An Inorganic Double Helix Sheathing Alkali Metal Cations: ANb2P2S12(A=K, Rb, Cs), A Series of Thiophosphates Close to the Metal-Nonmetal Boundary-Chalcogenide Analogues of Transition-Metal Phosphate Bronzes?

The new quaternary niobium thiophosphates ANb 2 P 2 S 1 2 (A=K, Rb, Cs) have been prepared and characterized. The title compounds were synthesized by reacting Nb metal, A 2 S, P 2 S 5 , and S at 600-700°C in evacuated silica tubes. They crystallize as "stuffed" variants of the tetragonal TaPS 6 structure type in the tetragonal space group I42d with eight formula units per unit cell and lattice constants a=15.923(2) and c=13.238(3) A for CsNb 2 P 2 S 1 2 , a= 15.887(3) and c=13.132(3) A for RbNb 2 P 2 S 1 2 , and a=15.850(2) and c= 13.119(3) A for KNb 2 P 2 S 1 2 . Their structures are based on double helices formed from interpenetrating, noninteracting spiral chains of binuclear [Nb 2 S 1 2…

Syntheses, crystal structures, and solid state NMR investigations of K4M2P6S25 and K3M2P5S18 (M=Ti, Sn)

Abstract Reaction of K 2 S 5 with P 4 S 10 and Ti at 450 °C results in the formation of K 4 Ti 2 P 6 S 25 , a new titanium thiophosphate, whose crystal structure was solved by single-crystal X-ray diffraction. The title compound crystallizes in the orthorhombic space group Fdd2, with the lattice constants a =33.819(7), b =35.508(7), and c =6.251(1) A ( Z =8). The structure contains a layered arrangement of crosslinked quasi-one-dimensional Ti 2 P 6 S 4− 25 chains. The K + ions are situated between the layers. The Ti atoms within the chains are octahedrally coordinated by P 2 S 4− 7 and P 2 S 4− 9 ligands. Reaction of K 2 S with P 4 S 10 , S and Ti at 600 °C results in the formation of K 3 T…

ChemInform Abstract: Syntheses, Crystal Structures, and Solid State NMR Investigations of K4M2P6S25 and K3M2P5S18 (M: Ti, Sn).