Abstract
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) ] · 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.