Di-μ-chlorido-bis­{[2-(di-tert-butyl­phosphan­yl)biphenyl-3-yl-κ2C3,P]palladium(II)} dichloro­methane disolvate

Holzapfel, C.W.; Omondi, B.

doi:10.1107/S1600536812051136

metal-organic compounds

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Volume 69| Part 2| February 2013| Page m86

doi:10.1107/S1600536812051136

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Di-μ-chlorido-bis{[2-(di-tert-butylphosphanyl)biphenyl-3-yl-κ²C³,P]palladium(II)} dichloromethane disolvate

Cedric W. Holzapfel ^a and Bernard Omondi ^b ^*

^aResearch Centre for Synthesis and Catalysis, Department of Chemistry, University of Johannesburg, Auckland Park Kingsway Campus, PO Box 524, Auckland Park 2006, South Africa, and ^bSchool of Chemistry and Physics, University of KwaZulu-Natal, Westville Campus, Private Bag X54001, Durban 4000, South Africa
^*Correspondence e-mail: owaga@ukzn.ac.za

(Received 22 November 2012; accepted 18 December 2012; online 9 January 2013)

The asymmetric unit of the title compound, [Pd₂Cl₂(C₂₀H₂₆P)₂]·2CH₂Cl₂, contains one half-molecule of the palladium complex and a dichloromethane solvent molecule. In the complex, two Pd^II atoms are bridged by two Cl atoms, with the other two coordination sites occupied by a C atom of the biphenyl system and a P atom, resulting in a distorted square-planar coordination geometry of the Pd^II atom and a cyclometallated four-membered ring. The Pd₂Cl₂ unit is located about an inversion center. The planes of the rings of the biphenyl system make a dihedral angle of 66.36 (11)°.

Related literature

For background to palladacycles, see: Beletskaya & Cheprakov (2004 ); Orlye & Jutland (2005 ); Herrmann et al. (2003 ). For their applications as catalysts for methoxycarbonylation, see: Omondi et al. (2011 ); Williams et al. (2008 ). For related structures with Pd^II in ortho-position, see: Sole et al. (2004 ); Mohr et al. (2006 ); Bennett et al. (2010 ); Christmann et al. (2006 ); Garrou et al. (1981 ).

Experimental

Crystal data

[Pd₂Cl₂(C₂₀H₂₆P)₂]·2CH₂Cl₂
M_r = 1048.31
Triclinic, $[P \overline 1]$
a = 9.4741 (15) Å
b = 10.1805 (15) Å
c = 12.0677 (18) Å
α = 103.250 (4)°
β = 95.443 (3)°
γ = 97.080 (3)°
V = 1115.2 (3) Å³
Z = 1
Mo Kα radiation
μ = 1.27 mm⁻¹
T = 100 K
0.08 × 0.07 × 0.02 mm

Data collection

Bruker X8 APEXII 4K KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.905, T_max = 0.975
15104 measured reflections
5515 independent reflections
4344 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.094
S = 1.01
5515 reflections
241 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 1.16 e Å⁻³
Δρ_min = −1.09 e Å⁻³

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus and XPREP (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812051136/kj2217sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812051136/kj2217Isup2.hkl

checkCIF report

Comment top

Palladacycles (Beletskaya & Cheprakov, 2004; Orlye & Jutland, 2005; Herrmann et al., 2003) appear as long-sought thermally stable and structurally defined catalysts for Heck, cross-coupling and for methoxycarbonylation of alkenes (Omondi et al., 2011, Williams et al., 2008). However, with the exception of 2-(2'-di-tert-butylphosphine)bipheryl palladium(II) acetate, shown in the Fluka and Aldrich catalogues, this complex and other four membered ring phospha-palladacycles (Garrou, 1981) have shown little success in this regard.

