Chlorido(1-cyclo­pentyl­idene-4-ethyl­thio­semicarbazidato-κ2N1,S)diphenyl­tin(IV)

Venkatraman, R.; Sitole, L.; Fronczek, F.R.

doi:10.1107/S1600536809047400

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Pages m1653-m1654

doi:10.1107/S1600536809047400

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Chlorido(1-cyclopentylidene-4-ethylthiosemicarbazidato-κ²N¹,S)diphenyltin(IV)

Ramaiyer Venkatraman,^a ^* Lungile Sitole ^a and Frank R. Fronczek ^b

^aDepartment of Chemistry and Biochemistry, Jackson State University, Jackson, MS 39217, USA, and ^bDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803, USA
^*Correspondence e-mail: venkatraman04@yahoo.com

(Received 30 September 2009; accepted 9 November 2009; online 21 November 2009)

The Sn atom in the title compound, [Sn(C₆H₅)₂(C₈H₁₄N₃S)Cl], is pentacoordinated with a trigonal-bipyramidal coordination geometry. The 1-cyclopentylidene-4-ethylthiosemicarbazidate (cpetsc) ligand coordinates through the S atom and the N atom bonds to the cyclopentyl group, forming a five-membered ring with the Sn center. The chloride ligand and the coordinated N atom are in axial positions. In the crystal structure, intermolecular N—H⋯Cl hydrogen bonds form chains along [101].

Related literature

For the biological activity of thiosemicarbazones, see: Dogmak et al. (1946 ); Klaymann et al. (1979 ); Logan et al. (1975 ); Liberta & West (1992 ). For their structural characteristics, see: Livingstone (1965 ); Akbar & Livingstone (1974 ); Campbell (1975 ); Padhey & Kauffman (1985 ); Haidue & Silverstru (1990 ); Huheey et al. (1993 ); West et al. (1990 , 1993 ); Lobana et al. (2009 ). For the antitumor activity of organotin(IV) complexes, see: Nath et al. (2001 ); Pellerito & Nagy (2002 ). For related structures, see: Swesi et al. (2005 , 2006 ); Valente et al. (1998 ); Huheey et al. (1993); Venkatraman et al. (1999 ); Pal et al. (2002 ); Teoh et al. (1999 ).

Experimental

Crystal data

[Sn(C₆H₅)₂(C₈H₁₄N₃S)Cl]
M_r = 492.62
Monoclinic, P 2₁ /n
a = 8.9031 (9) Å
b = 22.951 (3) Å
c = 11.1381 (11) Å
β = 111.094 (4)°
V = 2123.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 1.44 mm⁻¹
T = 90 K
0.27 × 0.23 × 0.17 mm

Data collection

Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.698, T_max = 0.792
33496 measured reflections
8756 independent reflections
7543 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.062
S = 1.04
8756 reflections
240 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.64 e Å⁻³
Δρ_min = −1.38 e Å⁻³

Table 1
Selected bond lengths (Å)

Sn1—C21	2.1331 (14)
Sn1—C31	2.1397 (14)
Sn1—N1	2.3123 (12)
Sn1—S1	2.4363 (4)
Sn1—Cl1	2.5095 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯Cl1ⁱ	0.80 (2)	2.71 (2)	3.4731 (15)	160 (2)
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: COLLECT (Nonius 2000 ); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR (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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809047400/lh2925sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809047400/lh2925Isup2.hkl

checkCIF report

Comment top

Thiosemicarbazones can contain chemically active –N(H)C(S) or NN(H)C(S) chromophores which make them unique in their reactivity. They are also well known for biological activities (Klaymann et al., 1979; Logan et al., 1975) since the original discovery of their anti-tubercular activity by Dogmak et al. (1946). Many review articles have appeared in the literature highlighting their structural characteristics (Livingstone 1965; Akbar & Livingstone, 1974, Campbell, 1975; Padhey & Kauffman, 1985; Haidue & Silverstru, 1990; West et al., 1990; 1993; Lobana et al., 2009). Among the non-transition metallo-pharmaceuticals, organotin (IV) complexes have demonstrated relatively high antitumor activity (Nath et al., 2001, Pellerito & Nagy, 2002). The present report describes the structure of a diiorganotin(IV) complex with N4 ethyl-substituted cyclopentanothiosemicarbazone, cpetsc.

