Crystal structure of bis­[S-hexyl 3-(4-methyl­benzyl­idene)di­thio­carbazato-κ2 N 3,S]palladium(II)

M Sabina Begum; M Belayet Hossain Howlader; M Chanmiya Sheikh; Ryuta Miyatake; Ennio Zangrando

doi:10.1107/S2056989015002236

. 2015 Feb 11;71(Pt 3):m63–m64. doi: 10.1107/S2056989015002236

Crystal structure of bis[S-hexyl 3-(4-methylbenzylidene)dithiocarbazato-κ² N ³,S]palladium(II)

M Sabina Begum ^a,^*, M Belayet Hossain Howlader ^a, M Chanmiya Sheikh ^b, Ryuta Miyatake ^c, Ennio Zangrando ^d

PMCID: PMC4350759 PMID: 25844210

Abstract

The whole molecule of the title complex, [Pd(C₁₅H₂₁N₂S₂)₂], is generated by twofold rotational symmetry. The palladium(II) atom exhibits a square-planar coordination geometry, and is located on the crystallographic twofold axis that induces a cis configuration of the N,S chelating ligands. In the crystal, molecules stack along the c-axis direction and there are no significant intermolecular interactions present. The structure was refined as an inversion twin with a final BASF parameter of 0.34 (2).

Keywords: crystal structure, palladium(II) complex, cis-ligand configuration

Related literature

For the crystal structures of the free Schiff base ligand and of its Ni^II complex, see: Howlader et al. (2015a ▸,b ▸). For similar bis(dithiocarbazato)Pd complexes with a cis configuration of the azomethine N and thiolate S atoms, see: Ali et al. (2002 ▸); Liu et al. (2011 ▸); Duan et al. (1998 ▸); Tampouris et al. (2007 ▸). For complexes with a trans configuration, see: Khaledi & Mohd Ali (2011 ▸); Tampouris et al. (2007 ▸); Tarafder et al. (2010 ▸).

Experimental

Crystal data

[Pd(C₁₅H₂₁N₂S₂)₂]
M _r = 693.32
Monoclinic,
a = 18.3559 (11) Å
b = 9.6747 (5) Å
c = 10.3368 (6) Å
β = 116.810 (2)°
V = 1638.37 (16) Å³
Z = 2
Cu Kα radiation
μ = 7.14 mm⁻¹
T = 173 K
0.25 × 0.16 × 0.11 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995 ▸) T _min = 0.268, T _max = 0.507
9318 measured reflections
2710 independent reflections
2121 reflections with I > 2σ(I)
R _int = 0.120

Refinement

R[F ² > 2σ(F ²)] = 0.091
wR(F ²) = 0.225
S = 1.03
2710 reflections
180 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 2.07 e Å⁻³
Δρ_min = −1.32 e Å⁻³
Absolute structure: Flack (1983 ▸), 1218 Friedel pairs
Absolute structure parameter: 0.34 (2)

Data collection: RAPID-AUTO (Rigaku, 2010 ▸); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: PLATON (Spek, 2009 ▸) and publCIF (Westrip, 2010 ▸).

Supplementary Material

Crystal structure: contains datablock(s) Global, I. DOI: 10.1107/S2056989015002236/su5071sup1.cif

e-71-00m63-sup1.cif^{(17.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015002236/su5071Isup2.hkl

e-71-00m63-Isup2.hkl^{(130.4KB, hkl)}

Click here for additional data file.^{(343.1KB, tif)}

x y z . DOI: 10.1107/S2056989015002236/su5071fig1.tif

A view of the molecular structure of the title complex, with atom labelling (symmetry code: (i) −x + 1, y, −z). Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.^{(1.1MB, tif)}

b . DOI: 10.1107/S2056989015002236/su5071fig2.tif

Crystal packing of the title complex viewed along the b axis.

CCDC reference: 1046981

Additional supporting information: crystallographic information; 3D view; checkCIF report

Acknowledgments

MBHH and MSB are grateful to the Department of Chemistry, Rajshahi University, for the provision of laboratory facilities. MCS acknowledges the Department of Applied Chemistry, Toyama University, for providing funds for single-crystal X-ray analyses.

supplementary crystallographic information

S1. Synthesis and crystallization

A solution of PdCl₂ (0.044 g, 0.25 mmol, 25 mL methanol) was added to a solution of the ligand, S-hexyl (E)-3-(4-methylbenzylidene)dithiocarbazate (0.147 g, 0.5 mmol, 10 mL methanol). The resulting mixture was stirred at room temperature for 3 h. An orange red precipitate was formed, filtered off, washed with methanol and dried in vacuo over anhydrous CaCl₂. Orange red single crystals, suitable for X-ray diffraction, of the compound were obtained by slow evaporation from a mixture of chloroform and acetonitrile (1:1) after 5 days (m.p.: 433 K).

S2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were fixed geometrically (C—H = 0.95 - 0.99 Å) and refined as riding, with U_iso(H) =1.2 U_eq(C). The rather high R factor is affected by the small crystal dimensions and consequently by low diffraction at high θ angles. The collected data were cut at a resolution of 0.85 Å. The structure was refined as an inversion twin with a final BASF parameter = 0.34 (2).

S3. Comment

In the crystal of the title complex, Fig. 1, the Pd^II atom resides on a crystallographic twofold rotational axis and the two chelating Schiff base ligands, in their deprotonated imino thiolate form, coordinate the metal center via the azomithine nitrogen atom, N1 and thiolate sulfur atom, S1 in a cis-planar configuration (Fig. 1). However, the donor atoms are not coplanar as observed for the corresponding nickel derivative (Howlader et al., 2015b), but the square planar geometry presents a slight tetrahedral distortion with displacement of atoms N1 and S1 of ± 0.121 (14) and ∓ 0.134 (6) Å, respectively, from the coordination mean plane. The Pd1–S1 and Pd1—N1 coordination bond distances are of 2.264 (4) and 2.154 (12) Å, respectively, with an N1—Pd1—S1 chelating angle of 83.2 (3)°. These values are in agreement with those observed in similar Pd-bis(dithiocarbazato) complexes, either with a cis configuration (Ali et al., 2002; Liu, et al., 2011; Duan et al., 1998; Tampouris et al., 2007) or with a trans configuration (Khaledi et al., 2011; Tampouris et al., 2007; Tarafder et al., 2010). It is worth noting that the E conformation about the imine bond N1═C8 [= 1.207 (17) Å; torsion angle N2—N1—C8—C5 = 172.1 (14)°] is different to that observed in the nickel derivative mentioned above, viz.1.2 (7)°. This allows an approach between the rings of the methylbenzylidene moieties, with a centroid-to-centroid distance of 4.114 (8) Å, indicating a very weak π-π interaction.

In the crystal, there are no significant intermolecular interactions present. The molecules pack along the c axis direction (Fig. 2).