cis-(Pyridin-2-ylcarbonimidodithio­ato-κ2 S,S′)bis­(triphenyl­phosphane-κP)palladium(II)

Vladimir V Bon; Svitlana I Orysyk; Vasily I Pekhnyo

doi:10.1107/S1600536810050518

. 2010 Dec 8;67(Pt 1):m46. doi: 10.1107/S1600536810050518

cis-(Pyridin-2-ylcarbonimidodithioato-κ² S,S′)bis(triphenylphosphane-κP)palladium(II)

Vladimir V Bon ^a, Svitlana I Orysyk ^a,^*, Vasily I Pekhnyo ^a

PMCID: PMC3050130 PMID: 21522566

Abstract

The title compound, [Pd(C₆H₄N₂S₂)(C₁₈H₁₅P)₂], was obtained as a minor product from the reaction of trans-PdCl₂(PPh₃)₂ with piperazine-1,4-dicarbothioic acid bis(pyridin-2-yl)amide. The Pd^II atom displays a slightly distorted square-planar PdP₂S₂ geometry with a bidentately coordinated pyridin-2-ylcarbonimidodithioate ligand and two triphenylphosphine molecules, coordinated in cis positions. The crystal structure features weak π–π [centroid–centroid distance =3.7327(15) Å] and C–H⋯π interactions and contains an almost spherically shaped void of 50.4 Å³ per unit cell.

Related literature

For the biological activity of Pd compounds, see: Garoufis et al. (2009 ▶). For related structures, see: Ahmed et al. (1977 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[Pd(C₆H₄N₂S₂)(C₁₈H₁₅P)₂]
M _r = 799.17
Triclinic,
a = 10.9163 (10) Å
b = 12.7235 (12) Å
c = 15.7104 (14) Å
α = 102.609 (1)°
β = 107.672 (1)°
γ = 108.567 (1)°
V = 1847.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.74 mm⁻¹
T = 173 K
0.50 × 0.30 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.712, T _max = 0.890
30024 measured reflections
7568 independent reflections
6811 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.023
wR(F ²) = 0.055
S = 1.06
7568 reflections
442 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810050518/im2253sup1.cif

e-67-00m46-sup1.cif^{(30.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810050518/im2253Isup2.hkl

e-67-00m46-Isup2.hkl^{(370.2KB, hkl)}

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

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

Cg1, Cg2, Cg3, Cg4 and Cg5 are the centroids of the N2/C2/C6/C5/C4/C3, C7–C12, C13–C18, C19–C24 and C25–C30 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15⋯Cg1ⁱ	0.95	2.73	3.4991 (3)	139
C20—H20⋯Cg2ⁱⁱ	0.95	2.93	3.7152 (2)	141
C9—H9⋯Cg3ⁱⁱ	0.95	2.70	3.4657 (2)	138
C4—H4⋯Cg4ⁱⁱⁱ	0.95	2.72	3.5712 (2)	150
C35—H35⋯Cg5^iv	0.95	2.98	3.7681 (2)	141

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

The authors thank the Ukrainian National Academy of Sciences for financial support of the study.

supplementary crystallographic information

Comment

Structural investigation of palladium coordination compounds with carbothioamide derivatives has an actuality due to their potential biological activity (Garoufis et al., 2009). The current paper reports a structural study of a coordination compound obtained as a minor product as a result of the decomposition of the initially used organic ligand molecule in DMF solution.

The asymmetric unit of crystal structure contains one molecule of the complex, in which palladium displays a slightly distorted square-planar PdP₂S₂ coordination geometry (Fig. 1). Mean deviation from the plane Pd1/P1/P2/S1/S2 is 0.0455 Å (maximum deviation for S1 = -0.0646 (5) Å). The values of Pd–P and Pd–S bond lengths correspond to those in related structures (Ahmed et al., 1977). S1–Pd1–S2 strongly deviates from 90° due to steric strain of the four-membered ring. The opposite angle P1–Pd1–P2 has a value of 99.77 (2)° that can be explained by repulsion of bulky phenyl rings of triphenylphosphine moieties. The organic ligand molecule coordinates to palladium bidentantly as a dianion. Two triphenylphosphine ligands coordinate to the palladium in a cis-conformation, although there is a trans-conformation in the initial reagent. The bonds C1–S1 and C2–S2 correspond to C–S single bonds (Allen et al., 1987). At the same time, C1—N1 shows a value of 1.275 (2) Å corresponding to a classical C=N double bond. The ligand molecule contains two planar fragments C1/N1/S1/S2 and N1/N2/C2–C6, creating a dihedral angle of 58.22 (8)°. The crystal structure of the title compound shows a large number of weak π–π and C–H···π interactions and contains an almost spherically shaped void of 50.4 Å³ per unit cell (Fig. 2).

Experimental

20 ml (10 ^-2 mol/L) DMF solution of piperazine-1,4-dicarbothioic acid bis-pyridin-2-ylamide was stirred with 20 ml (2x10 ^-2 mol/L) solution of PdCl₂(PPh₃)₂in chloroform. As a result of slow evaporation (1 month) several yellow prismatic crystals of the title compound were obtained from reaction mixture (yield ~5%).