The reaction of cpetsc with SnPh₂Cl₂ formed a monomeric anionic complex (see Fig. 1). The geometry of the tin(IV) center is penta-coordinated with a distorted trigonal bipyramidal (TBP) geometry. The two phenyl carbons C21 and C31 are positioned at the equatorial plane, while the azomethine nitrogen N1 and chlorine atoms, Cl1 occupy the axial positions. The bond distances involving the Sn atom are comparable to the reported values for dimethyl and diphenyl tin(IV) complexes of acetone (Swesi et al., 2005, Swesi et al., 2006) and diphenyl tin(IV) dichloro thiophene-2-carboxaldehyde (Teoh et al. 1999).

Significant lengthening of the C ═S bond and shortening of the C—N bond is observed as compared with the parent ligand (Valente et al., 1998, Venkatraman et al., 1999). The C—S bond distance (1.7709 Å) is relatively shorter than a single bond distance (1.81 Å) but longer than a C—S double bond (1.62 Å) distance (Huheey et al., 1993). The nature of coordination exhibited by the thiosemicarbazones are mainly due to the E and Z configuration of the ligand and the mode of coordination depends on the steric bulk of the carbonylic carbon atom linked trans to the hydrazinic nitrogen. A stable five-membered ring will be formed if the carbonylic carbon carries a small group, or else a four membered ring with larger group (Pal et al., 2002). In the present case, the metal is bound by the thiosemicarbazone, forming a five-membered chelate ring.

N—H···Cl intermolecular hydrogen bonds form chains along [1 0 1], as shown in Figure 2.

Related literature top

For the biological activity of thiosemicarbazones, see: Dogmak et al. (1946); Klaymann et al. (1979); Logan et al. (1975); Liberta & West (1992). For their structural characteristics, see: Livingstone (1965); Akbar & Livingstone (1974); Campbell (1975); Padhey & Kauffman (1985); Haidue & Silverstru (1990); Huheey et al. (1993); West et al. (1990, 1993); Lobana et al. (2009). For the antitumor activity of organotin(IV) complexes, see: Nath et al. (2001); Pellerito & Nagy (2002). For related structures, see: Swesi et al. (2005, 2006); Valente et al. (1998); Huheey et al. (1993); Venkatraman et al. (1999); Pal et al. (2002); Teoh et al. (1999).

Experimental top

A solution of diphenyltindichloride (0.344 g, 1.0 mmol) in dry methanol (10 ml) was added slowly to a boiling solution of cyclopentano-4-ethyl-3-thiosemicarbazone (0.185 g, 1.0 mmol). in methanol (50 ml) (Valente et al., 1998, Venkatraman et al., 1999). The resulting mixture was refluxed for a period of 2 h and then allowed to cool to room temperature in presence of air. Colorless rods of the title complex were obtained on slow evaporation of the solvent (yield approx. 65%, mp 460–462 K) at room temperature (C₂₀H₂₄ClN₃SSn, C, 47.55%, H, 5.45%, N, 8.48%, S, 6.45%). ¹HNMR: 7.67ppm, 9.73ppm. Main IR peaks (KBr): ν_N—H 3400, 3305, 3080 cm^-1, ν_C=S 820, 730, 705 cm^-1.

Computing details top

Data collection: COLLECT (Nonius 2000); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR (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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the numbering scheme and ellipsoids at the 50% level.
	Fig. 2. A portion of the hydrogen-bonded chain extending in along [1 0 1]. Hydrogen bonds are shown as dotted lines.

