trans-Chlorido(4-fluorobenzenethiolato-κS)bis(triphenylphosphane-κP)palladium(II) methanol hemisolvate

The title compound, [Pd(SC6H4F-p)Cl(PPh3)2]·0.5CH3OH, features a PdII complex with two triphenylphosphane (PPh3) ligands arranged in a trans conformation, with one chloride and one 4-fluorobenzenethiolate ligand completing the coordination sphere, giving rise to a slightly distorted square-planar geometry of the PdII ion. The methanol solvent molecule is disordered about an inversion centre with an occupancy of 0.25 for each molecule. In the crystal, weak C—H⋯Cl hydrogen-bonding interactions between the complex molecules generate chain frameworks parallel to [010].

The title compound, [Pd(SC 6 H 4 F-p)Cl(PPh 3 ) 2 ]Á0.5CH 3 OH, features a Pd II complex with two triphenylphosphane (PPh 3 ) ligands arranged in a trans conformation, with one chloride and one 4-fluorobenzenethiolate ligand completing the coordination sphere, giving rise to a slightly distorted square-planar geometry of the Pd II ion. The methanol solvent molecule is disordered about an inversion centre with an occupancy of 0.25 for each molecule. In the crystal, weak C-HÁ Á ÁCl hydrogen-bonding interactions between the complex molecules generate chain frameworks parallel to [010].

S1. Introduction
The high efficiency of palladium complexes in C-C cross coupling reactions is well known, for example in the Suzuki-Miyaura (Frisch & Beller, 2005), Mizoroki-Heck (Yin & Liebscher, 2007) and Negishi reactions (Knochel & Singer, 1993), as well as for the formation of C-Heteroatom bonds as in the Buchwald-Hartwig couplings (Surry & Buchwald, 2008). In this context, different research groups have devoted their research efforts to the synthesis of new palladium complexes with a variety of ligands. Therefore, in this opportunity we would like to report the crystal structure of the Pd II complex trans-[Pd(SC 6 H 4 F-p)(Cl)(PPh 3 ) 2 ] ·0.5CH 3 OH.

S2.1. Synthesis and crystallization
To a suspension consisting of PdCl 2 (0.072 g, 0.41 mmol) and Na 2 CO 3 (0.050 g, 0.0471 mmol) in 15 mL of toluene was added dropwise under magnetic stirring a toluene solution (5 mL) of an isomeric mix of (3-ethenylbenzyl)(4-fluorophenyl)sulfane and (4-ethenylbenzyl)(4-fluorophenyl)sulfane (60:40) (0.100 g, 0.41 mmol). The resulting mixture was set to reflux for 4 hours. After this time the reaction mixture was allowed to cool down to room temperature, filtered and the solid product washed with CHCl 3 . The insoluble reddish solid was then suspended in 15 mL of CHCl 3 and then treated with Ph 3 P (0.215 g, 820 mmol). The reaction was allowed to proceed under stirring until the solid was completely dissolved. This solution was then filtered through a short plug of celite and CH 3 OH was added to promote precipitation.

S2.2. Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were included in calculated positions (C-H = 0.93 Å for aromatic H) and refined using a riding model with U iso (H) = 1.2 U eq of carrier atoms. The CH 3 OH solvent is disordered over two sets of sites in a 0.25 : 0.25 ratio.

S3. Results and discussion
The compound trans-[Pd(SC 6 H 4 F-p)(Cl)(PPh 3 ) 2 ] ·0.5CH 3 OH crystallized in a monoclinic system including the complex trans-[Pd(SC 6 H 4 F-p)(Cl)(PPh 3 ) 2 ] and half molecule of methanol in the asymmetric unit. The Pd 2+ ion exhibits a slightly distorted square-planar PdClSP 2 geometry, with one chloride and one p-fluorobenzenethiolate ligand and two molecules of triphenylphosphane in trans conformation completing the coordination sphere. The bond distances Pd-Cl and Pd-S are 2.3269 (11) and 2.2977 (11) Å, respectively, and the Pd-P distances are 2.3432 (11) and 2.3342 (11) Å. These The p-fluorobenzenethiolate presents an intramolecular π-π interaction with one phenyl ring of the tripehylphosphane ligand. The distance between centroids Cg(C1-C6)-Cg(C7-C12) is 3.677 (3) Å. The structure is stabilized by weak C -H···Cl hydrogen bonding interactions between the complex molecules generate chain frameworks parallel to [010]. The methanol molecule is disordered over two positions in a 0.25:0.25 ratio.

Figure 1
Molecular structure of the title compound showing the atom-labelling and displacement ellipsoids drawn at 40% probability level. The hydrogen atoms were omitted.