0.0146 (4)	0.1971 (3)	−0.4377 (2)	0.0491 (8)
H15	0.0490	0.2459	−0.4937	0.059*
C16	0.1017 (4)	0.1736 (3)	−0.3504 (2)	0.0451 (7)
H16	0.1941	0.2076	−0.3481	0.054*
C17	−0.1700 (5)	0.2373 (4)	−0.6136 (3)	0.0663 (10)
H17A	−0.1778	0.3112	−0.5882	0.099*
H17B	−0.2476	0.2429	−0.6647	0.099*
H17C	−0.0508	0.2058	−0.6484	0.099*
C21	0.2612 (3)	0.1876 (2)	−0.1422 (2)	0.0319 (5)
C22	0.4426 (4)	0.1803 (2)	−0.1504 (2)	0.0379 (6)
H22	0.5220	0.1107	−0.1627	0.046*
C23	0.5046 (4)	0.2750 (3)	−0.1406 (3)	0.0462 (7)
H23	0.6252	0.2685	−0.1460	0.055*
C24	0.3887 (4)	0.3800 (2)	−0.1227 (2)	0.0419 (7)
C25	0.2087 (4)	0.3885 (2)	−0.1136 (2)	0.0417 (7)
H25	0.1297	0.4582	−0.1011	0.050*
C26	0.1472 (4)	0.2935 (2)	−0.1233 (2)	0.0383 (6)
H26	0.0264	0.3004	−0.1169	0.046*
C27	0.3489 (6)	0.5791 (3)	−0.1038 (4)	0.0781 (13)
H27A	0.2900	0.5975	−0.1650	0.117*
H27B	0.4168	0.6336	−0.0997	0.117*
H27C	0.2628	0.5801	−0.0382	0.117*
C31	0.3704 (3)	−0.0450 (2)	−0.2019 (2)	0.0305 (5)
C32	0.4241 (4)	−0.0750 (2)	−0.3103 (2)	0.0381 (6)
H32	0.3637	−0.0348	−0.3627	0.046*
C33	0.5670 (4)	−0.1644 (3)	−0.3409 (2)	0.0465 (7)
H33	0.6017	−0.1840	−0.4136	0.056*
C34	0.6591 (4)	−0.2253 (2)	−0.2634 (3)	0.0408 (6)
C35	0.6116 (4)	−0.1934 (3)	−0.1561 (3)	0.0438 (7)
H35	0.6766	−0.2308	−0.1046	0.053*
C36	0.4660 (4)	−0.1053 (2)	−0.1256 (2)	0.0406 (6)
H36	0.4315	−0.0861	−0.0528	0.049*
C37	0.8756 (5)	−0.3895 (3)	−0.2234 (4)	0.0722 (11)
H37A	0.9291	−0.3483	−0.1822	0.108*
H37B	0.9644	−0.4495	−0.2604	0.108*
H37C	0.7882	−0.4206	−0.1751	0.108*
O1	−0.2204 (3)	0.1654 (2)	−0.52266 (18)	0.0592 (6)
O2	0.4641 (3)	0.46844 (19)	−0.1165 (2)	0.0626 (7)
O3	0.7933 (3)	−0.31468 (19)	−0.3017 (2)	0.0576 (6)
P1	0.17506 (8)	0.06402 (5)	−0.15376 (5)	0.02933 (15)
Cl1	−0.05138 (11)	0.16975 (6)	0.08394 (6)	0.04878 (19)
Pd1	0.0000	0.0000	0.0000	0.02850 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.264 (12)	0.110 (5)	0.087 (5)	−0.034 (6)	−0.030 (6)	−0.009 (4)
C2	0.244 (11)	0.137 (7)	0.080 (5)	−0.018 (7)	−0.037 (6)	−0.015 (5)
C3	0.256 (11)	0.129 (6)	0.109 (6)	−0.046 (7)	−0.024 (7)	−0.038 (5)
C11	0.0305 (13)	0.0349 (14)	0.0304 (13)	−0.0055 (11)	−0.0069 (10)	0.0006 (10)
C12	0.0387 (15)	0.0453 (16)	0.0373 (14)	−0.0170 (13)	−0.0083 (12)	0.0075 (12)
C13	0.0408 (16)	0.0573 (19)	0.0461 (16)	−0.0236 (14)	−0.0117 (13)	0.0031 (14)
C14	0.0414 (15)	0.0484 (17)	0.0375 (15)	−0.0109 (13)	−0.0138 (12)	0.0001 (13)
C15	0.0554 (19)	0.066 (2)	0.0372 (15)	−0.0340 (16)	−0.0158 (14)	0.0154 (14)
C16	0.0459 (16)	0.0534 (18)	0.0454 (16)	−0.0264 (14)	−0.0173 (13)	0.0123 (14)
C17	0.078 (3)	0.084 (3)	0.051 (2)	−0.036 (2)	−0.0331 (19)	0.0202 (19)
C21	0.0367 (14)	0.0303 (13)	0.0295 (12)	−0.0101 (11)	−0.0070 (10)	0.0036 (10)
C22	0.0368 (14)	0.0323 (14)	0.0446 (15)	−0.0063 (11)	−0.0088 (12)	−0.0016 (12)
C23	0.0355 (15)	0.0440 (17)	0.063 (2)	−0.0147 (13)	−0.0126 (14)	0.0005 (14)
C24	0.0517 (17)	0.0324 (15)	0.0478 (16)	−0.0156 (13)	−0.0181 (14)	0.0039 (12)
C25	0.0450 (16)	0.0287 (14)	0.0496 (16)	−0.0043 (12)	−0.0109 (13)	0.0018 (12)
C26	0.0340 (14)	0.0343 (14)	0.0464 (16)	−0.0079 (11)	−0.0089 (12)	0.0042 (12)
C27	0.079 (3)	0.0346 (18)	0.129 (4)	−0.0176 (18)	−0.033 (3)	0.000 (2)
C31	0.0321 (13)	0.0273 (13)	0.0333 (13)	−0.0080 (10)	−0.0079 (10)	0.0000 (10)
C32	0.0359 (14)	0.0416 (16)	0.0358 (14)	−0.0051 (12)	−0.0091 (11)	−0.0008 (12)
C33	0.0428 (16)	0.0565 (19)	0.0360 (15)	−0.0031 (14)	−0.0041 (12)	−0.0101 (13)
C34	0.0316 (14)	0.0369 (15)	0.0525 (17)	−0.0071 (12)	−0.0040 (12)	−0.0053 (13)
C35	0.0431 (16)	0.0401 (16)	0.0491 (17)	−0.0053 (13)	−0.0182 (13)	0.0048 (13)
C36	0.0462 (16)	0.0403 (16)	0.0345 (14)	−0.0048 (13)	−0.0124 (12)	−0.0008 (12)
C37	0.061 (2)	0.054 (2)	0.090 (3)	0.0119 (18)	−0.018 (2)	−0.001 (2)
O1	0.0633 (15)	0.0806 (17)	0.0476 (13)	−0.0328 (13)	−0.0299 (11)	0.0164 (12)
O2	0.0640 (15)	0.0374 (12)	0.0955 (19)	−0.0198 (11)	−0.0262 (14)	−0.0028 (12)
O3	0.0453 (12)	0.0516 (13)	0.0654 (15)	0.0089 (10)	−0.0076 (11)	−0.0073 (11)
P1	0.0311 (3)	0.0287 (3)	0.0285 (3)	−0.0080 (3)	−0.0054 (3)	0.0009 (3)
Cl1	0.0675 (5)	0.0326 (4)	0.0444 (4)	−0.0180 (3)	0.0051 (3)	−0.0086 (3)
Pd1	0.03329 (16)	0.02494 (15)	0.02737 (15)	−0.00770 (11)	−0.00467 (11)	−0.00023 (10)

