Di­chlorido­diphenyl­bis­(thio­urea-κS)tin(IV)

Yaya Sow; Libasse Diop; Kieran C Molloy; Gabriele Kociok-Köhn

doi:10.1107/S1600536813024343

. 2013 Sep 12;69(Pt 10):m539–m540. doi: 10.1107/S1600536813024343

Dichloridodiphenylbis(thiourea-κS)tin(IV)

Yaya Sow ^a,^*, Libasse Diop ^a, Kieran C Molloy ^b, Gabriele Kociok-Köhn ^b

PMCID: PMC3790350 PMID: 24098172

Abstract

The title compound, [Sn(C₆H₅)₂Cl₂(CH₄N₂S)₂], has been obtained from the reaction between Sn(C₆H₅)₂Cl₂ and SC(NH₂)₂. The asymmetric unit consists of one half of the molecular unit, the remainder generated by a twofold rotation axis located along the Cl—Sn—Cl bonds. The Sn^IV atom is coordinated by two phenyl groups, two Cl atoms and two thiourea ligands in an all trans octahedral C₂Cl₂S₂ environment. Individual molecules are connected through N—H⋯Cl hydrogen bonds, leading to a three-dimensional network structure. Intramolecular N—H⋯Cl hydrogen bonds are also present.

Related literature

For background to organotin(IV) chemistry, see: Kapoor et al. (2005 ▶); Sadiq-ur-Rehman et al. (2007) ▶; Zhang et al. (2006 ▶). For organotin(IV) compounds exhibiting biological activity, see: Nath et al. (2001 ▶); Pellerito & Nagy (2002 ▶). For chloridotin(IV) complexes, see: Amini et al. (2002 ▶); Müller et al. (2008 ▶). For tin(IV) complexes containing thiourea groups, see: Donaldson et al. (1984 ▶); Sow et al. (2012 ▶); Wirth et al. (1998 ▶).

Experimental

Crystal data

[Sn(C₆H₅)₂Cl₂(CH₄N₂S)₂]
M _r = 496.03
Tetragonal,
a = 14.6401 (2) Å
c = 17.7899 (3) Å
V = 3812.95 (10) Å³
Z = 8
Mo Kα radiation
μ = 1.84 mm⁻¹
T = 150 K
0.35 × 0.35 × 0.25 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T _min = 0.565, T _max = 0.656
23870 measured reflections
2183 independent reflections
1892 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.019
wR(F ²) = 0.051
S = 1.06
2183 reflections
123 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.72 e Å⁻³

Data collection: COLLECT (Nonius, 1999 ▶); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO 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, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813024343/wm2764sup1.cif

e-69-0m539-sup1.cif^{(14.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813024343/wm2764Isup2.hkl

e-69-0m539-Isup2.hkl^{(105.4KB, 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
N1—H1B⋯Cl2	0.86 (3)	2.50 (3)	3.345 (2)	166 (2)
N2—H2A⋯Cl1ⁱ	0.81 (3)	2.41 (3)	3.2119 (19)	170 (3)

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

We thank Dr Raymundo Cea Olivares, Instituto de Química UNAM, Mexico, for performing the elemental analyses.

supplementary crystallographic information

1. Comment

Many Sn(C₆H₅)₂Cl₂ adducts have previously been reported and structurally characterized (Kapoor et al., 2005; Müller et al., 2008; Sadiq-ur-Rehman et al., 2007; Sow et al., 2012; Zhang et al., 2006). Organotin (IV) compounds exhibiting biological (e.g antitumour) activity have also been reported (Nath et al., 2001; Pellerito & Nagy, 2002). On allowing Sn(C₆H₅)₂Cl₂ and SC(NH₂)₂ to react, crystals of the title compound, [Sn(C₆H₅)₂Cl₂(CH₄N₂S)₂], (I), were obtained and the structure determined.

The molecule in the structure of compound (I) is located on a twofold rotation axis. The Sn^IV atom has an octahedral trans, trans, trans-C₂S₂Cl₂ coordination sphere (Fig. 1), defined by two carbon atoms of symmetry-related phenyl groups [2.1622 (17) Å], two Cl [2.5194 (6), 2.6224 (6) Å] and two sulfur atoms of the thiourea ligands [2.6755 (4) Å]. The Sn—S bond is somewhat shorter than the analogous bond [2.6945 (7) Å] in the related structure of [Sn₂(C₂O₄)(C₆H₅)₆(CH₄N₂S)₂] (Sow et al., 2012), but is in the range of other Sn—S bonds reported for tin(IV) structures containing thiourea ligands (Donaldson et al., 1984; Wirth et al., 1998).

The Sn—Cl2 distance [2.5194 (6) Å] is shorter than the Sn—Cl1 distance [2.6224 (6) Å] as a consequence of the involvement of Cl1 in strong intermolecular N2—H2A···Cl1 hydrogen bond formation (Table 1), which leads to the formation of a three-dimensional network structure. Somewhat weaker intramolecular N1—H1B···Cl2 hydrogen bonds are also present (Fig. 2). When compared to the unique Sn—Cl distance in {[((CH₃)₃C)₂(CH₃)PO]₂^.Sn(C₆H₅)₂Cl₂} [2.5567 (16) Å] (Müller et al., 2008) or the two Sn—Cl distances in {18-crown-6^.Sn(C₆H₅)₂Cl₂^.2H₂O} [2.5521 (7), 2.5627 (7) Å] (Amini et al., 2002), two adducts in which the Cl atoms are not involved in hydrogen bonding, it appears that in (I) the intermolecular hydrogen bonding has led to a weakened Sn—Cl1 bond and a concomitant strengthening of Sn—Cl2. Moreover, the strength of Sn—Cl2 in comparison with examples of other Sn—Cl bonds where the halogen is not involved in hydrogen bonding suggests that the intramolecular hydrogen bonds are weaker than suggested by their interatomic separation.

2. Experimental

All chemicals were purchased from Aldrich (Germany) and used without any further purification. The title compound, [Sn(C₆H₅)₂Cl₂(CH₄N₂S)₂], has been synthesized from the reaction between Sn(C₆H₅)₂Cl₂ (0.250 g, 0.727 mmol) and SC(NH₂)₂ (0.111 g, 1.454 mmol) in a 1:2 ratio in absolute ethanol solution. After stirring for two hours, a clear solution was obtained that was slowly evaporated at room temperature yielding colourless crystals (weight, yield 69%) with a melting point of 515 K. Analytical data for C₁₄H₁₈Cl₂N₄S₂Sn (found) %C: 33.90 (33.87); %H: 3.66 (3.63); %N: 11.29(11.27); %S: 12.93 (12.90); %Sn: 23.93 (23.98).