trans-Dichloridobis[diphenyl(thiophen-2-yl)phosphane-κP]palladium(II)

The title compound, trans-[PdCl2(C16H13PS)2], forms a monomeric complex with a trans-square-planar geometry. The Pd—P bond lengths are 2.3387 (11) Å, as the Pd atom lies on an inversion point, while the Pd—Cl bond lengths are 2.2950 (12) Å.

The title compound, trans-[PdCl 2 (C 16 H 13 PS) 2 ], forms a monomeric complex with a trans-square-planar geometry. The Pd-P bond lengths are 2.3387 (11) Å , as the Pd atom lies on an inversion point, while the Pd-Cl bond lengths are 2.2950 (12) Å .

Andrew R. Burgoyne, Reinout Meijboom, Haleden Chiririwa and Leo Kirsten Comment
The catalytic abilities of palladium metal centre complexes make them amongst the most popular catalytic precursors in organic synthesis. They are used in carbon-carbon bond formation reactions like the Heck, Stille and Suzuki reactions (Bedford et al., 2004).
[PdCl 2 (L) 2 ] (L = tertiary phosphine, arsine or stibine) complexes can conveniently be prepared by the substitution of 1,5-cyclooctadiene (COD) from [PdCl 2 (COD)]. The title compound, trans-[PdCl 2 {P(C 6 H 5 ) 2 (C 4 SH 3 )} 2 ], crystallizes with the Pd atom on a center of symmetry and each pair of equivalent ligands in a mutually trans orientation. The geometry is, therefore, slightly distorted square planar and the Pd atom is not displaced out of the coordinating atoms plane. All angles in the coordination polyhedron are close to the ideal value of 90°, with P-Pd-Cl = 87.50 (5)° and P-Pd-Cl i = 92.50 (5)°. As required by the crystallographic symmetry, the P-Pd-P i and Cl-Pd-Cl i angles are 180°.
The title compound compares well with other closely related Pd(II) complexes from the literature containing two chloro and two tertiary phosphine ligands in a trans geometry (Muller & Meijboom, 2010). The title compound, having a Pd-Cl bond length of 2.2950 (12) Å and a Pd-P bond length of 2.3387 (11) Å, fits well into the typical range for complexes of this kind. Notably the title compound did not crystallize as a solvated complex; these type of Pd(II) complexes have a tendency to crystallize as solvates (Ogutu & Meijboom, 2011).

Refinement
A disorder refinement model was applied to the thiophene ring. Ellipsoid displacement constraints (SIMU) were used to improve the model of the structure. The occupation parameters were linked to a free variable with a distribution of 0.57 (1):0.43 (1). P1, C1A, C2A and C3A were all constrained to have equal ADPs. All hydrogen atoms were positioned geometrically with C-H = 0.95 Å for aromatic H atoms. All hydrogen atoms were allowed to ride on their parent atoms with U iso (H) = 1.2U eq . The remaining highest electron peak was 1.54 at 0.06 Å from C1A and the deepest hole was -1.49 at 0.24 Å from C4B.

trans-Dichloridobis[diphenyl(thiophen-2-yl)phosphane-κP]palladium(II)
Crystal data [PdCl 2 (C 16 H 13 PS) 2 ] M r = 713.91 Monoclinic, P2 1 /n Hall symbol: -P 2yn a = 9.019 (2) Å b = 18.427 (4) Å c = 9.658 (2) Å β = 110.14 (4)°V = 1507.0 (7) Å 3 Z = 2 where P = (F o 2 + 2F c 2 )/3 (Δ/σ) max < 0.001 Δρ max = 1.54 e Å −3 Δρ min = −1.49 e Å −3 Special details Experimental. The intensity data was collected on a Bruker X8 Apex II 4 K Kappa CCD diffractometer using an exposure time of 10 s/frame. A collection frame width of 0.5 ° covering up to θ = 28.4° resulted in 99% completeness accomplished. 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 F 2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F 2 , conventional R-factors R are based on F, with F set to zero for negative F 2 . The threshold expression of F 2 > σ(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 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 (Å 2 )
x y z U iso */U eq Occ.