Dichloridobis(pyridine-2-thiolato-κ²N,S)tin(IV): a new polymorph

Abstract

The title compound, [SnCl2(C5H4NS)2], is the product of reaction of 2,2′-dipyridyl disulfide with tin tetra­chloride. The SnIV atom adopts a distorted octa­hedral geometry, with the two bidentate pyridine-2-thiol­ate ligands forming two planar four-membered chelate rings. The two Sn—Cl, two Sn—N and two Sn—S bonds are in cis, cis and trans configurations, respectively. The crystal grown from acetonitrile represents a new monoclinic polymorph in space group C2/c with the mol­ecule having twofold rotational symmetry, the SnIV atom lying on the twofold axis. The mol­ecular structure of the monoclinic polymorph is very close to that of the triclinic polymorph studied previously in space group P-1, the mol­ecule occupying a general position [Masaki & Matsunami (1976 ▶). Bull. Chem. Soc. Jpn, 49, 3274–3279; Masaki et al. (1978 ▶). Bull. Chem. Soc. Jpn, 51, 3298–3301]. Apparently, the formation of the two polymorphs is determined by the different systems of inter­molecular inter­actions. In the crystal of the monoclinic polymorph, mol­ecules are bound into ribbons along the c axis by C—H⋯Cl hydrogen bonds, whereas in the crystal of the triclinic polymorph, mol­ecules form chains along the a axis by attractive S⋯S inter­actions. The crystal studied was a pseudo-merohedral twin; the refined BASF value is 0.221 (1).

Reactivity of Organotin(I) Dimers RSnSnR (R = 2,6-(Me2NCH2)2C6H3, 4-t-Bu-2,6-{P(O)(O-i-Pr)2}2C6H2) with Diaryl Dichalcogenides, ArEEAr (E = S, Se, Te; Ar = Ph, 2-C5H4N): Control of Secondary Sn···Sn Interactions by Intramolecular Coordination and Identity of the Aryl Chalcogenate

“…In contrast to the case for compound 7 , the nitrogen atoms of both pyridyl ligands coordinate the tin atom at distances of 2.267(2) (Sn(1)–N(31))] and 2.281(3) Å (Sn(1)–N(41)), respectively. These values are comparable to that observed in SnCl 2 (C 5 H 4 NS) 2 (2.259(2) Å) …”

Dichloridobis(pyridine-2-selenolato-κ2N,Se)tin(IV)

“…1). Compound I is isostructural with the monoclinic modification of the related thio-analogue reported by us very recently (Ismaylova et al, 2012). For the synthesis and structure of the triclinic modification of this thio-analogue, see: Masaki & Matsunami (1976) and Masaki et al (1978).…”

“…For metal complexes with 2,2 0 -dipyridyl dichalcogenides, see: Kadooka et al (1976a,b); Cheng et al (1996); Kienitz et al (1996); Bell et al (2000); Kita et al (2001); Kedarnath et al (2009). For syntheses and structures of related tin(IV) compounds, see: Masaki & Matsunami (1976); Masaki et al (1978); Labisbal et al (1993); Chopra et al (1996); Ismaylova et al (2012). Hydrogen-bond geometry (Å , ).…”

Molecular structures of pyridinethiolato complexes of Sn(II), Sn(IV), Ge(IV), and Si(IV)

“…Thus, this angle clearly indicated attraction between the central atom E and both donor atoms S and Brought to you by | provisional account Unauthenticated Download Date | 6/3/15 5:52 PM (4) (1) 166.13 (5) 165.10 (3) 163.06 (3) 159.13 (7) N(1)-E(1)-Cl (2) 165.34 (5) 163.74 (3) 161.05 (3) a Entries in these columns relate to crystal structures determined in this work. b Entries in this column refer to related parameters in the crystal structure of the monoclinic modification of Cl 2 Sn(PyS) 2 (Ismaylova et al, 2012).…”

“…In terms of group 14 element coordination chemistry, to date, the Cambridge Structural Database contains examples of only Sn and Pb compounds of pyridine-2-thiolate; Ge and Si compounds are lacking (ConQuest 1.15, 2012). In tin(IV) chemistry, PyS -and related ligands have been shown capable of enhancing the tin coordination number to 5, 6, 7, and even 8 (Scheme 3, VII, VIII and IX, X, XI, respectively) (Masaki et al, 1976(Masaki et al, , 1978Castaño et al, 1990;Damude et al, 1990;Bouâlam et al, 1992;Schmiedgen et al, 1994;Couce et al, 1996;Huber et al, 1997;de Castro et al, 2001;Sousa-Pedrares et al, 2003;Ismaylova et al, 2012), thus underlining their already intriguing ligand features in mononuclear group 14 element coordination chemistry. In addition, HPyS has been shown to enter the tin coordination sphere as a charge-neutral ligand via S-donor action (Valle et al, 1987;Wu et al, 2000).…”