(2,2′-Bipyridine-κ2 N,N′)bis­(N-isopropyl-N-methyl­dithio­carbamato-κ2 S,S′)cadmium

Nor Asiken Abdul Wahab; Ibrahim Baba; Mohamed Ibrahim Mohamed Tahir; Edward R T Tiekink

doi:10.1107/S1600536811012414

. 2011 Apr 7;67(Pt 5):m551–m552. doi: 10.1107/S1600536811012414

(2,2′-Bipyridine-κ² N,N′)bis(N-isopropyl-N-methyldithiocarbamato-κ² S,S′)cadmium

Nor Asiken Abdul Wahab ^a, Ibrahim Baba ^a,^‡, Mohamed Ibrahim Mohamed Tahir ^b, Edward R T Tiekink ^c,^*

PMCID: PMC3089361 PMID: 21754287

Abstract

The Cd^II atom in the title compound, [Cd(C₅H₁₀NS₂)₂(C₁₀H₈N₂)], exists in an N₂S₄ donor set defined by two chelating dithiocarbamate anions as well as a 2,2′-bipyridine ligand. The coordination geometry approximates a trigonal prism. The crystal packing features weak C—H⋯S interactions, leading to linear supramolecular chains along the a axis. The primary connections between these are by π–π stacking interactions [ring centroid distance between centrosymmetrically related pyridyl rings = 3.7455 (10) Å]. Overall, the crystal structure may be described as comprising double layers of molecules that stack along the b axis.

Related literature

For related structures of pyridyl adducts of cadmium dithiocarbamtes, see: Song & Tiekink (2009 ▶); Broker & Tiekink (2011 ▶); Jamaluddin et al. (2011 ▶).

Experimental

Crystal data

[Cd(C₅H₁₀NS₂)₂(C₁₀H₈N₂)]
M _r = 565.10
Monoclinic,
a = 9.6061 (2) Å
b = 28.6277 (4) Å
c = 9.8187 (2) Å
β = 112.860 (2)°
V = 2488.07 (8) Å³
Z = 4
Mo Kα radiation
μ = 1.23 mm⁻¹
T = 150 K
0.17 × 0.13 × 0.05 mm

Data collection

Oxford Diffraction Xcaliber Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.853, T _max = 0.941
53095 measured reflections
5700 independent reflections
5013 reflections with I > 2σ(I)
R _int = 0.048

Refinement

R[F ² > 2σ(F ²)] = 0.022
wR(F ²) = 0.053
S = 1.03
5700 reflections
268 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 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 datablocks global, I. DOI: 10.1107/S1600536811012414/hb5834sup1.cif

e-67-0m551-sup1.cif^{(24.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811012414/hb5834Isup2.hkl

e-67-0m551-Isup2.hkl^{(273.5KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cd—S1	2.6463 (5)
Cd—S2	2.7128 (5)
Cd—S3	2.6518 (5)
Cd—S4	2.6490 (5)
Cd—N3	2.4122 (14)
Cd—N4	2.4191 (15)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C18—H18⋯S2ⁱ	0.95	2.78	3.712 (2)	167

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank Universiti Kebangsaan Malaysia (UKM-GUP-NBT-08–27-111), the Ministry of Higher Education (UKM-ST-06-FRGS0092–2010), Universiti Putra Malaysia and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

In continuation of systematic structural studies of various pyridyl adducts of cadmium dithiocarbamates (Song & Tiekink, 2009; Broker & Tiekink, 2011; Jamaluddin et al., 2011), the title compound Cd[S₂CN(Me)iPr)₂]₂(2,2'-bipyridine), (I), was investigated. The Cd^II atom is coordinated by two dithiocarbamate ligands, each essentially forming symmetric Cd—S bonds, and a symmetrically chelating 2,2'-bipyridine ligand, Fig. 1 and Table 1. The equivalence in the Cd—S bond distances is reflected in the narrow range of associated C≐S bond distances, i.e. 1.7168 (18) to 1.7290 (17) Å. A small twist is noted between the pyridyl rings of the 2,2'-bipyridine ligand as seen in the dihedral angle of 9.25 (9) ° formed between the rings. The N₂S₄ donor set defines a distorted trigonal prismatic geometry.

The crystal packing of (I) features linear supramolecular chains along the a axis that are sustained by C—H···S interactions, Fig. 2 and Table 2. Chains lie in the ac plane and inter-digitate viaπ–π interactions with centrosymmetrically related layers to form a double layer [ring centroid(N3-pyridyl)···ring centroid(N3-centroid)ⁱ = 3.7455 (10) Å for i: 2 - x, 1 - y, 1 - z]. Double layers stack along the b axis and are separated by hydrophobic interactions, Fig. 3.

Experimental

The title compound was prepared using an in situ method by the addition of carbon disulfide (0.02 mol) to an ethanolic solution (20 ml) of methylisopropropylamine (0.02 mol) and 2,2-bipyridine (0.01 mol) in ethanol (20 ml). The mixture was stirred for 1 h at 277 K. The resulting solution was added drop-wise to a solution of cadmium(II) dichloride (0.01 mol) in ethanol (20 ml). The mixture was stirred 3 h. The yellowish precipitate was filtered, washed with cold ethanol and dried in a desiccator. Recrystallization was from ethanol:chloroform (1:2 v/v) to yield yellow prisms of (I). M.pt. 473.6–475.2 K. Elemental analysis. Found (calculated) for C₂₂H₃₂CdN₄S₄: C, 42.63 (42.51); H 4.48 (4.99); N 10.74 (9.91); S 21.80 (22.70) %. UV (CHCl₃) λ_max 283.5 and 261.0 nm (L(π) →L(π*)). IR (KBr): ν(C—H) 2928 s; ν(C≐N) 1565 s; ν(N—C) 1468 m; ν(C≐S) 970 s; ν(Cd—S) 381 s cm^-1.