Synthesis of bis(tert-butyl)(2-thioxo-1,3-dithiole-4,5-dithiolato)stannane, But2Sn(dmit), and bis(tert-butyl)(2-oxo-1,3-dithiole-4,5-dithiolato)stannane, But2Sn(dmio): Crystal structures, at 120 K, of polymeric But2Sn(dmit), and two polymorphs of But2Sn(d

The syntheses of bis(tert-butyl)(2-thioxo-1,3-dithiole-4,5-dithiolato)stannane, But2Sn(dmit) 1, and bis(tert-butyl)(2-oxo-1,3-dithiole-4,5-dithiolato)stannane, But2Sn(dmio) 2, are reported. Compounds 1 and 2 were prepared by the exchange reactions of But2SnCl2 with [NEt4]2[Zn(dmit)2] and [NEt4]2[Zn(dmio)2], respectively. X-ray structure determinations reveal the existance of two polymorphs of 2, 2m and 2o. In all three phases, intermolecular Sn–Sthioxo or Sn–Ooxo, as appropriate, create five-coordinate, trigonal bipyramidal tin centres. In 1 and 2o these intermolecular contacts link the molecules in chains, while in 2m they create a centrosymmetric cyclic tetramer, with a 24 membered, Sn4C8O4S8, ring. These findings of aggregated structures are in contrast to the published report that the simpler ethane-1,2-dithiolato compound, But2Sn(edt), is a molecular species in the solid state.