Ionic Liquid-Driven Formation of and Cation Exchange in Layered Sulfido Stannates - a CH2 Group Makes the Difference.

Two types of layered sulfido stannates or a molecular cluster compound are obtained upon ionothermal treatment of the simple sulfido stannate salt K4 [SnS4 ]  ·  4H2 O that is based on binary tetrahedral [SnS4 ]4- anions. The formation of the respective products, novel compounds (C4 C1 C1 Im)2 [Sn3 S7 ] (1 a), (C4 C1 C2 Im)2 [Sn3 S7 ] (1 b), and (C4 C1 C2 Im)2 [Sn4 S9 ] (2) with layered anionic substructures, or the recently reported compound (C4 C1 C1 Im)4+x [Sn10 O4 S16 (SMe)4 ][An]x (A) comprising a molecular cluster anion, is controlled by both the choice of the ionic liquid cation and the reaction temperature. We report the scale-up of the syntheses by a factor of 100 with regard to other reported ionothermal syntheses of related compounds, and a procedure of how to isolate them in phase-pure form - both being rare observations in chalcogenido stannate chemistry in ionic liquids. Moreover, the synthesis of compound 1 a can be achieved by rapid cation exchange starting out from 1 b, which has not been reported for organic cations in any chalcogenido stannate salt to date.