The title compound crystallizes as a dichloromethane solvate, with half a molecule of the complex in the asymmetric unit, in which the the two Pd centres are bridged by two chlorides and are part of a constrained four-membered ring along with two carbon atoms of a phenyl ring and a phosphorus atom (Fig. 1). The four-membered rings are trans across the planar Pd₂Cl₂ unit, the planar Pd₂Cl₂ unit being on the center of inversion at 1/2, 0, 0. The coordination around the palladium atom is distorted square planar, with the angles around the metal deviating significantly from orthogonallity yet very planar. The smallest of the angles around the metal centre is 68.84 (10)° and is similar to that previously reported dinuclear cyclopalladate, 68.89 (3)° (Christmann et al., 2006) and of related ortho-metallated Pd-structures from literature (Sole et al., 2004; Mohr et al., 2006; Bennett et al., 2010). The other angles around the Pd centers are 85.85 (11), 95.0 (2) and 106.44 (3)° all probably due to steric hindrance caused by tert-butyl groups. The Pd—C distance (1.978 (3) Å) is shorter than the Pd—P distance (2.2327 (9) Å) which is in good agreement with the Pd—P separation in similar four-membered compounds with a sp²-hybridized carbon. The carbon-phosphorus distance that is part of the constrained ring is significantly shorter [1.824 (3) Å] compared to the other two [1.860 (3) and 1.879 (4) Å] as observed in most cyclopalladates. The planes of the phenyl rings of the biphenyl moiety have a dihedral angle of 66.36 (11)°.

Related literature top

For background to palladacycles, see: Beletskaya & Cheprakov (2004); Orlye & Jutland, (2005); Herrmann et al. (2003). For their applications as catalysts for methoxycarnylation, see: Omondi et al. (2011); Williams et al. (2008). For related ortho-metallated Pd structures, see: Sole et al. (2004); Mohr et al. (2006); Bennett et al. (2010); Christmann et al. (2006); Garrou et al. (1981).

Experimental top

(2-Biphenyl)-di-tert-butylphosphine (597 mg, 2 mmol) was added to the solution of lithium chloride (170 mg, 4 mmol) and palladium chloride (355 mg, 2 mmol) in 2:1 methanol-dichloromethane (15 ml) under argon. The mixture was heated under reflux under argon for 1 h. The solvent was evaporated in vacuo. To the residue was added dichloromethane (15 ml) and water (10 ml) and the mixture stirred for 30 minutes. The organic phase was separated, dried (anhydrous sodium sulfate) and the solvent evaporated to leave a residue (823 mg) which was chromographed over silica gel (Davisil, 20 g) using 5% methanol in dichloromethane as mobile phase. The eluent (120 ml) was evaporated to leave 1 as a colourless crystalline mass (676 mg, 82%). Good quality crystals (m.p. 162–165 °C, decomp) were obtained by diffusion of the vapours of ether into a solution of the title compound in dichloromethane at room temperature.

1H NMR (300 MHz, CDCl3): δ = 1.37 (d, JPH = 1.3 Hz, 36H, C(CH₃)₃), 7.05 (d, J = 3.2 Hz, 2H), 7.25 (dd, J = 7.5 and 3.2 Hz, 2H), 7.30–7.50 (m, 8H), 7.58 (t, J = 7.5 Hz, 2H), 7.85 (t, J = 7.5 Hz, 2H);

¹³C{¹H} NMR (75 Mz, CDCl₃): δ = 30.37 (d, JPC = 5 Hz, C(CH₃)₃), 35.97 (d, JPC = 12 Hz, C(CH₃)₃), 127.44 (d, JPC = 8.5 Hz, C-aromatic), 127.78 (s, C-aromatic), 127.44 (d, JPC = 8.5 Hz, C-aromatic), 127.78 (s, C-aromatic), 128.18 (s, C-aromatic), 129.19 (s, C-aromatic), 129.28 (s, C-aromatic), 133.55 (d, JPC = 26.0 Hz, C– aromatic), 138.55 (d, JPC = 32.0, C-aromatic), 141.90 (d, JPC = 3.9 Hz, C-aromatic), 142.81 (s, C– aromatic);

³¹P{1H} (97 MHz, CDCl₃): δ = -17.80.

The title compound was also obtained in essentially quantitative yield by reacting the above phosphine with an equimolar amount of (cis, cis-1,5-cyclooctadiene) palladium (ll)-chloride in dichloromethane under reflux (1 hr) or at room temperature (18 hrs).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus and XPREP (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

Fig. 1. The molecular structure and atom-numbering scheme for (I), with displacement ellipsoids drawn at the 50% probability level. Hydrogen atoms have been omited for clarity. The assymetric unit only has only half a molecule of the palladium complex, the other half generated by the symetry operator -x, -y, -z.

