New layered tin(II) thiophosphates ASnPS ₄ (A = K, Rb, Cs): Synthesis, structure, glass formation, and the modulated CsSnPS ₄

The layered compounds KSnPS ₄ (1), RbSnPS ₄ (2), and CsSnPS ₄ (3) were synthesized using the chalcophosphate flux technique at high temperature and are rare examples of divalent Sn(II) thiophosphates. Orange polyhedral crystals of compound 1 crystallize in the monoclinic space group P2 ₁/c with a = 6.6673(13) Å, b = 11.9697(24) Å, c = 8.7604(18), and β=127.347(8)° in a 2-dimensional layered structure. Compound 2 is isostructural to 1. Yellow block shaped crystals of compound 3 crystallize in the monoclinic superspace group P2 ₁(αβ0)0 with a commensurate q-vector at 1/4a* + 1/4c* with a = 18.0477(14) Å, b = 6.2021(5) Å, and c = 6.8415(5) Å. The structure of all three compounds contains SnS ₃ pyramids, which is an extremely rare solid state chalcogenide coordination environment. All three compounds are semiconductors having well-defined band-gaps between 2.0 and 2.2 eV. The compounds are congruently melting and can be obtained as glasses by rapid quenching of the melt, which subsequently crystallize upon heating.