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

Md Abu Affan; Md Abdus Salam; Ismail Jusoh; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536812010902

. 2012 Mar 17;68(Pt 4):m435–m436. doi: 10.1107/S1600536812010902

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

Md Abu Affan ^a, Md Abdus Salam ^a, Ismail Jusoh ^a, Seik Weng Ng ^b,^c, Edward R T Tiekink ^b,^*

PMCID: PMC3343835 PMID: 22589809

Abstract

The distorted octahedral geometry about the Sn^IV atom in the title compound, [Sn(C₆H₅)₂(C₁₄H₁₉N₄S)Cl], is defined by the N,N,S-tridentate Schiff base ligand, two mutually trans ipso-C atoms of the Sn-bound phenyl groups, and the Cl atom which is trans to the azo N atom. The two five-membered chelate rings and pyridyl ring are almost coplanar with the dihedral angle between the outer five-membered chelate and pyridine rings being 5.39 (8)°. Centrosymmetric dimers feature in the crystal packing mediated by N—H⋯S hydrogen bonds, leading to eight-membered {⋯HNCS}₂ synthons. The dimeric aggregates are connected into a three-dimensional architecture by C—H⋯Cl and C—H⋯π interactions, as well as π–π interactions occurring between centrosymmetrically related pyridine rings [centroid–centroid distance = 3.6322 (13) Å].

Related literature

For the crystal structure of the dichloridophenyl analogue, see: Salam et al. (2010 ▶). For a related structure, see: de Sousa et al. (2007 ▶).

Experimental

Crystal data

[Sn(C₆H₅)₂(C₁₄H₁₉N₄S)Cl]
M _r = 583.73
Triclinic,
a = 9.7368 (4) Å
b = 9.9771 (4) Å
c = 13.4045 (5) Å
α = 90.103 (3)°
β = 97.013 (3)°
γ = 100.931 (4)°
V = 1268.57 (9) Å³
Z = 2
Mo Kα radiation
μ = 1.22 mm⁻¹
T = 100 K
0.40 × 0.30 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.642, T _max = 0.793
8973 measured reflections
5781 independent reflections
5122 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.061
S = 1.00
5781 reflections
299 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▶); 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: X-SEED (Barbour, 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/S1600536812010902/zl2462sup1.cif

e-68-0m435-sup1.cif^{(24.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812010902/zl2462Isup2.hkl

e-68-0m435-Isup2.hkl^{(283KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Sn—C1	2.152 (2)
Sn—C7	2.159 (2)
Sn—N2	2.3100 (19)
Sn—N1	2.3869 (19)
Sn—S1	2.5209 (6)
Sn—Cl1	2.5449 (6)

Open in a new tab

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

Cg1 is the centroid of the C7–C12 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H1⋯S1ⁱ	0.88	2.62	3.489 (2)	171
C13—H13⋯Cl1ⁱⁱ	0.95	2.73	3.415 (3)	129
C19—H19C⋯Cl1ⁱⁱⁱ	0.98	2.85	3.809 (2)	166
C15—H15⋯Cg1^iv	0.95	2.47	3.384 (3)	162

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

We thank MOSTI (grant No. 06–01-09-SF0046) and the Universiti Malaysia Sarawak for supporting this study. We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR/MOHE/SC/3).

supplementary crystallographic information

Comment

The synthesis and crystal structure of the title compound was determined in connection with recent structural studies of organotin chlorido derivatives of thiosemicarbazones (Salam et al., 2010).

The Sn atom in the title compound, Fig. 1, exists within a six atom C₂ClN₂S donor set defined by the tridentate monodeprotonated Schiff base ligand, two mutually trans ipso-C atoms of the Sn-bound phenyl groups, and the Cl atom which is trans to the azo-N atom, Table 1. There are distortions from the ideal octahedral geometry which are ascribed to the restricted bite angles formed by the Schiff base ligand which result in an angle of 145.90 (5)° for the nominally trans S1—–Sn—–N1 angle. The disposition of donor atoms resembles that found in the structure of the N-4-morpholinyl derivative (de Sousa et al., 2007). Both five-membered rings are essentially planar with the r.m.s. deviations being 0.111 and 0.020 Å for the SnSN₂C and SnN₂C₂ rings, respectively; the former ring has a small twist about the Sn—S1 bond with Sn and S1 atoms lying 0.068 (1) and -0.081 (1) Å out of the least-squares plane, respectively. The dihedral angle between the chelate rings is 3.42 (7)° and those between each of these and the pyridyl ring are 5.39 (8) and 2.29 (9)°, respectively, indicating an essentially planar arrangement of fused rings. Finally, the Sn-bound benzene rings are almost parallel with the dihedral angle being 8.72 (12)°.

The most significant feature in the crystal packing of the title compound is the formation of centrosymmetric dimers via N—H···S hydrogen bonds that lead to flat, eight-membered {···HNCS}₂ synthons, Table 1. The dimeric aggregates are connected into a three dimensional architecture by C—H···Cl and C—H···π interactions, Table 1, as well as π—π interactions occurring between centrosymmetrically related pyridyl rings [centroid···centroid distance = 3.6322 (13) Å for symmetry operation: 1 - x, 1 - y, 2 - z], Fig. 2.

Experimental

2-Acetylpyridine-N-cyclohexylthiosemicarbazone (0.28 g, 1 mmol) was dissolved in methanol (10 ml) in a Schlenk flask under a nitrogen atmosphere. Diphenyltin(IV) dichloride (0.34 g, 1 mmol) dissolved in methanol (10 ml) was added. The yellow solution was refluxed for 4 h. Slow evaporation of the solvent gave a yellow compound (0.423 g). Recrystallization from a chloroform/methanol (1/1) mixture gave small dark-yellow prisms embedded in large light-yellow blocks. A small light-yellow specimen was cut from a light-yellow block for the diffraction measurements. The dark-yellow specimen proved to be (C₆H₅)Sn(C₁₄H₁₉N₄S)Cl₂ from unit cell determination (Salam et al., 2010).