Bis(3-benzoyl-1,1-di-sec-butyl­thio­ureato-κ2 O,S)palladium(II)

N Selvakumaran; R Karvembu; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536811036853

. 2011 Sep 17;67(Pt 10):m1394. doi: 10.1107/S1600536811036853

Bis(3-benzoyl-1,1-di-sec-butylthioureato-κ² O,S)palladium(II)

N Selvakumaran ^a, R Karvembu ^a,^‡, Seik Weng Ng ^b,^c, Edward R T Tiekink ^b,^*

PMCID: PMC3201548 PMID: 22058701

Abstract

The complex molecule of the title complex, [Pd(C₁₆H₂₃N₂OS)₂], is completed by crystallographic twofold symmetry with the metal atom lying on the rotation axis. The Pd^II atom exists within a slightly distorted square-planar geometry defined by a cis-O₂S₂ donor set. The dihedral angle formed between the mean planes of the symmetry-related six-membered chelate rings is 12.88 (7)° and the bond lengths within the rings are indicative of significant electron delocalization. In the crystal, molecules aggregate into dimers linked by four C—H⋯O interactions.

Related literature

For background to the synthesis and cytotoxicity of related Pd^II complexes of N,N-di(alkyl/aryl)-N′-benzoylthiourea ligands, see: Selvakumaran et al. (2011 ▶).

Experimental

Crystal data

[Pd(C₁₆H₂₃N₂OS)₂]
M _r = 689.27
Tetragonal,
a = 13.2737 (1) Å
c = 19.5597 (5) Å
V = 3446.25 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.69 mm⁻¹
T = 100 K
0.30 × 0.25 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.819, T _max = 0.874
4752 measured reflections
3229 independent reflections
3152 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.023
wR(F ²) = 0.058
S = 1.02
3229 reflections
186 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.44 e Å⁻³
Absolute structure: Flack (1983 ▶), 1225 Friedel pairs
Flack parameter: −0.02 (2)

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811036853/hb6404sup1.cif

e-67-m1394-sup1.cif^{(20KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811036853/hb6404Isup2.hkl

e-67-m1394-Isup2.hkl^{(158.5KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Pd—O1	2.0230 (17)
Pd—S1	2.2497 (6)

Open in a new tab

O1—Pd—S1

93.76 (5)

Open in a new tab

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O1ⁱ	0.95	2.43	3.179 (3)	136

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

NS thanks NITT for a Fellowship. The authors thank the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

The title complex, (I), was investigated during a study of the synthesis and cytotoxicity profiles of N,N-di(alkyl/aryl)-N'-benzoylthiourea ligands, LH (Selvakumaran et al., 2011).

The Pd^II atom in (I), Fig. 1, exists in a square planar geometry defined by a cis-O₂S₂ donor set, Table 1, as found for related PdL₂ species (Selvakumaran et al., 2011). The molecule has crystallographically imposed 2-fold symmetry. There are significant deviations from the least-squares plane through the six-membered chelate ring (r.m.s. deviation = 0.233 Å) with the maximum deviations being found for the S1 (0.255 (1) Å) and Pd (–0.163 (1) Å) atoms. The major twist in the ring is found about the N1—C8 bond as seen in the value of the C7—N1—C8—S1 torsion angle of -19.3 (4) °. Nevertheless, the bond distance data, Table 1, are consistent with considerable delocalization of π-electron density over the six atoms; a similar conclusion was made for related species (Selvakumaran et al., 2011). The dihedral angle formed between the symmetry related chelate rings is 12.88 (7) °.

The most prominent intermolecular interactions in the crystal structure are of the type C—H···O, Table 2. These involve benzene-H and the coordinated O atoms, and result in the formation of two molecule aggregates sustained, from symmetry, by four such interactions, Fig. 2.

Experimental

The title complex, (I), was prepared and characterized as in the literature (Selvakumaran et al., 2011). Orange blocks were obtained by slow evaporation of a dichloromethane solution of the complex.