trans-Di-μ-chlorido-bis­{chlorido[tris­(3,5-dimethyl­phen­yl)phosphane-κP]palla­dium(II)} dichloro­methane monosolvate

Davis, W.L.; Muller, A.

doi:10.1107/S1600536812048556

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 12| December 2012| Pages m1563-m1564

doi:10.1107/S1600536812048556

Open

access

trans-Di-μ-chlorido-bis{chlorido[tris(3,5-dimethylphenyl)phosphane-κP]palladium(II)} dichloromethane monosolvate

Wade L. Davis ^a and Alfred Muller ^a ^*

^aResearch Centre for Synthesis and Catalysis, Department of Chemistry, University of Johannesburg (APK Campus), PO Box 524, Auckland Park, Johannesburg, 2006, South Africa
^*Correspondence e-mail: mullera@uj.ac.za

(Received 24 November 2012; accepted 26 November 2012; online 30 November 2012)

In the dimeric title compound, [Pd₂Cl₄{P(C₈H₉)₃}₂]·CH₂Cl₂, the metal complex molecule is situated about an inversion centre and is accompanied by a dichloromethane solvent molecule situated on a twofold rotation axis. The Pd^II atom has a slightly distorted square-planar coordination sphere. The effective cone angle for the tris(3,5-dimethylphenyl)phosphane ligand was calculated to be 169°. In the crystal, the metal complex and solvent molecules are linked via C—H⋯Cl interactions, generating chains along [10-2]. There are also C—H⋯π and weak π–π interactions present [centroid–centroid distance = 3.990 (2) Å, plane–plane distance = 3.6352 (15) Å and ring slippage = 1.644 Å], forming of a three-dimensional structure.

Related literature

For background on catalysis of palladium compounds, see: Bedford et al. (2004 ). For the synthesis of the starting materials, see: Drew & Doyle (1990 ). For a description of the Cambridge Structural Database, see: Allen (2002 ). For background on cone angles, see: Tolman (1977 ); Otto (2001 ).

Experimental

Crystal data

[Pd₂Cl₄(C₂₄H₂₇P)₂]·CH₂Cl₂
M_r = 1132.38
Monoclinic, P 2/c
a = 14.747 (2) Å
b = 9.1038 (13) Å
c = 21.376 (3) Å
β = 117.576 (8)°
V = 2543.8 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.12 mm⁻¹
T = 100 K
0.19 × 0.16 × 0.13 mm

Data collection

Bruker APEX DUO 4K-CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.816, T_max = 0.868
30952 measured reflections
6349 independent reflections
4776 reflections with I > 2σ(I)
R_int = 0.071

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.098
S = 1.03
6349 reflections
273 parameters
H-atom parameters constrained
Δρ_max = 0.90 e Å⁻³
Δρ_min = −1.12 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of rings C17–C19/C21/C22/C24 and C9–C11/C13/C14/C16, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C25—H25A⋯Cl2	0.99	2.82	3.733 (4)	154
C21—H21⋯Cl1ⁱ	0.95	2.85	3.693 (4)	148
C5—H5⋯Cg1ⁱⁱ	0.95	2.95	3.847 (5)	159
C15—H15A⋯Cg2ⁱⁱⁱ	0.99	2.79	3.620 (5)	143
Symmetry codes: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (ii) -x+2, -y+1, -z+1; (iii) -x+1, -y+2, -z+1.

Data collection: APEX2 (Bruker, 2011 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT and XPREP (Bruker, 2008); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: publCIF (Westrip, 2010 ) and WinGX (Farrugia, 2012 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812048556/su2534sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812048556/su2534Isup2.hkl

checkCIF report

Comment top

Complexes involving palladium metal centres are among some of the most popular catalytic precursors in organic synthesis due to their catalytic abilities. They are used in carbon-carbon bond formation reactions, e.g. the Heck, Stille and Suzuki reactions (Bedford et al., 2004). [PdCl₂(L)₂] (L = tertiary phosphine, arsine or stibine) complexes can conveniently be prepared by the substitution of 1,5-cyclooctadiene (COD) from [PdCl₂(COD)]. The title compound is the product of the reaction of [PdCl₂(COD)] with tris(3,5-dimethylphenyl)phosphane as ligand, which shows dimerization of the square-planar Pd^II monomer. The crystal structure reported on herein is, to the best of our knowledge, the first Pd complex containing this phosphane ligand.