Di-µ-chlorido-bis{[2-(di-tert-butylphosphanyl)biphenyl-3-yl- κ²C³,P]palladium(II)} dichloromethane disolvate top

Crystal data top

[Pd₂Cl₂(C₂₀H₂₆P)₂]·2CH₂Cl₂	Z = 1
M_r = 1048.31	F(000) = 532
Triclinic, P1	D_x = 1.561 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.4741 (15) Å	Cell parameters from 15104 reflections
b = 10.1805 (15) Å	θ = 1.8–28.3°
c = 12.0677 (18) Å	µ = 1.27 mm⁻¹
α = 103.250 (4)°	T = 100 K
β = 95.443 (3)°	Block, yellow
γ = 97.080 (3)°	0.08 × 0.07 × 0.02 mm
V = 1115.2 (3) Å³

Data collection top

Bruker X8 APEXII 4K KappaCCD diffractometer	4344 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
ϕ and ω scans	θ_max = 28.3°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −12→12
T_min = 0.905, T_max = 0.975	k = −13→13
15104 measured reflections	l = −15→16
5515 independent 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0476P)²] where P = (F_o² + 2F_c²)/3
5515 reflections	(Δ/σ)_max = 0.001
241 parameters	Δρ_max = 1.16 e Å⁻³
1 restraint	Δρ_min = −1.09 e Å⁻³

Crystal data top

[Pd₂Cl₂(C₂₀H₂₆P)₂]·2CH₂Cl₂	γ = 97.080 (3)°
M_r = 1048.31	V = 1115.2 (3) Å³
Triclinic, P1	Z = 1
a = 9.4741 (15) Å	Mo Kα radiation
b = 10.1805 (15) Å	µ = 1.27 mm⁻¹
c = 12.0677 (18) Å	T = 100 K
α = 103.250 (4)°	0.08 × 0.07 × 0.02 mm
β = 95.443 (3)°

Data collection top

Bruker X8 APEXII 4K KappaCCD diffractometer	5515 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	4344 reflections with I > 2σ(I)
T_min = 0.905, T_max = 0.975	R_int = 0.049
15104 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	1 restraint
wR(F²) = 0.094	H-atom parameters constrained
S = 1.01	Δρ_max = 1.16 e Å⁻³
5515 reflections	Δρ_min = −1.09 e Å⁻³
241 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. >>> The Following ALERTS were generated <<< Format: alert-number_ALERT_alert-type_alert-level text 232_ALERT_2_C Hirshfeld Test Diff (M—X) Pd1 – Cl1.. 5.30 su Apllying DELU restraints does not remove this alert. 250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ···. 2.23 Visual inspections of ellipsoids show no abnormalities. R = 3.8%. 911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 3 912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 62 Noted, no measures taken

