The new palladium thiophosphates, APdPS4(A = K, Cs) and the new mixed-metallic phosphate, Li3-4x(V1-xMx)2(PO4)3 (M = Nb, Ta) have been prepared with the use alkali metal halide fluxes and their crystal structures have been investigated by single crystal X-ray diffraction techniques. APdPS4 phases are found to have polymorphic structures. The structures have two kind of one-dimensional chains separated from one another by alkali metal cations, A+. Although they have different arrangements, both chains share the common building blocks, square planar PdS4 and tetrahedral PS4. In this paper, polymorphic structures of the related phases are described along with the title compound. The classical charge balance of the compounds can be represented by [A+][Pd2+][P5+][S2-]4. The mixed-metallic phosphates, Li3-4x(V1-xMx)2(PO4)3 (M = Nb, Ta) crystallize in space group Pbcn of the orthorhombic system. The structure is composed of the three-dimensional framework and alkali metal cations in the channels. By adjusting the ratio of each metal ion with different oxidation numbers, the amount of the Li+ ions can be controlled and the positions of the Li ions can be varied. In addition, the relationship of the stoichiometries of each Li position and the ratio of each metal is discussed. The classical charge valence of the phases can be described as [Li+]3-4x([V3+]1-x[M5+]x)2[PO43-]3.