Chlorido(1-cyclopentylidene-4-ethylthiosemicarbazidato- κ²N¹,S)diphenyltin(IV) top

Crystal data top

[Sn(C₆H₅)₂(C₈H₁₄N₃S)Cl]	F(000) = 992
M_r = 492.62	D_x = 1.541 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8037 reflections
a = 8.9031 (9) Å	θ = 2.5–34.8°
b = 22.951 (3) Å	µ = 1.44 mm⁻¹
c = 11.1381 (11) Å	T = 90 K
β = 111.094 (4)°	Fragment, colorless
V = 2123.4 (4) Å³	0.27 × 0.23 × 0.17 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler	8756 independent reflections
Radiation source: fine-focus sealed tube	7543 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω and ϕ scans	θ_max = 34.8°, θ_min = 3.0°
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	h = −13→13
T_min = 0.698, T_max = 0.792	k = −35→35
33496 measured reflections	l = −17→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.062	w = 1/[σ²(F_o²) + (0.0232P)² + 1.4419P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.002
8756 reflections	Δρ_max = 0.64 e Å⁻³
240 parameters	Δρ_min = −1.38 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00150 (18)

Crystal data top

[Sn(C₆H₅)₂(C₈H₁₄N₃S)Cl]	V = 2123.4 (4) Å³
M_r = 492.62	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.9031 (9) Å	µ = 1.44 mm⁻¹
b = 22.951 (3) Å	T = 90 K
c = 11.1381 (11) Å	0.27 × 0.23 × 0.17 mm
β = 111.094 (4)°