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

	x	y	z	U_iso*/U_eq
C1	0.4506 (3)	0.2051 (4)	0.3645 (3)	0.0143 (7)
C2	0.5538 (3)	0.1684 (4)	0.2933 (3)	0.0144 (7)
C3	0.6977 (3)	0.1820 (4)	0.3385 (3)	0.0178 (7)
H3	0.7687	0.1578	0.2902	0.021*
C4	0.7336 (3)	0.2319 (4)	0.4564 (3)	0.0189 (7)
H4	0.831	0.2437	0.4889	0.023*
C5	0.6289 (3)	0.2652 (4)	0.5278 (3)	0.0178 (7)
H5	0.6566	0.2975	0.6082	0.021*
C6	0.4844 (3)	0.2521 (3)	0.4840 (3)	0.0133 (7)
C7	0.3771 (3)	0.2810 (4)	0.5662 (3)	0.0161 (7)
C8	0.3568 (4)	0.1982 (4)	0.6430 (3)	0.0198 (8)
H8	0.4105	0.1251	0.6417	0.024*
C9	0.2587 (4)	0.2219 (4)	0.7209 (3)	0.0245 (8)
H9	0.2457	0.1656	0.773	0.029*
C10	0.1794 (4)	0.3281 (4)	0.7226 (3)	0.0288 (9)
H10	0.1098	0.3426	0.7741	0.035*
C11	0.2018 (4)	0.4135 (4)	0.6489 (3)	0.0259 (9)
H11	0.1495	0.4878	0.6517	0.031*
C12	0.3009 (4)	0.3899 (4)	0.5708 (3)	0.0201 (8)
H12	0.3164	0.4484	0.5207	0.024*
C13	0.1586 (3)	0.0291 (4)	0.2698 (3)	0.0161 (7)
C14	0.2346 (4)	−0.0917 (4)	0.2839 (3)	0.0221 (8)
H14A	0.3069	−0.0628	0.3518	0.033*
H14B	0.2812	−0.1234	0.2156	0.033*
H14C	0.1642	−0.1661	0.2933	0.033*
C15	0.0822 (4)	0.0747 (4)	0.3750 (3)	0.0215 (8)
H15A	0.0348	0.1531	0.3674	0.032*
H15B	0.1524	0.1008	0.4443	0.032*
H15C	0.0104	−0.0006	0.3809	0.032*
C16	0.0503 (4)	−0.0164 (4)	0.1600 (3)	0.0210 (8)
H16A	−0.0155	−0.097	0.1637	0.032*
H16B	0.1018	−0.0389	0.0931	0.032*
H16C	−0.0043	0.0577	0.1532	0.032*
C17	0.2358 (4)	0.3161 (4)	0.2158 (3)	0.0178 (7)
C18	0.1118 (4)	0.3638 (4)	0.2795 (3)	0.0239 (8)
H18A	0.1377	0.3755	0.3622	0.036*
H18B	0.0258	0.2954	0.2527	0.036*
H18C	0.0927	0.451	0.2645	0.036*
C19	0.1888 (4)	0.2829 (4)	0.0851 (3)	0.0217 (8)
H19A	0.1082	0.208	0.0641	0.033*
H19B	0.2692	0.2557	0.0442	0.033*
H19C	0.1593	0.3638	0.0641	0.033*
C20	0.3659 (4)	0.4295 (4)	0.2461 (3)	0.0207 (8)
H20A	0.3418	0.5083	0.2185	0.031*
H20B	0.4469	0.3958	0.2095	0.031*
H20C	0.3922	0.4568	0.3295	0.031*
C21	0.3306 (4)	0.6222 (4)	−0.0511 (3)	0.0265 (9)
H21A	0.3451	0.6825	−0.1041	0.032*
H21B	0.3437	0.5292	−0.0916	0.032*
Cl1	0.32540 (8)	−0.02556 (9)	−0.05326 (7)	0.01603 (17)
Cl2	0.15439 (10)	0.61906 (11)	−0.01468 (10)	0.0332 (2)
Cl3	0.46013 (9)	0.68133 (10)	0.07196 (8)	0.0267 (2)
P7	0.30128 (8)	0.16081 (9)	0.24901 (7)	0.01217 (18)
Pd1	0.46067 (2)	0.08342 (3)	0.13497 (2)	0.01217 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0082 (14)	0.0204 (18)	0.0149 (16)	0.0042 (13)	−0.0005 (12)	0.0051 (14)
C2	0.0097 (15)	0.0189 (17)	0.0145 (16)	0.0039 (13)	−0.0009 (12)	0.0040 (14)
C3	0.0091 (15)	0.0250 (19)	0.0186 (18)	0.0056 (14)	0.0036 (13)	0.0016 (15)
C4	0.0058 (14)	0.029 (2)	0.0196 (18)	0.0048 (14)	−0.0031 (13)	0.0029 (16)
C5	0.0126 (16)	0.0218 (18)	0.0170 (17)	0.0037 (14)	−0.0014 (13)	0.0018 (15)
C6	0.0103 (15)	0.0157 (17)	0.0134 (16)	0.0029 (13)	0.0014 (12)	0.0022 (13)
C7	0.0079 (14)	0.0224 (18)	0.0123 (16)	−0.0026 (13)	0.0005 (12)	−0.0042 (14)
C8	0.0131 (16)	0.027 (2)	0.0156 (17)	−0.0011 (14)	−0.0021 (13)	0.0022 (15)
C9	0.0169 (17)	0.037 (2)	0.0172 (18)	−0.0062 (16)	0.0018 (14)	0.0069 (17)
C10	0.0174 (18)	0.040 (2)	0.021 (2)	−0.0046 (17)	0.0088 (15)	−0.0054 (18)
C11	0.0153 (17)	0.027 (2)	0.032 (2)	0.0062 (15)	0.0051 (15)	−0.0019 (18)
C12	0.0136 (16)	0.025 (2)	0.0191 (18)	0.0023 (14)	0.0015 (14)	0.0012 (15)
C13	0.0090 (15)	0.0232 (19)	0.0148 (16)	0.0007 (13)	−0.0006 (12)	0.0036 (14)
C14	0.0157 (17)	0.0221 (19)	0.029 (2)	−0.0014 (15)	0.0012 (15)	0.0091 (16)
C15	0.0147 (16)	0.032 (2)	0.0166 (18)	−0.0025 (15)	0.0038 (13)	0.0055 (16)
C16	0.0121 (16)	0.031 (2)	0.0161 (17)	−0.0043 (15)	0.0001 (13)	0.0023 (16)
C17	0.0142 (16)	0.0217 (18)	0.0171 (17)	0.0050 (14)	0.0038 (13)	0.0017 (15)
C18	0.0174 (17)	0.029 (2)	0.026 (2)	0.0107 (16)	0.0057 (15)	0.0034 (17)
C19	0.0218 (18)	0.028 (2)	0.0159 (18)	0.0101 (16)	−0.0006 (14)	0.0053 (16)
C20	0.0211 (18)	0.0208 (19)	0.0203 (18)	0.0043 (15)	0.0045 (14)	0.0039 (15)
C21	0.0205 (18)	0.031 (2)	0.027 (2)	0.0032 (16)	0.0027 (15)	0.0062 (18)
Cl1	0.0066 (3)	0.0255 (5)	0.0139 (4)	0.0042 (3)	0.0010 (3)	−0.0001 (3)
Cl2	0.0144 (4)	0.0346 (6)	0.0501 (7)	0.0044 (4)	0.0032 (4)	0.0093 (5)
Cl3	0.0176 (4)	0.0300 (5)	0.0311 (5)	0.0015 (4)	−0.0002 (4)	0.0073 (4)
P7	0.0049 (3)	0.0191 (4)	0.0116 (4)	0.0028 (3)	0.0008 (3)	0.0014 (3)
Pd1	0.00434 (11)	0.01965 (14)	0.01151 (13)	0.00282 (9)	0.00054 (8)	0.00138 (10)