In the title compound, Fig. 1, the dimeric Pd^II complex is situated about an inversion centre and crystallizes with a dichloromethane solvate molecule that is located on a 2-fold rotation axis. Each equivalent pair of terminal bonded ligands is in a mutually trans orientation, with only slight distortions in the P1—Pd1—Cl1 and Cl2—Pd1—Cl1 angles of 173.90 (3) and 173.20 (3)°, respectively. The distortion of the square-planar metal coordination is further exemplified by the displacement of the Pd^II metal centre by 0.1122 (4) Å from the plane formed by the coordinating atoms Cl2/P1/Cl1/Cl1ⁱ (symmetry code: (i) = -x+1, -y+1, -z+1; r.m.s. deviation of mean plane = 0.0085 Å).

To describe the steric demand of the phosphane ligand the Tolman cone angle (Tolman, 1977) is still the most commonly used model. Applying this model to the geometry obtained for the title compound (and adjusting the Pd—P bond distance to 2.28 Å) we calculated an effective cone angle (Otto, 2001) of 169°. A search of the Cambridge Structural Database (CSD, V5.33, last update Aug. 2012; Allen, 2002) gave only three hits for structures containing the tris(3,5-dimethylphenyl)phosphane moiety. Cone angle calculations for these structures gave values ranging from 160 to 180°, with the value obtained for the title compound (169°) fitting well in this range.

In the crystal, weak C—H···Cl interactions between the dichloromethane solvate and the dimeric metal complex generate chains along the [1 0 -2] direction (Fig. 2 and Table 1). Additionally, several C—H···π (Fig. 3 and Table 1) and π-π stacking interactions (centroid-to-centroid distance = 3.990 (2) Å, plane-to plane separation 3.6352 (15) Å, ring slippage = 1.644 Å) are observed (Fig. 4), leading to the formation of a three-dimensional structure.

Related literature top

For background on catalysis of palladium compounds, see: Bedford et al. (2004). For the synthesis of the starting materials, see: Drew & Doyle (1990). For a description of the Cambridge Structural Database, see: Allen (2002). For background on cone angles, see: Tolman (1977); Otto (2001).

Experimental top

Dichloro(1,5-cyclooctadiene)palladium(II), [PdCl₂(COD)], was prepared according to the literature procedure of Drew & Doyle (1990). Tris(3,5-dimethylphenyl)phosphane (12.1 mg, 0.035 mmol) was dissolved in CH₂Cl₂ (5 cm³). A solution of [Pd(COD)Cl₂] (5.0 mg, 0.017 mmol) in CH₂Cl₂ (5 cm³) was added to the phosphane solution. The mixture was stirred for 2hr at room temperature, after which the solution was left to slowly evaporate. Dark red crystals of the title compound suitable for a single-crystal X-ray study were obtained. Spectroscopic data for the title compound are available in the archived CIF.

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT and XPREP (Bruker, 2008); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: publCIF (Westrip, 2010) and WinGX (Farrugia, 2012).

Figures top

	Fig. 1. A view of the molecular structure of the title complex, showing the atom-numbering. Displacement ellipsoids are drawn at the 50% probability level. [symmetry code (i) = -x+1, -y+1, -z+1; H atoms have been omitted for clarity].
	Fig. 2. A view of the crystal packing of the title compound, showing the C—H···Cl interactions (red dashed lines) between the metal complex and the dichloromethane solvate. H atoms not involved in H-bonding have been omitted for clarity.
	Fig. 3. A view of the crystal packing of the title compound, showing the C—H···π interactions (red dashed lines). H atoms not involved in H-bonding have been omitted for clarity.
	Fig. 4. A view of the crystal packing of the title compound, showing the π···π interactions (red dashed lines). H atoms have been omitted for clarity.