Geometric parameters (Å, º) top

C1—C3	1.351 (11)	C24—O2	1.366 (4)
C1—C2	1.375 (12)	C24—C25	1.390 (4)
C1—H1	0.9300	C25—C26	1.380 (4)
C2—C3ⁱ	1.413 (11)	C25—H25	0.9300
C2—H2	0.9300	C26—H26	0.9300
C3—C2ⁱ	1.413 (11)	C27—O2	1.436 (4)
C3—H3	0.9300	C27—H27A	0.9600
C11—C16	1.388 (4)	C27—H27B	0.9600
C11—C12	1.395 (4)	C27—H27C	0.9600
C11—P1	1.820 (3)	C31—C32	1.389 (4)
C12—C13	1.387 (4)	C31—C36	1.394 (4)
C12—H12	0.9300	C31—P1	1.815 (3)
C13—C14	1.374 (4)	C32—C33	1.386 (4)
C13—H13	0.9300	C32—H32	0.9300
C14—O1	1.360 (3)	C33—C34	1.393 (4)
C14—C15	1.392 (4)	C33—H33	0.9300
C15—C16	1.382 (4)	C34—O3	1.368 (3)
C15—H15	0.9300	C34—C35	1.381 (4)
C16—H16	0.9300	C35—C36	1.388 (4)
C17—O1	1.441 (4)	C35—H35	0.9300
C17—H17A	0.9600	C36—H36	0.9300
C17—H17B	0.9600	C37—O3	1.434 (4)
C17—H17C	0.9600	C37—H37A	0.9600
C21—C26	1.394 (4)	C37—H37B	0.9600
C21—C22	1.404 (4)	C37—H37C	0.9600
C21—P1	1.821 (3)	P1—Pd1	2.3496 (6)
C22—C23	1.380 (4)	Cl1—Pd1	2.2995 (7)
C22—H22	0.9300	Pd1—Cl1ⁱⁱ	2.2995 (7)
C23—C24	1.389 (4)	Pd1—P1ⁱⁱ	2.3496 (6)
C23—H23	0.9300