Data collection top

Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler	8756 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	7543 reflections with I > 2σ(I)
T_min = 0.698, T_max = 0.792	R_int = 0.022
33496 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.062	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.64 e Å⁻³
8756 reflections	Δρ_min = −1.38 e Å⁻³
240 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Sn1	0.542305 (11)	0.626341 (4)	0.258844 (9)	0.01109 (3)
Cl1	0.25741 (4)	0.662360 (15)	0.18735 (4)	0.01732 (7)
S1	0.58505 (5)	0.680095 (16)	0.45705 (4)	0.01588 (7)
N1	0.80541 (14)	0.60297 (5)	0.38227 (11)	0.0127 (2)
N2	0.88356 (16)	0.63137 (5)	0.49842 (12)	0.0148 (2)
N3	0.86198 (18)	0.69504 (6)	0.64811 (13)	0.0192 (2)
H3N	0.817 (3)	0.7237 (10)	0.660 (2)	0.023*
C1	0.79332 (18)	0.66634 (6)	0.53568 (14)	0.0147 (2)
C3	1.0332 (2)	0.68887 (7)	0.72462 (17)	0.0249 (3)
H3A	1.0694	0.7230	0.7822	0.030*
H3B	1.0951	0.6882	0.6665	0.030*
C4	1.0678 (3)	0.63345 (8)	0.8051 (2)	0.0403 (6)
H4A	1.0173	0.6360	0.8699	0.060*
H4B	1.1844	0.6288	0.8480	0.060*
H4C	1.0241	0.5998	0.7491	0.060*
C11	0.89645 (16)	0.56885 (6)	0.34655 (13)	0.0125 (2)
C12	1.07472 (17)	0.56124 (7)	0.41598 (14)	0.0154 (2)
H12A	1.0983	0.5465	0.5045	0.018*
H12B	1.1324	0.5985	0.4204	0.018*
C13	1.12338 (17)	0.51630 (7)	0.33416 (15)	0.0167 (3)
H13A	1.1191	0.4762	0.3656	0.020*
H13B	1.2333	0.5241	0.3355	0.020*
C14	0.99740 (17)	0.52473 (7)	0.19811 (14)	0.0161 (3)
H14A	1.0232	0.5591	0.1553	0.019*
H14B	0.9901	0.4898	0.1441	0.019*
C15	0.84068 (17)	0.53416 (6)	0.22362 (13)	0.0140 (2)
H15A	0.7610	0.5562	0.1527	0.017*
H15B	0.7927	0.4966	0.2348	0.017*
C21	0.47816 (16)	0.53643 (6)	0.24833 (13)	0.0128 (2)
C22	0.36518 (19)	0.51214 (7)	0.13708 (15)	0.0179 (3)
H22	0.3148	0.5359	0.0636	0.021*
C23	0.3266 (2)	0.45318 (7)	0.13406 (16)	0.0223 (3)
H23	0.2500	0.4368	0.0584	0.027*
C24	0.3997 (2)	0.41813 (7)	0.24138 (17)	0.0215 (3)
H24	0.3732	0.3779	0.2388	0.026*
C25	0.51138 (19)	0.44199 (7)	0.35228 (16)	0.0188 (3)
H25	0.5609	0.4182	0.4257	0.023*
C26	0.55061 (17)	0.50098 (6)	0.35548 (14)	0.0152 (2)
H26	0.6273	0.5172	0.4313	0.018*
C31	0.60608 (17)	0.67142 (6)	0.11590 (14)	0.0140 (2)
C32	0.4852 (2)	0.69413 (7)	0.00748 (15)	0.0183 (3)
H32	0.3754	0.6884	−0.0034	0.022*
C33	0.5245 (2)	0.72517 (8)	−0.08492 (16)	0.0243 (3)
H33	0.4414	0.7401	−0.1586	0.029*
C34	0.6850 (2)	0.73426 (8)	−0.06946 (17)	0.0257 (3)
H34	0.7114	0.7559	−0.1319	0.031*
C35	0.8061 (2)	0.71168 (7)	0.03722 (17)	0.0235 (3)
H35	0.9157	0.7175	0.0475	0.028*
C36	0.76722 (18)	0.68049 (6)	0.12944 (15)	0.0171 (3)
H36	0.8509	0.6652	0.2024	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.01215 (4)	0.00957 (4)	0.01273 (5)	0.00074 (3)	0.00592 (3)	0.00121 (3)
Cl1	0.01357 (14)	0.01546 (15)	0.02368 (16)	0.00282 (11)	0.00761 (12)	0.00180 (12)
S1	0.01974 (16)	0.01448 (15)	0.01573 (15)	0.00316 (12)	0.00920 (13)	−0.00064 (12)
N1	0.0134 (5)	0.0116 (5)	0.0126 (5)	0.0001 (4)	0.0042 (4)	−0.0010 (4)
N2	0.0179 (5)	0.0123 (5)	0.0132 (5)	0.0000 (4)	0.0043 (4)	−0.0020 (4)
N3	0.0266 (7)	0.0136 (5)	0.0163 (6)	0.0001 (5)	0.0065 (5)	−0.0036 (4)
C1	0.0210 (6)	0.0101 (5)	0.0132 (6)	−0.0003 (5)	0.0065 (5)	0.0015 (4)
C3	0.0310 (9)	0.0161 (7)	0.0201 (7)	−0.0033 (6)	0.0003 (6)	−0.0042 (6)
C4	0.0507 (13)	0.0213 (8)	0.0283 (9)	−0.0043 (8)	−0.0106 (9)	0.0016 (7)
C11	0.0122 (5)	0.0121 (5)	0.0134 (6)	0.0001 (4)	0.0049 (4)	0.0007 (4)
C12	0.0120 (6)	0.0172 (6)	0.0158 (6)	0.0005 (5)	0.0038 (5)	−0.0010 (5)
C13	0.0131 (6)	0.0202 (7)	0.0182 (6)	0.0029 (5)	0.0073 (5)	−0.0001 (5)
C14	0.0157 (6)	0.0189 (6)	0.0159 (6)	0.0021 (5)	0.0084 (5)	0.0003 (5)
C15	0.0137 (6)	0.0150 (6)	0.0137 (6)	0.0009 (5)	0.0056 (5)	−0.0020 (5)
C21	0.0131 (6)	0.0124 (5)	0.0154 (6)	0.0006 (4)	0.0080 (5)	0.0011 (5)
C22	0.0222 (7)	0.0173 (6)	0.0140 (6)	−0.0023 (5)	0.0065 (5)	0.0006 (5)
C23	0.0302 (8)	0.0199 (7)	0.0187 (7)	−0.0074 (6)	0.0110 (6)	−0.0058 (6)
C24	0.0285 (8)	0.0121 (6)	0.0283 (8)	−0.0029 (5)	0.0157 (6)	−0.0023 (6)
C25	0.0190 (7)	0.0139 (6)	0.0248 (7)	0.0017 (5)	0.0094 (6)	0.0057 (5)
C26	0.0145 (6)	0.0144 (6)	0.0171 (6)	−0.0002 (5)	0.0063 (5)	0.0026 (5)
C31	0.0169 (6)	0.0117 (5)	0.0143 (6)	−0.0002 (5)	0.0070 (5)	0.0000 (5)
C32	0.0214 (7)	0.0174 (6)	0.0153 (6)	0.0010 (5)	0.0056 (5)	0.0017 (5)
C33	0.0334 (9)	0.0227 (7)	0.0167 (7)	0.0036 (6)	0.0090 (6)	0.0058 (6)
C34	0.0388 (10)	0.0217 (8)	0.0233 (8)	−0.0003 (7)	0.0191 (7)	0.0065 (6)
C35	0.0273 (8)	0.0206 (7)	0.0289 (8)	−0.0028 (6)	0.0178 (7)	0.0037 (6)
C36	0.0182 (6)	0.0149 (6)	0.0196 (7)	−0.0015 (5)	0.0085 (5)	0.0017 (5)

