Chlorido[2,3,5,6-tetrakis(tert-butylsulfanylmethyl)phenyl-κ3 S 2,C 1,S 6]palladium(II) dichloromethane monosolvate

The title compound, [Pd(C26H45S4)Cl]·CH2Cl2, crystallizes with a disordered dichloromethane solvent molecule [occupancy ratio = 0.67 (4):0.33 (4)]. Two of the tert-butyl groups are also disordered [occupancy ratios = 0.70 (5):0.30 (5) and 0.63 (4):0.37 (4)]. Although the pincer ligand offers the possibility for coordination of two different metal atoms, the present structure shows only the coordination of a single PdII atom in a typical S—C—S tridentate pincer manner. The PdII atom is in a slightly distorted square-planar environment with the two tert-butylsulfanyl groups arranged in a trans conformation and with a chloride ligand trans to the σ-bonded aromatic C atom. The structure exhibits a durene-like ligand frame, forming a dihedral angle of 13.6 (4)° with the metal coordination (Pd/S/S/Cl/C) environment. It is noteworthy that the tert-butyl groups are found in a syn arrangement, this being different to that found previously by Loeb, Shimizu & Wisner [(1998). Organometallics, 17, 2324–2327].

The title compound, [Pd(C 26 H 45 S 4 )Cl]ÁCH 2 Cl 2 , crystallizes with a disordered dichloromethane solvent molecule [occupancy ratio = 0.67 (4):0.33 (4)]. Two of the tert-butyl groups are also disordered [occupancy ratios = 0.70 (5):0.30 (5) and 0.63 (4):0.37 (4)]. Although the pincer ligand offers the possibility for coordination of two different metal atoms, the present structure shows only the coordination of a single Pd II atom in a typical S-C-S tridentate pincer manner. The Pd II atom is in a slightly distorted square-planar environment with the two tert-butylsulfanyl groups arranged in a trans conformation and with a chloride ligand trans to the -bonded aromatic C atom. The structure exhibits a durene-like ligand frame, forming a dihedral angle of 13.6 (4) with the metal coordination (Pd/S/S/Cl/C) environment. It is noteworthy that the tert-butyl groups are found in a syn arrangement, this being different to that found previously by Loeb, Shimizu & Wisner [(1998). Organometallics, 17, 2324-2327.
The structure of (I) is shown in Fig. 1 with the numbering scheme. Compound (I) was crystallized as a dichloromethane solvate. Selected bond distances and angles are shown in Table 1. In agreement with the dihedral angles of the planes C7 -C1-C2-C3-C8 and S1-Pd-S2-Cl1 (13.6 (4)°) the Pd atom is located in a slightly distorted square-planar geometry. Compound (I) is a geometric isomer of a previously described compound (Loeb et al. 1998). However, there are several noticeable differences in our compound (I), the tert-butyl substituents at the S are found in a syn fashion while those described in the previously reported compound are oriented in an anti fashion with respect to the square plane. The bond distances for Pd-S and Pd-C [2.326 (2) Å, 2.333 (2) Å and 2.022 (4) Å] are slightly larger than those of the anti isomer [2.297 (3) Å, 2.302 (3) Å and 1.994 (4) Å]. The Pd-Cl bond distance [2.441 (2) Å] is larger than of the anti isomer. While the uncoordinated tert-butylS groups are found in a similar geometry as those previously observed in the Loeb's species (Loeb et al. 1998). Finally, both the tert-butyl groups and the dichloromethane solvent molecule are disordered and were refined as disordered with two components.

Experimental
The title compound was synthesized according to a published procedure (Loeb et al. 1998). Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a solution of the title compound (I) in CH 2 Cl 2 .

Refinement
Two tert-butyl and CH 2 Cl 2 solvent, are disordered and were modelled and refined in two major contributors. The ratio of S.O.F., were 70/30 and 63/37 for tertbutyl groups and 67/33 for CH 2 Cl 2 solvent. H atoms on C atoms were included in calculated positions (C-H = 0.93 Å for C-H arom., 0.97 Å for CH 2 , and 0.96 Å for CH 3 ), H atoms were refined using a riding model, with U iso (H) = 1.2U eq of the carrier atom for C-H-arom. and methylene groups and U iso (H) = 1.5U eq for methyl groups.

Figure 1
The molecular structure of (I). Displacement ellipsoids are drawn at the 40% probability level. The H-atoms and the minor disorder components have been omitted to enhance clarity.

Chlorido[2,3,5,6-tetrakis(tert-butylsulfanylmethyl)phenyl-κ 3 S 2 ,C 1 ,S 6 ]palladium(II) dichloromethane monosolvate
where P = (F o 2 + 2F c 2 )/3 (Δ/σ) max = 0.002 Δρ max = 0.64 e Å −3 Δρ min = −0.24 e Å −3 Special details 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.