(N-Benzyl-N-ethyl­dithio­carbamato)di-tert-butyl­chloridotin(IV)

Amirah Faizah Abdul Muthalib; Ibrahim Baba; Mohamed Ibrahim Mohamed Tahir; Edward R T Tiekink

doi:10.1107/S1600536811006398

. 2011 Feb 26;67(Pt 3):m372–m373. doi: 10.1107/S1600536811006398

(N-Benzyl-N-ethyldithiocarbamato)di-tert-butylchloridotin(IV)

Amirah Faizah Abdul Muthalib ^a, Ibrahim Baba ^a,^‡, Mohamed Ibrahim Mohamed Tahir ^b, Edward R T Tiekink ^c,^*

PMCID: PMC3051941 PMID: 21522295

Abstract

The Sn^IV atom in the title diorganotin dithiocarbamate, [Sn(C₄H₉)₂Cl(C₁₀H₁₂NS₂)], is pentacoordinated by an asymmetrically coordinating dithiocarbamate ligand, a Cl and two C atoms of the Sn-bound tert-butyl groups. The resulting C₂ClS₂ donor set defines a coordination geometry intermediate between square pyramidal and trigonal bipyramidal with a slight tendency towards the former. In the crystal structure, C—H⋯π contacts link centrosymmetrically related molecules into dimeric aggregates.

Related literature

For a review on the applications and structural chemistry of tin dithiocarbamates, see: Tiekink (2008 ▶). For additional structural analysis, see: Addison et al. (1984 ▶); Spek (2009 ▶). For a recently reported related structure, see: Abdul Muthalib et al. (2010 ▶).

Experimental

Crystal data

[Sn(C₄H₉)₂Cl(C₁₀H₁₂NS₂)]
M _r = 478.69
Triclinic,
a = 8.6140 (2) Å
b = 10.9604 (3) Å
c = 11.4765 (3) Å
α = 91.858 (2)°
β = 96.193 (2)°
γ = 96.011 (2)°
V = 1070.24 (5) Å³
Z = 2
Mo Kα radiation
μ = 1.51 mm⁻¹
T = 150 K
0.30 × 0.23 × 0.16 mm

Data collection

Oxford Diffraction Xcaliber Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.935, T _max = 1.000
26998 measured reflections
4865 independent reflections
4707 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.018
wR(F ²) = 0.046
S = 1.11
4865 reflections
215 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.50 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/S1600536811006398/zs2099sup1.cif

e-67-0m372-sup1.cif^{(22.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811006398/zs2099Isup2.hkl

e-67-0m372-Isup2.hkl^{(233.4KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Sn—Cl1	2.4847 (4)
Sn—S1	2.4760 (4)
Sn—S2	2.7409 (4)
Sn—C11	2.1884 (14)
Sn—C15	2.1879 (15)

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

Cg1 is the centroid of the C5–C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3a⋯Cg1	0.98	2.78	3.6491 (18)	149
C13—H13b⋯Cg1ⁱ	0.98	2.96	3.5401 (18)	119

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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

Organotin dithiocarbamates attract attention as they exhibit properties suggesting their potential as anti-cancer agents, anti-microbials and insecticides (Tiekink, 2008). Motivated by these and in continuation of structural studies of these systems (Abdul Muthalib et al., 2010), the analysis of the title compound, (I), was undertaken.

The Sn^IV atom in (I) is five-coordinated, being chelated by an asymmetrically coordinating dithiocarbamate ligand, a Cl and two C atoms of the Sn-bound tert-butyl groups (Fig. 1 and Table 1). The asymmetric chelating mode of the non-symmetric dithiocarbamate ligand is reflected in the non-equivalence of the associated C≐S bond distances (Table 1). The coordination geometry is intermediate between square pyramidal and trigonal bi-pyramidal with a leaning towards the former. This assignment is based on the value calculated for τ of 0.45 for the Sn atom, which compares to the τ values of 0.0 and 1.0 for ideal square pyramidal and trigonal bi-pyramidal geometries, respectively (Spek, 2009; Addison et al., 1984). The mode of coordination of the dithiocarbamate ligand, the disposition of the ligand donor set, and the intermediate coordination geometry observed for (I) matches with the literature precedents (Tiekink, 2008).

The most prominent feature of the crystal packing is the presence of C–H···π interactions (Table 2). As shown in Fig. 2, these lead to dimeric aggregates. It is also noted that intramolecular C–H···π contacts are present so that the benzene ring participates in two such interactions (Table 2, Fig. 2). The dimeric aggregates stack into columns along the a axis (Fig. 3).

Experimental

The dithiocarbamate ligand was prepared by the addition of carbon disulfide (0.01 mol) to an ethanolic solution (20 ml) of ethylbenzylamine (0.01 mol). The mixture was stirred for 1 h at 277 K, after which the solution was added drop wise to a solution of di-tert-butyltin(IV) dichloride (0.005 mol) in ethanol (20 ml). The resulting mixture was stirred for 1 h. The white precipitate was filtered, washed with cold ethanol and dried in a desiccator. Crystallization was carried out by using an ethanol:chloroform (1:2) mixture. Yield 76%; m.p. 451–453 K. Elemental analysis. Found (calculated) for C₁₈H₃₀ClNS₂Sn: C, 44.81 (45.16); H 6.27 (6.32), N 2.72 (2.93), S 13.23 (13.40); Sn 23.98 (24.80) %. UV (CHCl₃) λ_max 244 (L(π) →L(π*)). IR (KBr): ν(C—H) 2933m, 2958m; ν(C≐N) 1496m; ν(N—C) 1185 s; ν(C≐S) 950 s; ν(Sn—S) 351 s cm^-1.