Ionic Liquid‐Driven Formation of and Cation Exchange in Layered Sulfido Stannates – a CH(2) 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 K(4)[SnS(4)] [Formula: see text] 4H(2)O that is based on binary tetrahedral [SnS(4)](4−) anions. The formation of the respective products, novel compounds (C(4)C(1)C(1)Im)(2)[Sn(3)S(7)] (1 a), (C(4)C(1)C(2)Im)(2)[Sn(3)S(7)] (1 b), and (C(4)C(1)C(2)Im)(2)[Sn(4)S(9)] (2) with layered anionic substructures, or the recently reported compound (C(4)C(1)C(1)Im)(4+x)[Sn(10)O(4)S(16)(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.