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.