trans-Di-µ-chlorido-bis{chlorido[tris(3,5-dimethylphenyl)phosphane- κP]palladium(II)} dichloromethane monosolvate top

Crystal data top

[Pd₂Cl₄(C₂₄H₂₇P)₂]·CH₂Cl₂	F(000) = 1148
M_r = 1132.38	D_x = 1.478 Mg m⁻³
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 4452 reflections
a = 14.747 (2) Å	θ = 2.2–27.5°
b = 9.1038 (13) Å	µ = 1.12 mm⁻¹
c = 21.376 (3) Å	T = 100 K
β = 117.576 (8)°	Cube, orange
V = 2543.8 (6) Å³	0.19 × 0.16 × 0.13 mm
Z = 2

Data collection top

Bruker APEX DUO 4K-CCD diffractometer	6349 independent reflections
Radiation source: sealed tube	4776 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.071
Detector resolution: 8.4 pixels mm^-1	θ_max = 28.4°, θ_min = 1.6°
ϕ and ω scans	h = −19→19
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −12→12
T_min = 0.816, T_max = 0.868	l = −28→28
30952 measured reflections

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0419P)² + 1.7351P] where P = (F_o² + 2F_c²)/3
6349 reflections	(Δ/σ)_max = 0.001
273 parameters	Δρ_max = 0.90 e Å⁻³
0 restraints	Δρ_min = −1.12 e Å⁻³

Crystal data top

[Pd₂Cl₄(C₂₄H₂₇P)₂]·CH₂Cl₂	V = 2543.8 (6) Å³
M_r = 1132.38	Z = 2
Monoclinic, P2/c	Mo Kα radiation
a = 14.747 (2) Å	µ = 1.12 mm⁻¹
b = 9.1038 (13) Å	T = 100 K
c = 21.376 (3) Å	0.19 × 0.16 × 0.13 mm
β = 117.576 (8)°

Data collection top

Bruker APEX DUO 4K-CCD diffractometer	6349 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	4776 reflections with I > 2σ(I)
T_min = 0.816, T_max = 0.868	R_int = 0.071
30952 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.03	Δρ_max = 0.90 e Å⁻³
6349 reflections	Δρ_min = −1.12 e Å⁻³
273 parameters

Special details top

Experimental. Spectroscopic data for the title compund: ³¹P NMR (CDCl₃, 162.0 MHz): δ (p.p.m.) 33.54 (s, 1P). ¹H NMR (CDCl₃, 400 MHz): δ (p.p.m.) 2.34 (m, 36H), 7.11 (m, 4H), 7.34 (m, 4H), 7.36 (m, 2H) 7.66 (m, 6H), 7.32 (m, 4H).

