Controlling Lewis basicity in polythioarsenate fluxes: stabilization of KSnAsS(5) and K(2)SnAs(2)S(6). Extended chains and slabs based on pyramidal beta-[AsS(4)](3-) and [AsS(3)](3-) units.

Two low-dimensional compounds, KSnAsS(5) and K(2)SnAs(2)S(6), were prepared using liquid polythioarsenate salts, and the results differ from those obtained with the well studied thiophosphate flux. KSnAsS(5) crystallizes in the orthorhombic space group Pbam with cell parameters of a = 8.136(2) A, b = 13.784(4) A, c = 7.428(2) A. KSnAsS(5) features the unusual pyramidal species [AsS(2)(S(2))](3-). K(2)SnAs(2)S(6) crystallizes in the trigonal space group P3 macro with cell parameters a = 6.717(5) A, b = 7.204(8) A, gamma = 120 degrees. The compounds were obtained by controlling the Lewis basicity of the K(2)S/As(2)S(3)/S flux. The optical, thermal, and spectroscopic properties of the compounds are reported.