(2,2′-Bipyridyl-κ2 N,N′)bis­(N-butyl-N-methyl­dithio­carbamato-κ2 S,S′)cadmium(II)

Nur Amirah Jamaluddin; Ibrahim Baba; Mohamed Ibrahim Mohamed Tahir; Edward R T Tiekink

doi:10.1107/S1600536811006878

. 2011 Feb 26;67(Pt 3):m384–m385. doi: 10.1107/S1600536811006878

(2,2′-Bipyridyl-κ² N,N′)bis(N-butyl-N-methyldithiocarbamato-κ² S,S′)cadmium(II)

Nur Amirah Jamaluddin ^a, Ibrahim Baba ^a,^‡, Mohamed Ibrahim Mohamed Tahir ^b, Edward R T Tiekink ^c,^*

PMCID: PMC3052129 PMID: 21522303

Abstract

The Cd^II atom in the title compound, [Cd(C₆H₁₂NS₂)₂(C₁₀H₈N₂)], is hexacoordinated by two dithiocarbamate ligands and the N atoms from a bidentate 2,2′-bipyridyl molecule. The coordination geometry is based on a distorted trigonal–prismatic arrangement of the N₂S₄ donor set. Supramolecular chains, aligned along the a-axis direction, are mediated by C—H⋯S interactions and these are connected into layers that stack along the c axis via π–π interactions [Cg(pyridyl)⋯Cg(pyridyl) = 3.6587 (13) Å].

Related literature

For background to supramolecular polymers of zinc-triad 1,1-dithiolates, including dithiocarbamates, see: Chen et al. (2006 ▶); Benson et al. (2007 ▶). For a closely related 2,2′-bipyridyl adduct, see: Song & Tiekink (2009 ▶).

Experimental

Crystal data

[Cd(C₆H₁₂NS₂)₂(C₁₀H₈N₂)]
M _r = 593.16
Triclinic,
a = 10.3215 (4) Å
b = 10.6465 (4) Å
c = 12.4546 (5) Å
α = 81.566 (3)°
β = 74.790 (3)°
γ = 83.641 (3)°
V = 1302.64 (9) Å³
Z = 2
Mo Kα radiation
μ = 1.18 mm⁻¹
T = 150 K
0.27 × 0.16 × 0.01 mm

Data collection

Oxford Diffraction Xcaliber Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.829, T _max = 0.990
15837 measured reflections
5393 independent reflections
4623 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.066
S = 1.06
5393 reflections
284 parameters
H-atom parameters constrained
Δρ_max = 0.90 e Å⁻³
Δρ_min = −0.51 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/S1600536811006878/pk2304sup1.cif

e-67-0m384-sup1.cif^{(25.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811006878/pk2304Isup2.hkl

e-67-0m384-Isup2.hkl^{(258.7KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cd—S1	2.6104 (7)
Cd—S2	2.7685 (7)
Cd—S3	2.6468 (7)
Cd—S4	2.6783 (7)
Cd—N3	2.379 (2)
Cd—N4	2.441 (2)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16⋯S3ⁱ	0.95	2.74	3.685 (3)	172

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Symmetry code: (i) Inline graphic .

Acknowledgments

We thank UKM (UKM-GUP-NBT-08–27-111 and UKM-ST-06-FRGS0092–2010), UPM and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

Adducts related to the title compound, (I), attract attention in crystal engineering studies (Chen et al., 2006; Benson et al., 2007). The Cd^II atom in (I) is six-coordinated, being chelated by two almost symmetrically coordinating dithiocarbamate ligands, and the N donor atoms of 2,2'-bipyridyl ligand, Fig. 1 and Table 1. The coordination geometry is intermediate between trigonal prismatic and octahedral with a leaning towards the former. The angle between the triangular faces defined by the S1,S3,N4 and S2,S4,N3 atoms is 5.36 (9) °, and these are twisted by approximately 13 ° about the axis through them, compared to 0 ° for an an ideal trigonal prism and 60 ° for an ideal octahedron. The symmetric mode of coordination of the dithiocarbamate ligands is reflected in the associated C≐S bond distances which lie in the narrow range of 1.721 (2) to 1.733 (3) Å. The mode of coordination of the dithiocarbamate ligand, the disposition of the ligand donor set, and the intermediate coordination geometry observed for (I) matches a literature precedent (Song & Tiekink, 2009).

Linear supramolecular chains along the a axis are formed in the crystal structure via C—H···S interactions, Table 2 and Fig. 2. These are consolidated into layers in the ab plane by π–π interactions formed between the pyridyl rings [Cg(N3,C14–C18)···Cg(N4,C19–C23)ⁱ = 3.6587 (13) Å with angle between rings = 5.35 (11) ° for i: 2 - x, 1 - y, 1 - z]. Supramolecular layers stack along the c axis, Fig. 3.

Experimental

The title compound was prepared using an in situ method. The first step was the addition of carbon disulfide (0.03 mol) to an ethanolic solution (20 ml) of butylmethylamine (0.03 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 (0.015 mol) in ethanol (20 ml) followed by stirring for 4 h. A white precipitate was formed, filtered and washed with cold ethanol. The precipitate, Cd(C₆H₁₂NS₂)₂ (0.01 mol), and 2,2'-bipyridyl (0.01 mol) were dissolved together in chloroform (20 ml) and stirred for 1 h. A yellowish precipitate was formed, filtered and dried in a desiccator. Crystallization was from its ethanol:chloroform (1:2) solution. Yield 86%; M.pt. 424–426 K. Elemental analysis. Found (calculated) for C₂₂H₃₂CdN₄S₄: C, 44.21 (44.156); H 5.32 (5.40); Cd 18.54 (18.96); N 9.23 (9.40); S 21.45 (21.63) %. UV (CHCl₃) λ_max 284 (L(π) →L(π*)). IR (KBr): ν(C—H) 2929m; ν(C≐N) 1485m; ν(N—C) 1158 s; ν(C≐S) 974 s; ν(Cd—S) 354 s cm^-1.