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	Occ. (<1)
Pd1	0.627522 (18)	0.56103 (3)	0.537254 (13)	0.01368 (8)
Cl1	0.49039 (6)	0.53788 (9)	0.42440 (4)	0.01841 (17)
Cl2	0.74975 (6)	0.60182 (10)	0.65077 (4)	0.02141 (19)
P1	0.72374 (6)	0.67044 (10)	0.49592 (4)	0.01491 (18)
C1	0.8616 (2)	0.6459 (4)	0.53793 (17)	0.0175 (7)
C2	0.9098 (3)	0.5328 (4)	0.58601 (18)	0.0214 (7)
H2	0.8715	0.472	0.6012	0.026*
C3	1.0148 (3)	0.5092 (4)	0.6118 (2)	0.0258 (8)
C4	1.0691 (3)	0.3890 (5)	0.6654 (2)	0.0391 (11)
H4A	1.0903	0.311	0.6434	0.059*
H4B	1.0226	0.3482	0.682	0.059*
H4C	1.1295	0.43	0.7055	0.059*
C5	1.0682 (3)	0.6006 (4)	0.5881 (2)	0.0268 (9)
H5	1.1393	0.5843	0.6051	0.032*
C6	1.0219 (3)	0.7144 (4)	0.54062 (19)	0.0245 (8)
C7	1.0833 (3)	0.8123 (5)	0.5172 (2)	0.0371 (10)
H7A	1.1272	0.7517	0.5045	0.056*
H7B	1.1258	0.8788	0.5558	0.056*
H7C	1.0367	0.87	0.4761	0.056*
C8	0.9174 (2)	0.7360 (4)	0.51530 (18)	0.0202 (7)
H8	0.8837	0.8125	0.4824	0.024*
C9	0.6976 (2)	0.8629 (4)	0.49952 (18)	0.0174 (7)
C10	0.7633 (2)	0.9478 (4)	0.55679 (18)	0.0187 (7)
H10	0.8275	0.909	0.5899	0.022*
C11	0.7352 (3)	1.0906 (4)	0.56585 (19)	0.0224 (8)
C12	0.8050 (3)	1.1774 (4)	0.6300 (2)	0.0315 (9)
H12A	0.8125	1.1266	0.6725	0.047*
H12B	0.7758	1.2752	0.6277	0.047*
H12C	0.8722	1.1871	0.6315	0.047*
C13	0.6423 (3)	1.1449 (4)	0.5154 (2)	0.0234 (8)
H13	0.6236	1.2422	0.5207	0.028*
C14	0.5749 (3)	1.0627 (4)	0.45713 (19)	0.0228 (8)
C15	0.4734 (3)	1.1257 (4)	0.4041 (2)	0.0280 (8)
H15A	0.4296	1.1409	0.4267	0.042*
H15B	0.4401	1.0573	0.3645	0.042*
H15C	0.4848	1.2198	0.3866	0.042*
C16	0.6032 (3)	0.9208 (4)	0.45022 (19)	0.0199 (7)
H16	0.5582	0.862	0.4116	0.024*
C17	0.6861 (2)	0.6207 (4)	0.40528 (17)	0.0196 (7)
C18	0.6758 (3)	0.7236 (4)	0.35443 (18)	0.0244 (8)
H18	0.6843	0.8251	0.3661	0.029*
C19	0.6527 (3)	0.6785 (5)	0.28588 (19)	0.0305 (9)
C20	0.6411 (4)	0.7934 (6)	0.2318 (2)	0.0491 (13)
H20A	0.5764	0.8459	0.217	0.074*
H20B	0.6413	0.7457	0.1907	0.074*
H20C	0.6981	0.863	0.2525	0.074*
C21	0.6429 (3)	0.5291 (5)	0.2705 (2)	0.0338 (10)
H21	0.6283	0.4982	0.2243	0.041*
C22	0.6539 (3)	0.4227 (5)	0.3208 (2)	0.0286 (9)
C23	0.6476 (3)	0.2622 (5)	0.3036 (2)	0.0421 (11)
H23A	0.6304	0.2069	0.336	0.063*
H23B	0.7137	0.2285	0.3085	0.063*
H23C	0.5946	0.2462	0.2549	0.063*
C24	0.6751 (2)	0.4700 (4)	0.38800 (19)	0.0228 (8)
H24	0.6822	0.3997	0.4229	0.027*
Cl3	0.94842 (13)	0.9023 (2)	0.79374 (9)	0.0900 (6)