C3—C1—C2	124.8 (9)	C25—C26—C21	121.8 (3)
C3—C1—H1	117.6	C25—C26—H26	119.1
C2—C1—H1	117.6	C21—C26—H26	119.1
C1—C2—C3ⁱ	118.8 (8)	O2—C27—H27A	109.5
C1—C2—H2	120.6	O2—C27—H27B	109.5
C3ⁱ—C2—H2	120.6	H27A—C27—H27B	109.5
C1—C3—C2ⁱ	116.3 (9)	O2—C27—H27C	109.5
C1—C3—H3	121.8	H27A—C27—H27C	109.5
C2ⁱ—C3—H3	121.8	H27B—C27—H27C	109.5
C16—C11—C12	118.0 (2)	C32—C31—C36	118.4 (2)
C16—C11—P1	121.9 (2)	C32—C31—P1	123.13 (19)
C12—C11—P1	120.1 (2)	C36—C31—P1	118.4 (2)
C13—C12—C11	120.5 (3)	C33—C32—C31	120.5 (3)
C13—C12—H12	119.7	C33—C32—H32	119.8
C11—C12—H12	119.7	C31—C32—H32	119.8
C14—C13—C12	120.7 (3)	C32—C33—C34	120.4 (3)
C14—C13—H13	119.6	C32—C33—H33	119.8
C12—C13—H13	119.6	C34—C33—H33	119.8
O1—C14—C13	116.0 (3)	O3—C34—C35	124.8 (3)
O1—C14—C15	124.5 (3)	O3—C34—C33	115.6 (3)
C13—C14—C15	119.5 (3)	C35—C34—C33	119.7 (3)
C16—C15—C14	119.6 (3)	C34—C35—C36	119.5 (3)
C16—C15—H15	120.2	C34—C35—H35	120.2
C14—C15—H15	120.2	C36—C35—H35	120.2
C15—C16—C11	121.6 (3)	C35—C36—C31	121.4 (3)
C15—C16—H16	119.2	C35—C36—H36	119.3
C11—C16—H16	119.2	C31—C36—H36	119.3
O1—C17—H17A	109.5	O3—C37—H37A	109.5
O1—C17—H17B	109.5	O3—C37—H37B	109.5
H17A—C17—H17B	109.5	H37A—C37—H37B	109.5
O1—C17—H17C	109.5	O3—C37—H37C	109.5
H17A—C17—H17C	109.5	H37A—C37—H37C	109.5
H17B—C17—H17C	109.5	H37B—C37—H37C	109.5
C26—C21—C22	117.5 (2)	C14—O1—C17	118.0 (2)
C26—C21—P1	120.6 (2)	C24—O2—C27	117.4 (3)
C22—C21—P1	122.0 (2)	C34—O3—C37	117.7 (3)
C23—C22—C21	120.9 (3)	C31—P1—C11	106.73 (12)
C23—C22—H22	119.5	C31—P1—C21	104.02 (12)
C21—C22—H22	119.5	C11—P1—C21	104.27 (12)
C22—C23—C24	120.6 (3)	C31—P1—Pd1	111.03 (8)
C22—C23—H23	119.7	C11—P1—Pd1	111.08 (9)
C24—C23—H23	119.7	C21—P1—Pd1	118.81 (9)
O2—C24—C23	115.9 (3)	Cl1ⁱⁱ—Pd1—Cl1	180.00 (4)
O2—C24—C25	124.9 (3)	Cl1ⁱⁱ—Pd1—P1	88.38 (2)
C23—C24—C25	119.2 (3)	Cl1—Pd1—P1	91.62 (2)
C26—C25—C24	120.0 (3)	Cl1ⁱⁱ—Pd1—P1ⁱⁱ	91.62 (2)
C26—C25—H25	120.0	Cl1—Pd1—P1ⁱⁱ	88.38 (2)
C24—C25—H25	120.0	P1—Pd1—P1ⁱⁱ	180.00 (3)