Geometric parameters (Å, º) top

Sn1—C21	2.1331 (14)	C14—H14A	0.9900
Sn1—C31	2.1397 (14)	C14—H14B	0.9900
Sn1—N1	2.3123 (12)	C15—H15A	0.9900
Sn1—S1	2.4363 (4)	C15—H15B	0.9900
Sn1—Cl1	2.5095 (4)	C21—C26	1.396 (2)
S1—C1	1.7709 (16)	C21—C22	1.400 (2)
N1—C11	1.2887 (18)	C22—C23	1.394 (2)
N1—N2	1.3909 (17)	C22—H22	0.9500
N2—C1	1.3047 (19)	C23—C24	1.393 (2)
N3—C1	1.3508 (19)	C23—H23	0.9500
N3—C3	1.461 (2)	C24—C25	1.389 (2)
N3—H3N	0.80 (2)	C24—H24	0.9500
C3—C4	1.522 (3)	C25—C26	1.395 (2)
C3—H3A	0.9900	C25—H25	0.9500
C3—H3B	0.9900	C26—H26	0.9500
C4—H4A	0.9800	C31—C32	1.397 (2)
C4—H4B	0.9800	C31—C36	1.403 (2)
C4—H4C	0.9800	C32—C33	1.396 (2)
C11—C12	1.5047 (19)	C32—H32	0.9500
C11—C15	1.505 (2)	C33—C34	1.392 (3)
C12—C13	1.538 (2)	C33—H33	0.9500
C12—H12A	0.9900	C34—C35	1.386 (3)
C12—H12B	0.9900	C34—H34	0.9500
C13—C14	1.539 (2)	C35—C36	1.394 (2)
C13—H13A	0.9900	C35—H35	0.9500
C13—H13B	0.9900	C36—H36	0.9500
C14—C15	1.536 (2)

