n-Butyldichlorido{4-cyclo­hexyl-1-[1-(pyridin-2-yl-κN)ethyl­idene]thio­semi­carb­azi­dato-κ2 N 1,S}tin(IV)

Md Abu Affan; Md Abdus Salam; Mohd Razip Asaruddin; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536812025937

. 2012 Jun 16;68(Pt 7):m909–m910. doi: 10.1107/S1600536812025937

n-Butyldichlorido{4-cyclohexyl-1-[1-(pyridin-2-yl-κN)ethylidene]thiosemicarbazidato-κ² N ¹,S}tin(IV)

Md Abu Affan ^a, Md Abdus Salam ^a, Mohd Razip Asaruddin ^a, Seik Weng Ng ^b,^c, Edward R T Tiekink ^b,^*

PMCID: PMC3393180 PMID: 22807748

Abstract

Two independent molecules comprise the asymmetric unit in the title compound, [Sn(C₄H₉)(C₁₄H₁₉N₄S)Cl₂]. In each molecule, the Sn^IV atom exists within a distorted octahedral geometry defined by the N,N′,S-tridentate mono-deprotonated Schiff base ligand, two mutually trans Cl atoms, and the α-C atom of the n-butyl group; the latter is trans to the azo-N atom. The greatest distortion from the ideal geometry is found in the nominally trans angle formed by the S and pyridyl-N atoms at Sn [151.72 (7) and 152.04 (7)°, respectively]. In the crystal, molecules are consolidated into a three-dimensional architecture by a combination of N—H⋯Cl, C—H⋯π and π–π interactions [inter-centroid distances = 3.6718 (19) and 3.675 (2) Å].

Related literature

For the structures of the methyltin and phenyltin derivatives, see: Salam et al. (2010a ▶,b ▶).

Experimental

Crystal data

[Sn(C₄H₉)(C₁₄H₁₉N₄S)Cl₂]
M _r = 522.09
Monoclinic,
a = 12.1229 (3) Å
b = 15.4518 (4) Å
c = 23.6868 (6) Å
β = 103.894 (3)°
V = 4307.21 (19) Å³
Z = 8
Mo Kα radiation
μ = 1.54 mm⁻¹
T = 100 K
0.25 × 0.25 × 0.25 mm

Data collection

Agilent SuperNova Dual diffractometer with Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T _min = 0.794, T _max = 1.000
18205 measured reflections
9861 independent reflections
8503 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.085
S = 1.04
9860 reflections
471 parameters
H-atom parameters constrained
Δρ_max = 1.64 e Å⁻³
Δρ_min = −1.11 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); 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 ▶), QMol (Gans & Shalloway, 2001 ▶) 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/S1600536812025937/qm2072sup1.cif

e-68-0m909-sup1.cif^{(34.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812025937/qm2072Isup2.hkl

e-68-0m909-Isup2.hkl^{(482.2KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Sn1—C1	2.187 (3)
Sn1—N1	2.269 (2)
Sn1—N2	2.209 (2)
Sn1—S1	2.4785 (8)
Sn1—Cl1	2.5123 (8)
Sn1—Cl2	2.4959 (8)
Sn2—C19	2.182 (3)
Sn2—N5	2.255 (3)
Sn2—N6	2.215 (3)
Sn2—S2	2.4806 (8)
Sn2—Cl3	2.4959 (8)
Sn2—Cl4	2.5124 (8)

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

Cg1 is the centroid of the N1,C5–C9 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯Cl3	0.88	2.65	3.516 (3)	167
C15—H15A⋯Cg1ⁱ	0.99	2.85	3.692 (4)	143

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported financially by the Ministry of Science Technology and Innovation (MOSTI) under research grant No. 06–01-09-SF0046. The authors would like to thank Universiti Malaysia Sarawak (UNIMAS) for the facilities to carry out the research work. They also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR/MOHE/SC/12).

supplementary crystallographic information

Comment

Previous structural studies have described the methyltin (Salam et al., 2010a) and phenyltin (Salam et al., 2010b) derivatives of the title compound. The molecular structure of the title compound, (I), resembles these.

There are two independent molecules in the asymmetric unit of (I), Fig. 1. These differ in terms of the relative dispositions of the n-butyl and cycohexyl rings, Fig. 2. The Sn atom in each molecule exists within a six atom CCl₂N₂S donor set defined by the tridentate mono-deprotonated Schiff base ligand, two mutually trans chlorido atoms, and the α-C atom of the Sn-bound n-butyl group which is trans to the azo-N atom, Table 1. Distortions from the ideal octahedral geometry are ascribed primarily to the restricted bite distances formed by the Schiff base which results in an angle of 151.72 (7) ° [152.04 (7)° for the second molecule] for the nominally trans S—Sn—N angle.

The molecules are consolidated into a three-dimensional architecture by a combination of N—H···Cl and C—H···π, Table 1, as well as π—π interactions, the latter occurring between centrosymmetrically related pairs of (N1,C5–C9) and (N5,C23–C27) rings [inter-centroid distances = 3.6718 (19) and 3.675 (2) Å for symmetry operations: 2 - x, 1 - y, 1 - z and -x, 1 - y, -z, respectively], Fig. 3 and Table 2.

Experimental

2-Acetylpyridine-N(4)-cyclohexylthiosemicarbazone (0.28 g, 1.0 mmol) was dissolved in absolute methanol (10 ml) in a Schlenk round bottom flask under a nitrogen atmosphere. Then, a 10 ml me thanolic solution of butyltin(IV) trichloride (0.282 g, 1.0 mmol) was added drop-wise while stirring which resulted in the formation of a yellow solution. The reaction mixture was refluxed for 4 h and then cooled to room temperature. The yellow microcrystals that formed were filtered off, washed with a small amount of cold methanol and dried in vacuo over silica gel. Yellow crystals suitable for X-ray diffraction were obtained from the slow evaporation of a chloroform/methanol (1:1 ratio) solution at room temperature. Yield: 0.438 g, 78%: M.pt: 521–523 K: FT—IR (KBr, cm^-1) ν_max: 3308 (s, NH), 2931, 2855 (s, cyclohexyl), 1602 (m, C═N—N═C), 1020 (w, N—N), 1345, 833 (m, C—S), 652 (w, pyridine in plane), 570 (w, Sn—C), 475 (w, Sn—N). Anal. Calc. for C₁₈H₂₈Cl₂N₄SSn: C, 41.40; H, 5.40; N, 10.73%. Found: C, 41.24; H, 5.17; N, 10.59%.