Further studies on dialkyltin 1,3-dithiole-2-thione-4,5-dithiolates, R 2Sn(dmit). Crystal structures of orthorhombic- and monoclinic-Et 2Sn(dmit), and Me 2Sn(dmit)

Abstract

The crystal structures of orthorhombic and monoclinic diethyltin bis(1,3-dithiole-2-thione-4,5-dithiolate), [Et 2Sn(dmit)], ortho- 3 and mono- 3, and dimethyltin bis(1,3-dithiole-2-thione-4,5-dithiolate) ( 4) have been determined. Transformation of solid ortho- 3 to mono- 3 occurs at 139–140°C. Molecules of ortho- 3, obtained by recrystallisation from aqueous acetone, and 4, are linked into chains as a result of intermolecular Snthione S(5) interactions: the tin centres are penta-coordinate with distorted trigonal bipyramidal geometries. The intermolecular, SnS(5) thione bonds {3.0083(15) Å in ortho- 3 at 150 K [3.037(4) at 298 K], and 3.001(2) and 2.960(2) Å in the two independent molecules of 4 at 150 K}, are considerably longer than the primary intramolecular Sn bonds to the dithiolato S atoms [between 2.440(3) and 2.5235(15) Å]. The two independent molecules of mono- 3, obtained from aqueous methanol, have quite different arrangements: tin atoms in molecule A form two relatively weak intermolecular Snthione S bonds, 3.567(2) and 3.620(3) Å, with the formation of sheets, while those in molecule B form one similar bond, SnS=3.555(2) Å to give chains, with a much longer contact, Sn⋯ S=3.927(2) A ̊ to another chain. The latter is only ca. 0.12 Å less than the van der Waals radii sum for Sn and S. Sulfur–sulfur contacts, within the sum of the van der Waals radii of two S atoms, 3.60 Å, in 3 and 4, not only reinforce the chains but also help to establish 3D networks.