C21—Sn1—C31	124.36 (5)	C15—C14—C13	102.96 (12)
C21—Sn1—N1	90.12 (5)	C15—C14—H14A	111.2
C31—Sn1—N1	94.09 (5)	C13—C14—H14A	111.2
C21—Sn1—S1	119.41 (4)	C15—C14—H14B	111.2
C31—Sn1—S1	115.63 (4)	C13—C14—H14B	111.2
N1—Sn1—S1	77.54 (3)	H14A—C14—H14B	109.1
C21—Sn1—Cl1	94.66 (4)	C11—C15—C14	102.62 (11)
C31—Sn1—Cl1	96.50 (4)	C11—C15—H15A	111.2
N1—Sn1—Cl1	163.15 (3)	C14—C15—H15A	111.2
S1—Sn1—Cl1	86.050 (13)	C11—C15—H15B	111.2
C1—S1—Sn1	98.75 (5)	C14—C15—H15B	111.2
C11—N1—N2	114.34 (12)	H15A—C15—H15B	109.2
C11—N1—Sn1	124.93 (9)	C26—C21—C22	119.24 (13)
N2—N1—Sn1	120.33 (9)	C26—C21—Sn1	118.99 (10)
C1—N2—N1	115.15 (12)	C22—C21—Sn1	121.77 (10)
C1—N3—C3	121.50 (14)	C23—C22—C21	120.02 (14)
C1—N3—H3N	117.8 (16)	C23—C22—H22	120.0
C3—N3—H3N	117.2 (16)	C21—C22—H22	120.0
N2—C1—N3	118.03 (14)	C24—C23—C22	120.34 (15)
N2—C1—S1	127.40 (11)	C24—C23—H23	119.8
N3—C1—S1	114.56 (11)	C22—C23—H23	119.8
N3—C3—C4	111.85 (16)	C25—C24—C23	119.94 (14)
N3—C3—H3A	109.2	C25—C24—H24	120.0
C4—C3—H3A	109.2	C23—C24—H24	120.0
N3—C3—H3B	109.2	C24—C25—C26	119.85 (14)
C4—C3—H3B	109.2	C24—C25—H25	120.1
H3A—C3—H3B	107.9	C26—C25—H25	120.1
C3—C4—H4A	109.5	C25—C26—C21	120.61 (14)
C3—C4—H4B	109.5	C25—C26—H26	119.7
H4A—C4—H4B	109.5	C21—C26—H26	119.7
C3—C4—H4C	109.5	C32—C31—C36	118.50 (14)
H4A—C4—H4C	109.5	C32—C31—Sn1	119.69 (11)
H4B—C4—H4C	109.5	C36—C31—Sn1	121.78 (11)
N1—C11—C12	125.18 (13)	C33—C32—C31	120.55 (15)
N1—C11—C15	124.34 (12)	C33—C32—H32	119.7
C12—C11—C15	110.35 (12)	C31—C32—H32	119.7
C11—C12—C13	104.07 (11)	C34—C33—C32	120.25 (16)
C11—C12—H12A	110.9	C34—C33—H33	119.9
C13—C12—H12A	110.9	C32—C33—H33	119.9
C11—C12—H12B	110.9	C35—C34—C33	119.81 (15)
C13—C12—H12B	110.9	C35—C34—H34	120.1
H12A—C12—H12B	109.0	C33—C34—H34	120.1
C12—C13—C14	103.78 (11)	C34—C35—C36	120.07 (16)
C12—C13—H13A	111.0	C34—C35—H35	120.0
C14—C13—H13A	111.0	C36—C35—H35	120.0
C12—C13—H13B	111.0	C35—C36—C31	120.82 (15)
C14—C13—H13B	111.0	C35—C36—H36	119.6
H13A—C13—H13B	109.0	C31—C36—H36	119.6

