NaPdPS4 and RbPdPS4:: Systems with infinite straight 1/∞[PdPS4]- chains soluble in polar solvents and the structure of cubic RbPdPS4{Rb0.33P0.4S2.23Ox}

The synthesis, crystal structures, chemical and spectroscopic properties of NaPdPS4, RbPdPS4, and RbPdPS4{Rb0.33P0.4S2.23Ox} are described. NaPdPS4, RbPdPS4, are isostructural and crystallize in the tetragonal system 14/mcm with cell parameters a = 7.3074(8) Angstrom, c = 12.2308(14) Angstrom and a = 8.2954(3) Angstrom, c = 12.2284(4) Angstrom respectively. RbPdPS4{Rb0.33P0.4S2.23Ox} is cubic, space group Pm-3n and a = 12.0042(2) Angstrom. All compounds contain the same 1/infinity[PdPS4](-) chains made of alternating square planar Pd2+ cations and tetrahedral [PS4](3-) anions. RbPdPS4{Rb0.33P0.4S2.23Ox} contains co-crystallized highly disordered molecular species encapsulated within [Rb-8] cubic cavities. Spectroscopic solid state P-31 NMR, infrared and Raman data as well as elemental analysis suggest that these species could be S-n(2-)(n = 3 or 4) anions and possibly cationic [P4S6O](6+) fragments. NaPdPS4 and RbPdPS4 exhibit exfoliative dissolution in polar solvents giving rise to solutions that show signs of complex fluid behavior. (C) 2003 Elsevier Inc. All rights reserved.