(1,5-Diphenyl­thio­carbazonato-κS)trimethyl­tin(IV)

Karel G Von Eschwege; Jannie C Swarts; Manuel A S Aquino; T Stanley Cameron

doi:10.1107/S1600536812047216

. 2012 Nov 24;68(Pt 12):m1518. doi: 10.1107/S1600536812047216

(1,5-Diphenylthiocarbazonato-κS)trimethyltin(IV)

Karel G Von Eschwege ^a,^*, Jannie C Swarts ^a, Manuel A S Aquino ^b, T Stanley Cameron ^c

PMCID: PMC3588764 PMID: 23468729

Abstract

In the title compound, [Sn(C₁₃H₁₁N₄S)(CH₃)₃], the Sn^IV atom is coordinated by an S atom from the 1,5-diphenylthiocarbazonato (L) ligand [Sn—S 2.4710 (6) Å] and by three methyl groups [Sn—C 2.123 (3)–2.130 (2) Å] in a distorted tetrahedral geometry. The aromatic rings of the L ligand form a dihedral angle of 2.1 (1)°.

Related literature

For general background to dithizone and dithizonato metal complexes, see: Irving (1977 ▶). For the synthesis of dithizone, see: Pelkis et al. (1957 ▶). For structural aspects of dithizone and its oxidation products and observed solvatochromism and concentratochromism, see: Von Eschwege et al. (2011a ▶). For related ligand and complex structures, see: Harrowfield et al. (1983 ▶); Kong & Wong (1999 ▶); Herbstein & Schwotzer (1984 ▶); Fernandes et al. (2002 ▶); Von Eschwege et al. (2008 ▶); Laing et al. (1971 ▶). For electrochemical studies of dithizone and its Hg complex, see: Von Eschwege & Swarts (2010 ▶); Von Eschwege et al. (2011b ▶). For femto second laser spectroscopy studies on a photochromic dithizonatomercury complex, see: Schwoerer et al. (2011 ▶). For the weighting scheme, see: Carruthers & Watkin (1979 ▶).

Experimental

Crystal data

[Sn(C₁₃H₁₁N₄S)(CH₃)₃]
M _r = 419.11
Monoclinic,
a = 11.1058 (4) Å
b = 7.2672 (3) Å
c = 22.5024 (9) Å
β = 101.0116 (11)°
V = 1782.69 (12) Å³
Z = 4
Mo Kα radiation
μ = 1.55 mm⁻¹
T = 223 K
0.20 × 0.19 × 0.08 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ▶) T _min = 0.751, T _max = 0.886
17952 measured reflections
4092 independent reflections
3344 reflections with F ² > 2.0σ(F ²)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.027
S = 1.07
3344 reflections
223 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: CRYSTALS (Watkin et al., 1999 ▶); molecular graphics: CrystalStructure; software used to prepare material for publication: CrystalStructure.

Supplementary Material

Click here for additional data file.^{(25.1KB, cif)}

Crystal structure: contains datablock(s) General, I. DOI: 10.1107/S1600536812047216/cv5361sup1.cif

e-68-m1518-sup1.cif^{(25.1KB, cif)}

Click here for additional data file.^{(200.6KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812047216/cv5361Isup2.hkl

e-68-m1518-Isup2.hkl^{(200.6KB, hkl)}

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

Acknowledgments

We acknowledge the Central Research Fund of the University of the Free State for financial assistance.

supplementary crystallographic information

Comment

During a study of the reactions of dimethylamino-trimethyltin, orange crystals of the title compound suitable for X-ray crystallography, were isolated from a diethyl ether solution. The structure revealed distorted tetrahedral coordination geometry around tin, with S—Sn—C bond angles 110.5 (4)°, 105.0 (4)° and 98.0 (9)°. Contrary to most bidentate metal-dithizonate complexes, but with the exception of one ligand in In(HDz)₃ (Harrowfield et al., 1983) and in an osmium carbonyl cluster compound (Kong & Wong, 1999), coordination of dithizone to trimethyltin(IV) was found to be monodentate, through the sulfur atom alone. The dithizonate ligand clearly illustrates a high degree of planarity, with the ligand backbone being linear, comparable to that of uncoordinated dithizone (Herbstein & Schwotzer, 1984). The Sn—S bond length of 2.4710 (6) Å agrees well with the value of 2.433 (2) Å in a related compound, 4,6-dimethylpyrimidine-2-thione triphenyltin(IV),Ph₃Sn(Me₂Pymt), reported by Fernandes et al. (2002). The less bulky pyrimidine-thione ligand, however, is bidentately coordinated to Sn through both sulfur and nitrogen, forming a four-membered ring, as opposed to the usual 5-membered metal-dithizonate rings, as seen in PhHgHDz (Von Eschwege et al., 2008). In the case of Me₃Sn(HDz), the metal lies completely outside the ligand plane, whereas in most other metal dithizonates the carbon-sulfur-metal angle is in the direction of the nitrogen (N4) that does not carry the imine proton, H2 (Laing et al., 1971). The three methyl carbons, being at bond distances of 2.13 (2) Å, hold the metal in the sterically more favourable out-of-plane position. Bond lengths along the ligand backbone are neither typically single nor double bond in character. However, the N3—N4 bond length of 1.267 (9) Å and the N1—C1 bond length of 1.308 (9) Å are close to typical double bond lengths of 1.25 Å and 1.29 Å respectively. Even the N1—N2 bond (1.327 (14) Å), which is expected to be a single bond, has more double bond character than single. N—N single bonds are typically 1.45 Å in length. The N3—C1 bond length of 1.40 (2) Å is shorter than an N—C single bond length of 1.47 Å. Observed deviation from single and double bond distances is further evidence of the high degree of electron delocalization along the dithizonate backbone.

Experimental

Solvents (AR) purchased from Merck and reagents from Sigma-Aldrich were used without further purification. Dithizone (0.1 g, 0.39 mmol) was dissolved in dry benzene (100 ml) and dimethylamino-trimethyltin (0.082 g, 0.394 mmol) was added under nitrogen. The solvent was removed under reduced pressure, yielding 0.157 g (97%) orange dithizonatotrimethyltin(IV), after crystallization from diethyl ether. The product proved to be unstable in most solvents, except benzene and diethyl ether. M.p. 134°C, λmax/nm (diethyl ether) 442, δH (300 MHz, C₆D₆, Spectrum A7)/p.p.m.: 0.47 (6 H, s, 2 × CH₃), 0.54 (3 H, s, CH₃), 6.85 – 8.09 (10 H, 3 × m, C₆H₅).