C21—Sn1—S1—C1	89.47 (6)	C31—Sn1—C21—C26	131.64 (11)
C31—Sn1—S1—C1	−82.09 (6)	N1—Sn1—C21—C26	36.61 (11)
N1—Sn1—S1—C1	6.48 (6)	S1—Sn1—C21—C26	−39.13 (12)
Cl1—Sn1—S1—C1	−177.41 (5)	Cl1—Sn1—C21—C26	−127.21 (11)
C21—Sn1—N1—C11	59.16 (12)	C31—Sn1—C21—C22	−48.53 (14)
C31—Sn1—N1—C11	−65.32 (12)	N1—Sn1—C21—C22	−143.57 (12)
S1—Sn1—N1—C11	179.32 (12)	S1—Sn1—C21—C22	140.69 (11)
Cl1—Sn1—N1—C11	165.84 (8)	Cl1—Sn1—C21—C22	52.61 (12)
C21—Sn1—N1—N2	−128.54 (10)	C26—C21—C22—C23	−0.2 (2)
C31—Sn1—N1—N2	106.99 (10)	Sn1—C21—C22—C23	180.00 (12)
S1—Sn1—N1—N2	−8.38 (9)	C21—C22—C23—C24	0.1 (3)
Cl1—Sn1—N1—N2	−21.85 (18)	C22—C23—C24—C25	0.2 (3)
C11—N1—N2—C1	179.64 (13)	C23—C24—C25—C26	−0.3 (2)
Sn1—N1—N2—C1	6.56 (16)	C24—C25—C26—C21	0.2 (2)
N1—N2—C1—N3	179.70 (12)	C22—C21—C26—C25	0.0 (2)
N1—N2—C1—S1	1.32 (19)	Sn1—C21—C26—C25	179.85 (11)
C3—N3—C1—N2	1.9 (2)	C21—Sn1—C31—C32	84.09 (13)
C3—N3—C1—S1	−179.53 (12)	N1—Sn1—C31—C32	177.03 (12)
Sn1—S1—C1—N2	−7.17 (14)	S1—Sn1—C31—C32	−104.83 (11)
Sn1—S1—C1—N3	174.40 (10)	Cl1—Sn1—C31—C32	−16.10 (12)
C1—N3—C3—C4	−80.7 (2)	C21—Sn1—C31—C36	−97.81 (13)
N2—N1—C11—C12	−3.6 (2)	N1—Sn1—C31—C36	−4.86 (12)
Sn1—N1—C11—C12	169.12 (10)	S1—Sn1—C31—C36	73.28 (12)
N2—N1—C11—C15	−178.95 (12)	Cl1—Sn1—C31—C36	162.00 (11)
Sn1—N1—C11—C15	−6.2 (2)	C36—C31—C32—C33	−0.1 (2)
N1—C11—C12—C13	179.96 (14)	Sn1—C31—C32—C33	178.09 (12)
C15—C11—C12—C13	−4.12 (16)	C31—C32—C33—C34	−0.5 (3)
C11—C12—C13—C14	27.08 (15)	C32—C33—C34—C35	0.9 (3)
C12—C13—C14—C15	−39.94 (14)	C33—C34—C35—C36	−0.7 (3)
N1—C11—C15—C14	155.55 (14)	C34—C35—C36—C31	0.1 (3)
C12—C11—C15—C14	−20.40 (15)	C32—C31—C36—C35	0.3 (2)
C13—C14—C15—C11	36.64 (14)	Sn1—C31—C36—C35	−177.83 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···Cl1ⁱ	0.80 (2)	2.71 (2)	3.4731 (15)	160 (2)

Symmetry code: (i) x+1/2, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[Sn(C₆H₅)₂(C₈H₁₄N₃S)Cl]
M_r	492.62
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	90
a, b, c (Å)	8.9031 (9), 22.951 (3), 11.1381 (11)
β (°)	111.094 (4)
V (Å³)	2123.4 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.44
Crystal size (mm)	0.27 × 0.23 × 0.17

Data collection
Diffractometer	Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler
Absorption correction	Multi-scan (SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.698, 0.792
No. of measured, independent and observed [I > 2σ(I)] reflections	33496, 8756, 7543
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.803

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.062, 1.04
No. of reflections	8756
No. of parameters	240
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.64, −1.38

Computer programs: COLLECT (Nonius 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Selected bond lengths (Å) top

Sn1—C21	2.1331 (14)	Sn1—S1	2.4363 (4)
Sn1—C31	2.1397 (14)	Sn1—Cl1	2.5095 (4)
Sn1—N1	2.3123 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···Cl1ⁱ	0.80 (2)	2.71 (2)	3.4731 (15)	160 (2)

Symmetry code: (i) x+1/2, −y+3/2, z+1/2.

Acknowledgements

RV acknowledges the support for supplies by the Grant JSU RISE program (NIH grant No. 1RO25GM067122). The purchase of the diffractometer was made possible by grant No. LEQSF(1999–2000)-ENH-TR-13, administered by the Louisiana Board of Regents.

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