C25	1	0.7942 (9)	0.75	0.075 (3)
H25A	0.9457	0.7302	0.7153	0.09*	0.5
H25B	1.0543	0.7302	0.7847	0.09*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.01213 (12)	0.01374 (13)	0.01494 (13)	0.00036 (10)	0.00608 (9)	−0.00087 (10)
Cl1	0.0153 (4)	0.0246 (4)	0.0149 (4)	−0.0037 (3)	0.0066 (3)	−0.0005 (3)
Cl2	0.0167 (4)	0.0287 (5)	0.0168 (4)	−0.0024 (3)	0.0061 (3)	−0.0026 (3)
P1	0.0136 (4)	0.0145 (4)	0.0174 (4)	0.0015 (3)	0.0077 (3)	−0.0005 (3)
C1	0.0139 (15)	0.0186 (18)	0.0211 (17)	0.0003 (13)	0.0089 (14)	−0.0036 (14)
C2	0.0171 (16)	0.0199 (19)	0.0270 (18)	−0.0014 (13)	0.0101 (15)	−0.0013 (15)
C3	0.0186 (17)	0.024 (2)	0.032 (2)	0.0030 (15)	0.0097 (16)	−0.0002 (17)
C4	0.0206 (19)	0.042 (3)	0.049 (3)	0.0067 (18)	0.0111 (19)	0.010 (2)
C5	0.0147 (16)	0.029 (2)	0.037 (2)	0.0013 (14)	0.0121 (16)	−0.0086 (17)
C6	0.0190 (17)	0.025 (2)	0.031 (2)	−0.0029 (14)	0.0133 (16)	−0.0064 (16)
C7	0.025 (2)	0.033 (2)	0.062 (3)	−0.0014 (17)	0.027 (2)	−0.001 (2)
C8	0.0187 (17)	0.0180 (18)	0.0257 (18)	0.0014 (13)	0.0119 (15)	−0.0018 (15)
C9	0.0187 (16)	0.0142 (17)	0.0248 (17)	0.0012 (13)	0.0147 (14)	0.0018 (14)
C10	0.0170 (15)	0.0184 (17)	0.0245 (17)	0.0022 (14)	0.0129 (14)	0.0022 (15)
C11	0.0299 (19)	0.0149 (18)	0.0302 (19)	−0.0010 (14)	0.0206 (17)	−0.0012 (14)
C12	0.040 (2)	0.017 (2)	0.038 (2)	−0.0007 (17)	0.0180 (19)	−0.0064 (17)
C13	0.0294 (19)	0.0130 (17)	0.035 (2)	0.0037 (14)	0.0212 (17)	0.0038 (15)
C14	0.0248 (18)	0.0220 (18)	0.0297 (19)	0.0069 (15)	0.0194 (16)	0.0087 (16)
C15	0.029 (2)	0.022 (2)	0.034 (2)	0.0102 (16)	0.0150 (17)	0.0080 (17)
C16	0.0183 (16)	0.0172 (18)	0.0272 (18)	0.0019 (13)	0.0131 (15)	0.0026 (15)
C17	0.0122 (15)	0.028 (2)	0.0191 (17)	0.0012 (14)	0.0078 (14)	−0.0027 (15)
C18	0.0187 (17)	0.033 (2)	0.0215 (18)	0.0006 (15)	0.0097 (15)	0.0018 (16)
C19	0.0182 (18)	0.054 (3)	0.0200 (18)	0.0020 (17)	0.0095 (15)	0.0014 (19)
C20	0.051 (3)	0.071 (4)	0.024 (2)	0.002 (3)	0.016 (2)	0.010 (2)
C21	0.0173 (18)	0.064 (3)	0.0196 (18)	−0.0011 (18)	0.0084 (15)	−0.012 (2)
C22	0.0131 (16)	0.045 (3)	0.0268 (19)	0.0006 (16)	0.0085 (15)	−0.0130 (18)
C23	0.035 (2)	0.051 (3)	0.037 (2)	−0.003 (2)	0.014 (2)	−0.023 (2)
C24	0.0164 (16)	0.028 (2)	0.0242 (18)	0.0018 (14)	0.0098 (15)	−0.0050 (15)
Cl3	0.0711 (11)	0.1022 (14)	0.0712 (10)	−0.0143 (10)	0.0113 (9)	0.0306 (10)
C25	0.061 (5)	0.052 (5)	0.070 (5)	0	−0.006 (4)	0