Geometric parameters (Å, º) top

C1—C2	1.391 (5)	C14—H14C	0.98
C1—C6	1.403 (5)	C15—H15A	0.98
C1—P7	1.824 (3)	C15—H15B	0.98
C2—C3	1.398 (4)	C15—H15C	0.98
C2—Pd1	1.978 (3)	C16—H16A	0.98
C3—C4	1.389 (5)	C16—H16B	0.98
C3—H3	0.95	C16—H16C	0.98
C4—C5	1.397 (5)	C17—C18	1.532 (5)
C4—H4	0.95	C17—C20	1.535 (5)
C5—C6	1.399 (4)	C17—C19	1.544 (5)
C5—H5	0.95	C17—P7	1.879 (4)
C6—C7	1.495 (4)	C18—H18A	0.98
C7—C12	1.389 (5)	C18—H18B	0.98
C7—C8	1.400 (5)	C18—H18C	0.98
C8—C9	1.387 (5)	C19—H19A	0.98
C8—H8	0.95	C19—H19B	0.98
C9—C10	1.388 (6)	C19—H19C	0.98
C9—H9	0.95	C20—H20A	0.98
C10—C11	1.391 (6)	C20—H20B	0.98
C10—H10	0.95	C20—H20C	0.98
C11—C12	1.396 (5)	C21—Cl2	1.764 (4)
C11—H11	0.95	C21—Cl3	1.771 (4)
C12—H12	0.95	C21—H21A	0.99
C13—C15	1.529 (5)	C21—H21B	0.99
C13—C14	1.534 (5)	Cl1—Pd1ⁱ	2.4154 (8)
C13—C16	1.539 (4)	Cl1—Pd1	2.4444 (9)
C13—P7	1.860 (3)	P7—Pd1	2.2328 (9)
C14—H14A	0.98	Pd1—Cl1ⁱ	2.4154 (8)
C14—H14B	0.98

