A quaternary thiophosphate, Cs2CrPS6 has been synthesized with alkali metal halide flux and the structure of the compound has been determined by single crystal X-ray diffraction methods. A black block-shaped crystal of Cs2CrPS6 is crystallized in the space group P21/n of the monoclinic system and the unit cell parameters of the compound are a = 9.0707(3), b = 9.0139(4), c = 14.5484(5) Å, β = 102.6418(4)˚ and V = 1160.68(8) Å3. The compound includes the anionic binuclear [Cr2(PS4)2S4]4- clusters which are isolated from each other by Cs+ cations. The clusters are composed of two edge-sharing Cr-centered octahedra and pair of P-centered tetrahedra. The cluster anions, [Cr2(PS4)2S4]4- are stabilized through the electrostatic interactions with the cations, Cs+.
In order to isolate the anionic species, Cs2CrPS6 has been dissolved in the polar solvents such as DMF at elevated temperatures. Counter cations such as PPh4+ have been added to the DMF-Cs2CrPS6 solution in order to stabilize the inorganic cluster anions. After recrystallization, dark blue needle-shaped crystals have been obtained at room temperature. The structure of the crystals have been determined by X-ray diffraction technique and it showed that these compounds are Cr(C3H6NS2)3 and Cr(C3H6NS2)3(DMF). In both crystals, Cr atoms are octahedrally coordinated by three dimethyldithiocarbamate anions, [C3H6NS2]-. Cr(C3H6NS2)3 is crystallized in the space group Pbca of the orthorhombic system and the unit cell parameters of the compound are a = 10.1874(7), b = 17.5629(14), c = 20.4466(18) Å and V = 3658.3(5) Å3. The crystal is made up of the neutral molecule, Cr(C3H6NS2)3. And only van der Waals interactions exist among them. Cr(C3H6NS2)3(DMF) is crystallized in the space group PĪ of the triclinic system and the unit cell parameters of the compound are a = 9.5271(10), b = 9.6622(10), c = 13.1238(12) Å, α = 103.2879(10), β = 93.9714(10), γ = 94.5344(29)˚ and V = 1160.68(8) Å3. In this compound, Cr(C3H6NS2)3 clusters are separated by neutral DMF molecules.
