Bis(methyl xanthato)-κS;κ2 S:S′-(triphenyl­phosphane-κP)palladium(II)

Reyna Reyes-Martínez; Simón Hernández-Ortega; David Morales-Morales

doi:10.1107/S1600536811040487

. 2011 Oct 12;67(Pt 11):m1518. doi: 10.1107/S1600536811040487

Bis(methyl xanthato)-κS;κ² S:S′-(triphenylphosphane-κP)palladium(II)

Reyna Reyes-Martínez ^a, Simón Hernández-Ortega ^a,^*, David Morales-Morales ^a

PMCID: PMC3246946 PMID: 22219766

Abstract

The title compound, [Pd(C₂H₃OS₂)₂(C₁₈H₁₅P)], features a palladium complex with a triphenylphosphane ligand and two xanthate ligands, one of them coordinates in a bidentate and the other in a monodentate fashion, giving rise to a slightly distorted square-planar coordination of the Pd^II ion. As a result of this difference in the coordination modes, the C—S bond lengths are different, viz. 1.687 (2) and 1.692 (2) Å in the bidentate ligand and 1.723 (2) Å in the monodentate ligand, whereas the non-coordinating S atom has a C—S distance of 1.649 (2) Å. The crystal packing is stabilized by C—H⋯O interactions.

Related literature

For background information on xanthates, see: Karlin (2005 ▶); Friebolin et al. (2005 ▶). For crystal engineering, see: Tiekink (2003 ▶). For bond-length data, see: Allen (2002 ▶).

Experimental

Crystal data

[Pd(C₂H₃OS₂)₂(C₁₈H₁₅P)]
M _r = 583.00
Triclinic,
a = 9.5595 (10) Å
b = 9.5883 (10) Å
c = 14.4661 (16) Å
α = 73.619 (1)°
β = 87.492 (2)°
γ = 69.617 (1)°
V = 1190.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.22 mm⁻¹
T = 298 K
0.30 × 0.22 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: analytical (SADABS, Bruker, 1999 ▶) T _min = 0.712, T _max = 0.817
9954 measured reflections
4371 independent reflections
4021 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.025
wR(F ²) = 0.064
S = 1.10
4371 reflections
274 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: XP in SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811040487/bt5655sup1.cif

e-67-m1518-sup1.cif^{(22.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811040487/bt5655Isup2.hkl

e-67-m1518-Isup2.hkl^{(214.1KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C18—H18⋯O20ⁱ	0.93	2.64	3.211	120

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Symmetry code: (i) Inline graphic .

Acknowledgments

RRM would like to thank CONACYT for a postdoctoral scholarship (Agreement 290586-UNAM). Support of this research by CONACYT (154732) and PAPIIT (IN201711) is gratefully acknowledged.

supplementary crystallographic information

Comment

Xanthates ligands are a kind of compounds that can be coordinated to metal centers in different fashions, being found in coordination as monodentate, bidentate or even as a bridge, such richness in coordination modes very often leads to diverse structural motifs in the solid state (Karlin, 2005). It is precisely due to these structural features that these ligands are commonly involved in different supramolecular interactions such as D—H···S, D—H···O and S···Metal (D=C, N, O), all of these interactions being of important relevance to crystal engineering (Tiekink, 2003). Moreover, complexes including xanthate ligands in its structure have shown diverse applications at the industrial level, as chelating and flotation agents, while in bioinorganic chemistry they have found important applications as antitumoral agents (Friebolin et al. 2005).

The molecular structure of the title compound (I) shown in Figure 1, consists of two xanthate and one triphenylphosphane ligands coordinated to the Pd(II) center, in an almost square planar arrangement about the Pd(II) atom [0.0272 (3) Å]. The two xanthates ligands exhibiting different bond fashions, having one of them coordinated in a bidentate manner while the second one is attached to the palladium only by one sulfur atom in a monodentate way. The bond distances of Pd—S observed on the bidetate ligand 2.3386 (6)Å for Pd—S2 and 2.3581 (6)Å for Pd—S1 are larger than that observed Pd—S3 for the mondentate ligand. The difference between the above mentioned bond distances being due in part to the fact that the C22—S4 distance has a double bond character (1.649 (2) Å) and thus is shorter than C22—S4 (1.723 (2)Å which shows a commonly single bond character (Table 1). A revision of the Cambridge Structural Database (Allen, 2002), for Pd—S distances in bidentate and monodentate ligands, affords distance values of 2.31–2.33Å which are shorter than the data observed for the title compound (I). In absence of hydrogen bond donors, the molecules arrange as a centrosymmetric dimers generated by C—H···O and a weak intermolecular Pd–S interaction of 3.521 (2)Å.

Experimental

The title compound was synthesized by mixing Et₃N (0.2 mL) and excess CS₂ (2 mL) in methanol (10 mL). After stirring the resulting solution for 4 h at room temperature, trans-[(Ph₃P)₂PdCl₂] (100 mg, 0.14 mmol) was added, affording a yellow precipitate that was filtered and washed with methanol. Crystals suitable for X-ray analysis were obtained upon recrystallization from a mixture of dichloromethane and isopropyl alcohol.