C2—C1—C6	122.1 (3)	H15A—C15—H15C	109.5
C2—C1—P7	95.0 (2)	H15B—C15—H15C	109.5
C6—C1—P7	142.8 (3)	C13—C16—H16A	109.5
C1—C2—C3	120.7 (3)	C13—C16—H16B	109.5
C1—C2—Pd1	109.9 (2)	H16A—C16—H16B	109.5
C3—C2—Pd1	129.1 (3)	C13—C16—H16C	109.5
C4—C3—C2	117.9 (3)	H16A—C16—H16C	109.5
C4—C3—H3	121	H16B—C16—H16C	109.5
C2—C3—H3	121	C18—C17—C20	110.1 (3)
C3—C4—C5	121.1 (3)	C18—C17—C19	109.4 (3)
C3—C4—H4	119.4	C20—C17—C19	108.6 (3)
C5—C4—H4	119.4	C18—C17—P7	115.1 (3)
C4—C5—C6	121.7 (3)	C20—C17—P7	106.2 (2)
C4—C5—H5	119.1	C19—C17—P7	107.3 (2)
C6—C5—H5	119.1	C17—C18—H18A	109.5
C5—C6—C1	116.4 (3)	C17—C18—H18B	109.5
C5—C6—C7	118.7 (3)	H18A—C18—H18B	109.5
C1—C6—C7	124.8 (3)	C17—C18—H18C	109.5
C12—C7—C8	119.3 (3)	H18A—C18—H18C	109.5
C12—C7—C6	121.9 (3)	H18B—C18—H18C	109.5
C8—C7—C6	118.7 (3)	C17—C19—H19A	109.5
C9—C8—C7	120.5 (4)	C17—C19—H19B	109.5
C9—C8—H8	119.8	H19A—C19—H19B	109.5
C7—C8—H8	119.8	C17—C19—H19C	109.5
C8—C9—C10	119.9 (4)	H19A—C19—H19C	109.5
C8—C9—H9	120.1	H19B—C19—H19C	109.5
C10—C9—H9	120.1	C17—C20—H20A	109.5
C9—C10—C11	120.1 (4)	C17—C20—H20B	109.5
C9—C10—H10	120	H20A—C20—H20B	109.5
C11—C10—H10	120	C17—C20—H20C	109.5
C10—C11—C12	120.0 (4)	H20A—C20—H20C	109.5
C10—C11—H11	120	H20B—C20—H20C	109.5
C12—C11—H11	120	Cl2—C21—Cl3	111.6 (2)
C7—C12—C11	120.2 (4)	Cl2—C21—H21A	109.3
C7—C12—H12	119.9	Cl3—C21—H21A	109.3
C11—C12—H12	119.9	Cl2—C21—H21B	109.3
C15—C13—C14	109.0 (3)	Cl3—C21—H21B	109.3
C15—C13—C16	110.7 (3)	H21A—C21—H21B	108
C14—C13—C16	108.7 (3)	Pd1ⁱ—Cl1—Pd1	92.33 (3)
C15—C13—P7	114.4 (2)	C1—P7—C13	112.74 (15)
C14—C13—P7	105.4 (2)	C1—P7—C17	112.13 (16)
C16—C13—P7	108.4 (2)	C13—P7—C17	114.90 (15)
C13—C14—H14A	109.5	C1—P7—Pd1	85.84 (11)
C13—C14—H14B	109.5	C13—P7—Pd1	115.73 (12)
H14A—C14—H14B	109.5	C17—P7—Pd1	112.17 (11)
C13—C14—H14C	109.5	C2—Pd1—P7	68.84 (10)
H14A—C14—H14C	109.5	C2—Pd1—Cl1ⁱ	97.07 (10)
H14B—C14—H14C	109.5	P7—Pd1—Cl1ⁱ	165.87 (3)
C13—C15—H15A	109.5	C2—Pd1—Cl1	174.81 (10)
C13—C15—H15B	109.5	P7—Pd1—Cl1	106.44 (3)
H15A—C15—H15B	109.5	Cl1ⁱ—Pd1—Cl1	87.67 (3)
C13—C15—H15C	109.5