Geometric parameters (Å, º) top

Pd1—P1	2.2241 (9)	C12—H12B	0.98
Pd1—Cl2	2.2859 (9)	C12—H12C	0.98
Pd1—Cl1	2.3317 (9)	C13—C14	1.399 (5)
Pd1—Cl1ⁱ	2.4138 (8)	C13—H13	0.95
Cl1—Pd1ⁱ	2.4138 (8)	C14—C16	1.387 (5)
P1—C9	1.803 (4)	C14—C15	1.511 (5)
P1—C17	1.809 (3)	C15—H15A	0.98
P1—C1	1.816 (3)	C15—H15B	0.98
C1—C2	1.395 (5)	C15—H15C	0.98
C1—C8	1.397 (5)	C16—H16	0.95
C2—C3	1.398 (5)	C17—C18	1.389 (5)
C2—H2	0.95	C17—C24	1.410 (5)
C3—C5	1.392 (5)	C18—C19	1.404 (5)
C3—C4	1.519 (5)	C18—H18	0.95
C4—H4A	0.98	C19—C21	1.391 (6)
C4—H4B	0.98	C19—C20	1.509 (6)
C4—H4C	0.98	C20—H20A	0.98
C5—C6	1.388 (5)	C20—H20B	0.98
C5—H5	0.95	C20—H20C	0.98
C6—C8	1.391 (5)	C21—C22	1.401 (6)
C6—C7	1.512 (5)	C21—H21	0.95
C7—H7A	0.98	C22—C24	1.389 (5)
C7—H7B	0.98	C22—C23	1.500 (6)
C7—H7C	0.98	C23—H23A	0.98
C8—H8	0.95	C23—H23B	0.98
C9—C10	1.392 (5)	C23—H23C	0.98
C9—C16	1.402 (5)	C24—H24	0.95
C10—C11	1.405 (5)	Cl3—C25	1.755 (5)
C10—H10	0.95	C25—Cl3ⁱⁱ	1.755 (5)
C11—C13	1.384 (5)	C25—H25A	0.99
C11—C12	1.502 (5)	C25—H25B	0.99
C12—H12A	0.98

P1—Pd1—Cl2	90.82 (3)	C11—C12—H12C	109.5
P1—Pd1—Cl1	92.10 (3)	H12A—C12—H12C	109.5
Cl2—Pd1—Cl1	173.20 (3)	H12B—C12—H12C	109.5
P1—Pd1—Cl1ⁱ	173.90 (3)	C11—C13—C14	122.8 (3)
Cl2—Pd1—Cl1ⁱ	92.18 (3)	C11—C13—H13	118.6
Cl1—Pd1—Cl1ⁱ	84.35 (3)	C14—C13—H13	118.6
Pd1—Cl1—Pd1ⁱ	95.65 (3)	C16—C14—C13	117.9 (3)
C9—P1—C17	108.87 (16)	C16—C14—C15	121.1 (3)
C9—P1—C1	108.11 (16)	C13—C14—C15	121.0 (3)
C17—P1—C1	102.52 (15)	C14—C15—H15A	109.5
C9—P1—Pd1	103.29 (11)	C14—C15—H15B	109.5
C17—P1—Pd1	112.19 (12)	H15A—C15—H15B	109.5
C1—P1—Pd1	121.50 (12)	C14—C15—H15C	109.5
C2—C1—C8	120.5 (3)	H15A—C15—H15C	109.5
C2—C1—P1	121.8 (3)	H15B—C15—H15C	109.5
C8—C1—P1	117.4 (3)	C14—C16—C9	120.9 (3)
C1—C2—C3	119.8 (3)	C14—C16—H16	119.5
C1—C2—H2	120.1	C9—C16—H16	119.5
C3—C2—H2	120.1	C18—C17—C24	119.6 (3)
C5—C3—C2	118.3 (3)	C18—C17—P1	122.5 (3)
C5—C3—C4	121.1 (3)	C24—C17—P1	117.7 (3)
C2—C3—C4	120.6 (3)	C17—C18—C19	120.3 (4)
C3—C4—H4A	109.5	C17—C18—H18	119.8
C3—C4—H4B	109.5	C19—C18—H18	119.8
H4A—C4—H4B	109.5	C21—C19—C18	118.8 (4)
C3—C4—H4C	109.5	C21—C19—C20	122.3 (4)
H4A—C4—H4C	109.5	C18—C19—C20	118.9 (4)
H4B—C4—H4C	109.5	C19—C20—H20A	109.5
C6—C5—C3	122.8 (3)	C19—C20—H20B	109.5
C6—C5—H5	118.6	H20A—C20—H20B	109.5
C3—C5—H5	118.6	C19—C20—H20C	109.5
C5—C6—C8	118.1 (3)	H20A—C20—H20C	109.5
C5—C6—C7	121.0 (3)	H20B—C20—H20C	109.5
C8—C6—C7	120.9 (3)	C19—C21—C22	122.1 (4)
C6—C7—H7A	109.5	C19—C21—H21	118.9
C6—C7—H7B	109.5	C22—C21—H21	118.9
H7A—C7—H7B	109.5	C24—C22—C21	118.1 (4)
C6—C7—H7C	109.5	C24—C22—C23	121.0 (4)
H7A—C7—H7C	109.5	C21—C22—C23	120.8 (4)
H7B—C7—H7C	109.5	C22—C23—H23A	109.5
C6—C8—C1	120.4 (3)	C22—C23—H23B	109.5
C6—C8—H8	119.8	H23A—C23—H23B	109.5
C1—C8—H8	119.8	C22—C23—H23C	109.5
C10—C9—C16	119.8 (3)	H23A—C23—H23C	109.5
C10—C9—P1	120.1 (3)	H23B—C23—H23C	109.5
C16—C9—P1	119.4 (3)	C22—C24—C17	121.0 (4)
C9—C10—C11	120.4 (3)	C22—C24—H24	119.5
C9—C10—H10	119.8	C17—C24—H24	119.5
C11—C10—H10	119.8	Cl3—C25—Cl3ⁱⁱ	111.8 (5)
C13—C11—C10	118.2 (3)	Cl3—C25—H25A	109.3
C13—C11—C12	122.4 (3)	Cl3ⁱⁱ—C25—H25A	109.3
C10—C11—C12	119.5 (3)	Cl3—C25—H25B	109.3
C11—C12—H12A	109.5	Cl3ⁱⁱ—C25—H25B	109.3
C11—C12—H12B	109.5	H25A—C25—H25B	107.9
H12A—C12—H12B	109.5