C3—C1—C2—C3ⁱ	−0.6 (15)	P1—C31—C36—C35	176.8 (2)
C2—C1—C3—C2ⁱ	0.5 (15)	C13—C14—O1—C17	−177.2 (3)
C16—C11—C12—C13	−0.3 (4)	C15—C14—O1—C17	2.6 (5)
P1—C11—C12—C13	−177.6 (2)	C23—C24—O2—C27	176.8 (3)
C11—C12—C13—C14	0.0 (5)	C25—C24—O2—C27	−2.5 (5)
C12—C13—C14—O1	−179.7 (3)	C35—C34—O3—C37	8.5 (5)
C12—C13—C14—C15	0.6 (5)	C33—C34—O3—C37	−171.3 (3)
O1—C14—C15—C16	179.4 (3)	C32—C31—P1—C11	10.3 (3)
C13—C14—C15—C16	−0.9 (5)	C36—C31—P1—C11	−166.3 (2)
C14—C15—C16—C11	0.6 (5)	C32—C31—P1—C21	−99.6 (2)
C12—C11—C16—C15	0.0 (5)	C36—C31—P1—C21	83.8 (2)
P1—C11—C16—C15	177.2 (3)	C32—C31—P1—Pd1	131.5 (2)
C26—C21—C22—C23	−0.3 (4)	C36—C31—P1—Pd1	−45.2 (2)
P1—C21—C22—C23	−179.5 (2)	C16—C11—P1—C31	−80.9 (3)
C21—C22—C23—C24	−0.2 (5)	C12—C11—P1—C31	96.3 (2)
C22—C23—C24—O2	−178.6 (3)	C16—C11—P1—C21	28.8 (3)
C22—C23—C24—C25	0.6 (5)	C12—C11—P1—C21	−154.0 (2)
O2—C24—C25—C26	178.8 (3)	C16—C11—P1—Pd1	157.9 (2)
C23—C24—C25—C26	−0.4 (4)	C12—C11—P1—Pd1	−24.9 (2)
C24—C25—C26—C21	−0.1 (4)	C26—C21—P1—C31	170.1 (2)
C22—C21—C26—C25	0.5 (4)	C22—C21—P1—C31	−10.8 (2)
P1—C21—C26—C25	179.7 (2)	C26—C21—P1—C11	58.4 (2)
C36—C31—C32—C33	1.4 (4)	C22—C21—P1—C11	−122.5 (2)
P1—C31—C32—C33	−175.3 (2)	C26—C21—P1—Pd1	−65.9 (2)
C31—C32—C33—C34	−0.2 (5)	C22—C21—P1—Pd1	113.2 (2)
C32—C33—C34—O3	177.4 (3)	C31—P1—Pd1—Cl1ⁱⁱ	−41.94 (9)
C32—C33—C34—C35	−2.4 (5)	C11—P1—Pd1—Cl1ⁱⁱ	76.66 (10)
O3—C34—C35—C36	−176.1 (3)	C21—P1—Pd1—Cl1ⁱⁱ	−162.45 (10)
C33—C34—C35—C36	3.7 (5)	C31—P1—Pd1—Cl1	138.06 (9)
C34—C35—C36—C31	−2.6 (5)	C11—P1—Pd1—Cl1	−103.34 (10)
C32—C31—C36—C35	0.0 (4)	C21—P1—Pd1—Cl1	17.55 (10)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	[PdCl₂(C₂₁H₂₁O₃P)₂]·C₆H₆
M_r	960.10
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	7.9338 (2), 12.1886 (3), 12.5268 (3)
α, β, γ (°)	85.981 (3), 78.840 (2), 76.155 (2)
V (Å³)	1153.57 (5)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.63
Crystal size (mm)	0.34 × 0.24 × 0.10

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (APEX2 Ax-Scale; Bruker, 2008)
T_min, T_max	0.813, 0.939
No. of measured, independent and observed [I > 2σ(I)] reflections	31847, 5781, 4546
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.097, 1.08
No. of reflections	5781
No. of parameters	271
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.26, −0.53

Computer programs: SMART-NT (Bruker, 1999), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001) and Mercury (Macrae et al., 2006), publCIF (Westrip, 2009).

Acknowledgements

The authors acknowledge the University of the Witwatersrand for their facilities and the use of the diffractometer in the Jan Boeyens Structural Chemistry Laboratory.

References

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