C6—C1—C2—C3	−2.4 (5)	C14—C13—P7—C1	−55.2 (3)
P7—C1—C2—C3	179.9 (3)	C16—C13—P7—C1	−171.4 (2)
C6—C1—C2—Pd1	172.0 (3)	C15—C13—P7—C17	−65.6 (3)
P7—C1—C2—Pd1	−5.8 (2)	C14—C13—P7—C17	174.7 (2)
C1—C2—C3—C4	0.5 (5)	C16—C13—P7—C17	58.4 (3)
Pd1—C2—C3—C4	−172.6 (3)	C15—C13—P7—Pd1	161.1 (2)
C2—C3—C4—C5	1.2 (6)	C14—C13—P7—Pd1	41.4 (3)
C3—C4—C5—C6	−1.2 (6)	C16—C13—P7—Pd1	−74.9 (2)
C4—C5—C6—C1	−0.6 (5)	C18—C17—P7—C1	−93.1 (3)
C4—C5—C6—C7	176.1 (3)	C20—C17—P7—C1	28.9 (3)
C2—C1—C6—C5	2.4 (5)	C19—C17—P7—C1	144.9 (2)
P7—C1—C6—C5	178.7 (3)	C18—C17—P7—C13	37.4 (3)
C2—C1—C6—C7	−174.1 (3)	C20—C17—P7—C13	159.4 (2)
P7—C1—C6—C7	2.2 (7)	C19—C17—P7—C13	−84.6 (3)
C5—C6—C7—C12	114.5 (4)	C18—C17—P7—Pd1	172.3 (2)
C1—C6—C7—C12	−69.1 (5)	C20—C17—P7—Pd1	−65.7 (2)
C5—C6—C7—C8	−63.4 (4)	C19—C17—P7—Pd1	50.3 (3)
C1—C6—C7—C8	113.0 (4)	C1—C2—Pd1—P7	5.1 (2)
C12—C7—C8—C9	1.8 (5)	C3—C2—Pd1—P7	178.8 (4)
C6—C7—C8—C9	179.8 (3)	C1—C2—Pd1—Cl1ⁱ	−176.0 (2)
C7—C8—C9—C10	0.3 (5)	C3—C2—Pd1—Cl1ⁱ	−2.3 (3)
C8—C9—C10—C11	−2.2 (6)	C1—P7—Pd1—C2	−3.63 (15)
C9—C10—C11—C12	1.9 (6)	C13—P7—Pd1—C2	−116.91 (16)
C8—C7—C12—C11	−2.0 (5)	C17—P7—Pd1—C2	108.59 (16)
C6—C7—C12—C11	−180.0 (3)	C1—P7—Pd1—Cl1ⁱ	−8.08 (19)
C10—C11—C12—C7	0.2 (5)	C13—P7—Pd1—Cl1ⁱ	−121.36 (17)
C2—C1—P7—C13	121.0 (2)	C17—P7—Pd1—Cl1ⁱ	104.15 (17)
C6—C1—P7—C13	−55.8 (5)	C1—P7—Pd1—Cl1	174.08 (11)
C2—C1—P7—C17	−107.4 (2)	C13—P7—Pd1—Cl1	60.80 (12)
C6—C1—P7—C17	75.7 (5)	C17—P7—Pd1—Cl1	−73.70 (12)
C2—C1—P7—Pd1	4.8 (2)	Pd1ⁱ—Cl1—Pd1—P7	179.47 (3)
C6—C1—P7—Pd1	−172.0 (4)	Pd1ⁱ—Cl1—Pd1—Cl1ⁱ	0
C15—C13—P7—C1	64.6 (3)

Symmetry code: (i) −x+1, −y, −z.

Experimental details

Crystal data
Chemical formula	[Pd₂Cl₂(C₂₀H₂₆P)₂]·2CH₂Cl₂
M_r	1048.31
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	9.4741 (15), 10.1805 (15), 12.0677 (18)
α, β, γ (°)	103.250 (4), 95.443 (3), 97.080 (3)
V (Å³)	1115.2 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.27
Crystal size (mm)	0.08 × 0.07 × 0.02

Data collection
Diffractometer	Bruker X8 APEXII 4K KappaCCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.905, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	15104, 5515, 4344
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.094, 1.01
No. of reflections	5515
No. of parameters	241
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.16, −1.09

Computer programs: APEX2 (Bruker, 2008), SAINT-Plus (Bruker, 2008), SAINT-Plus and XPREP (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012), WinGX (Farrugia, 2012).

Acknowledgements

We would like to acknowledge the University of Johannesburg for financial assistance.

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