P1—Pd1—Cl1—Pd1ⁱ	−175.03 (3)	Pd1—P1—C9—C16	−73.6 (3)
Cl1ⁱ—Pd1—Cl1—Pd1ⁱ	0	C16—C9—C10—C11	0.6 (5)
Cl2—Pd1—P1—C9	−82.49 (12)	P1—C9—C10—C11	−169.5 (3)
Cl1—Pd1—P1—C9	91.38 (12)	C9—C10—C11—C13	−1.7 (5)
Cl2—Pd1—P1—C17	160.43 (13)	C9—C10—C11—C12	177.0 (3)
Cl1—Pd1—P1—C17	−25.71 (13)	C10—C11—C13—C14	1.4 (5)
Cl2—Pd1—P1—C1	38.80 (13)	C12—C11—C13—C14	−177.2 (3)
Cl1—Pd1—P1—C1	−147.34 (13)	C11—C13—C14—C16	0.0 (5)
C9—P1—C1—C2	134.7 (3)	C11—C13—C14—C15	179.0 (3)
C17—P1—C1—C2	−110.4 (3)	C13—C14—C16—C9	−1.2 (5)
Pd1—P1—C1—C2	15.8 (3)	C15—C14—C16—C9	179.8 (3)
C9—P1—C1—C8	−51.4 (3)	C10—C9—C16—C14	0.9 (5)
C17—P1—C1—C8	63.6 (3)	P1—C9—C16—C14	171.1 (3)
Pd1—P1—C1—C8	−170.3 (2)	C9—P1—C17—C18	21.2 (3)
C8—C1—C2—C3	0.0 (5)	C1—P1—C17—C18	−93.2 (3)
P1—C1—C2—C3	173.7 (3)	Pd1—P1—C17—C18	134.9 (3)
C1—C2—C3—C5	−0.1 (5)	C9—P1—C17—C24	−163.9 (3)
C1—C2—C3—C4	178.6 (4)	C1—P1—C17—C24	81.8 (3)
C2—C3—C5—C6	0.6 (6)	Pd1—P1—C17—C24	−50.2 (3)
C4—C3—C5—C6	−178.1 (4)	C24—C17—C18—C19	1.1 (5)
C3—C5—C6—C8	−0.8 (6)	P1—C17—C18—C19	176.0 (3)
C3—C5—C6—C7	179.0 (4)	C17—C18—C19—C21	−1.6 (5)
C5—C6—C8—C1	0.6 (5)	C17—C18—C19—C20	179.5 (3)
C7—C6—C8—C1	−179.2 (3)	C18—C19—C21—C22	1.0 (5)
C2—C1—C8—C6	−0.2 (5)	C20—C19—C21—C22	179.9 (4)
P1—C1—C8—C6	−174.2 (3)	C19—C21—C22—C24	0.1 (5)
C17—P1—C9—C10	−144.0 (3)	C19—C21—C22—C23	−177.2 (3)
C1—P1—C9—C10	−33.4 (3)	C21—C22—C24—C17	−0.5 (5)
Pd1—P1—C9—C10	96.6 (3)	C23—C22—C24—C17	176.7 (3)
C17—P1—C9—C16	45.8 (3)	C18—C17—C24—C22	−0.1 (5)
C1—P1—C9—C16	156.4 (3)	P1—C17—C24—C22	−175.2 (3)

