Chloridodiphen­yl{[1-(1,3-thia­zol-2-yl-κN)ethyl­idene]-4-phenyl­thio­semicarbazidato-κ2 N 1,S}tin(IV) methanol monosolvate

Sri Ranjini Arumugam; Samuel S R Dasary; Ramaiyer Venkatraman; Hongtao Yu; Frank R Fronczek

doi:10.1107/S1600536811037627

. 2011 Sep 30;67(Pt 10):m1409–m1410. doi: 10.1107/S1600536811037627

Chloridodiphenyl{[1-(1,3-thiazol-2-yl-κN)ethylidene]-4-phenylthiosemicarbazidato-κ² N ¹,S}tin(IV) methanol monosolvate

Sri Ranjini Arumugam ^a, Samuel S R Dasary ^a, Ramaiyer Venkatraman ^a,^*, Hongtao Yu ^a, Frank R Fronczek ^b

PMCID: PMC3201461 PMID: 22065366

Abstract

The title compound, [Sn(C₆H₅)₂(C₁₂H₁₁N₄S₂)Cl]·CH₄O, is formed during the reaction between 2-acetylthiazole 4-phenylthiosemicarbazone (Hacthptsc) and diphenyltin(IV) dichloride in methanol. In the crystal structure, the Sn atom exhibits an octahedral geometry with the [N₂S] anionic tridentate thiosemicarbazone ligand having chloride trans to the central N and the two phenyl groups trans to each other. The Sn—Cl distance is 2.5929 (6), Sn—S is 2.4896 (6) and Sn—N to the central N is 2.3220 (16) Å. The MeOH molecules link the Sn complexes into one-dimensional chains via N—H⋯O and O—H⋯Cl hydrogen bonds.

Related literature

For the biological activity and structural characteristics of tin compounds of thiosemicarbazones, see: Teoh et al. (1999 ▶); Gielen et al. (2005 ▶); Chaudhary et al. (2009 ▶); Bamgboye & Bamgboye (1988 ▶); Barberi et al. (1993 ▶); Casas et al. (1994 ▶, 1996 ▶, 1997 ▶); De Sousa et al. (2001 ▶); Li et al. (2011 ▶); Macias et al. (1989 ▶); Huheey et al. (1993 ▶). For related structures, see: Venkatraman et al. (2004 ▶, 2007 ▶, 2009 ▶); Swesi et al. (2006a ▶,b ▶,c ▶); Sreekanth & Kurup (2004 ▶); Mendes et al. (2008 ▶); Li et al. (2011 ▶). For standard bond lengths, see: Allen et al. (1979 ▶); Davies (1998 ▶); Dey et al. (2003 ▶). For graph-set analysis, see: Etter (1990 ▶).

Experimental

Crystal data

[Sn(C₆H₅)₂(C₁₂H₁₁N₄S₂)Cl]·CH₄O
M _r = 615.75
Monoclinic,
a = 8.5971 (10) Å
b = 20.182 (3) Å
c = 15.794 (2) Å
β = 102.050 (7)°
V = 2680.0 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.23 mm⁻¹
T = 297 K
0.30 × 0.20 × 0.17 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.709, T _max = 0.818
31922 measured reflections
8479 independent reflections
6194 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.070
S = 1.01
8479 reflections
316 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811037627/zk2029sup1.cif

e-67-m1409-sup1.cif^{(25.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037627/zk2029Isup2.hkl

e-67-m1409-Isup2.hkl^{(414.8KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4N⋯O1	0.85 (2)	2.08 (2)	2.930 (3)	175 (2)
O1—H1S⋯Cl1ⁱ	0.76 (4)	2.52 (4)	3.248 (2)	162 (4)

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Symmetry code: (i) Inline graphic .

Acknowledgments

Purchase of the diffractometer was made possible by grant No. LEQSF (1999–2000)-ENH-TR-13, administered by the Louisiana Board of Regents.

supplementary crystallographic information

Comment

Metal complexes of heterocyclic thiosemicarbazones have been the subject of intensive research for the past three decades. Among the non-transitional metals, organotin(IV) based compounds received prominence due to their structural features and potent biological activity (Teoh et al., 1999; Gielen et al., 2005; Chaudhary et al., 2009; Bamgboye & Bamgboye, 1988; Barberi et al., 1993; Casas et al., 1994; Casas,et al., 1996; Casas et al., 1997; De Sousa et al., 2001; Li et al., 2011). Continuing with this type of study (Venkatraman et al., 2009; Venkatraman et al., 2007; Swesi et al., 2006a,b,c; Venkatraman et al., 2004), we describe here the structure of a diphenyltin chloro derivative of thiazole-2-carbaldehyde N(4)-phenyl-3-thiosemicarbazone.

The tin atom is coordinated by the tridentate ligand through the thiazole ring nitrogen, the azomethine nitrogen and thiolate sulfur atom. The octahedral complex also contains one chloro ligand trans to the central N atom of the tridentate ligand and two diphenyl groups trans to each other, as shown in Fig. 1. The tridentate ligand is reasonably planar, its 18 nonhydrogen atoms having a mean deviation of 0.082 Å from coplanarity, and a maximum of 0.176 (3) Å for methyl group C5. The bite angles of the 5-membered chelate rings are N1—Sn1—S1, 76.39 (4)° and N1—Sn1—N3, 67.57 (6)°. The two phenyl groups form a trans angle C13—Sn1—C19 154.86 (8)°, and the chloro ligand forms a trans angle N1—Sn1—Cl1 165.94 (4)°. The Sn—Cl bond is in the range of normal covalent radii (2.37–2.60 Å, Casas et al., 1997; Davies, 1998). The Sn—C (phenyl) distances are similar to those in other tin complexes reported by us earlier(Venkatraman et al., 2004; 2007; 2009; Swesi et al., 2006a,b,c). The bond length Sn—C increases with an increase in coordination number, being longer in the title compound than in four-coordinate Ph₂SnCl₂ [2.122 (2) Å] and is higher than expected (Dey et al., 2003). The C—S bond distance of 1.755 (2) Å is slightly shorter than a C—S single bond (1.81 Å) but longer than a C—S double bond (1.62 Å) (Macias et al., 1989; Huheey et al., 1993). The relatively shorter bond length of Sn—N1 (imine) (2.3322 Å) compared with Sn—N3 (thiazole) is attributed stronger base nature of thiazole nitrogen (Sreekanth & Kurup, 2004; Mendes et al., 2008; Li et al., 2011).

Two types of intermolecular hydrogen bonds are present, each involving both the Sn complex and the methanol solvent molecule. The amino N4—H group donates to methanol O1, and the methanol O1—H donates to the chloro ligand at 1/2 + x, 1/2 - y, 1/2 + z. The combination of the two hydrogen bonds forms chains of alternating Sn complexes and methanol molecules in the [1 0 1] direction, having graph set C²₂(8) (Etter, 1990), as shown in Fig. 2.

Experimental

Equimolar amounts of diphenyltin dichloride and 2-acetylthiazole 4-phenylthiosemicarbazone in dry methanol were refluxed for a period of 2 h and then allowed to cool to room temperature in presence of air. Yellow crystals of the tin complex (1) appeared in about a week.