New quaternary thiophosphates, A0.92Nb2PS10 (A = K, Rb, Cs) have been synthesized by using reactive alkali metal halide fluxes (KCl, RbCl, CsCl) and structurally characterized by single crystal X-ray diffraction techniques. The crystal structure of A0.92Nb2PS10 are composed of the one-dimensional anionic chain, 1¦∞[Nb2PS100.92-], and alkali metal cations, K+, Rb+, or Cs+ staying in the van der Waals space among the chains through electrostatic interactions. The title compounds are closely related with the well-known stoichiometric phase ANb2PS10 (A = Na, K, Rb, Cs). While both phases share the common linear chains, 1¦∞[Nb2PS101-], the deficiency of cations found in the title compounds have caused the deformation of the chains and thus the chains show a sinusoidal curves. In this presentation, the comparison of the two structures will be discussed along with the relationships between cation stoichiometries and electronic effects on the linear chains.