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

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of rings C17-C19/C21/C22/C24 and C9-C11/C13/C14/C16, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C25—H25A···Cl2	0.99	2.82	3.733 (4)	154
C21—H21···Cl1ⁱⁱⁱ	0.95	2.85	3.693 (4)	148
C5—H5···Cg1^iv	0.95	2.95	3.847 (5)	159
C15—H15A···Cg2^v	0.99	2.79	3.620 (5)	143

Symmetry codes: (iii) −x+1, y, −z+1/2; (iv) −x+2, −y+1, −z+1; (v) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	[Pd₂Cl₄(C₂₄H₂₇P)₂]·CH₂Cl₂
M_r	1132.38
Crystal system, space group	Monoclinic, P2/c
Temperature (K)	100
a, b, c (Å)	14.747 (2), 9.1038 (13), 21.376 (3)
β (°)	117.576 (8)
V (Å³)	2543.8 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.12
Crystal size (mm)	0.19 × 0.16 × 0.13

Data collection
Diffractometer	Bruker APEX DUO 4K-CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.816, 0.868
No. of measured, independent and observed [I > 2σ(I)] reflections	30952, 6349, 4776
R_int	0.071
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.098, 1.03
No. of reflections	6349
No. of parameters	273
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.90, −1.12

Computer programs: APEX2 (Bruker, 2011), SAINT (Bruker, 2008), SAINT and XPREP (Bruker, 2008), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005), publCIF (Westrip, 2010) and WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of rings C17-C19/C21/C22/C24 and C9-C11/C13/C14/C16, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C25—H25A···Cl2	0.99	2.82	3.733 (4)	154
C21—H21···Cl1ⁱ	0.95	2.85	3.693 (4)	148
C5—H5···Cg1ⁱⁱ	0.95	2.95	3.847 (5)	159
C15—H15A···Cg2ⁱⁱⁱ	0.99	2.79	3.620 (5)	143

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+2, −z+1.

Acknowledgements

Financial assistance from the Research Fund of the University of Johannesburg is gratefully acknowledged. Mrs Z. Phasha is thanked for the data collection.

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bedford, R. B., Cazin, C. S. J. & Holder, D. (2004). Coord. Chem. Rev. 248, 2283–2321. Web of Science CrossRef CAS Google Scholar
Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2008). SADABS, SAINT and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2011). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Drew, D. & Doyle, J. R. (1990). Inorg. Synth. 28, 346–349. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Otto, S. (2001). Acta Cryst. C57, 793–795. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tolman, C. A. (1977). Chem. Rev. 77, 313–348. CrossRef CAS Web of Science Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 12| December 2012| Pages m1563-m1564

doi:10.1107/S1600536812048556

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

trans-Di-μ-chlorido-bis­­{chlorido[tris­­(3,5-di­methyl­phen­yl)phosphane-κP]palla­dium(II)} di­chloro­methane monosolvate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

trans-Di-μ-chlorido-bis{chlorido[tris(3,5-dimethylphenyl)phosphane-κP]palladium(II)} dichloromethane monosolvate