Quaternary chromium thiophosphates, Cs2CrPS6, CsCrPS5 and A3Cr2P3S12 ( A = Rb, Cs) have been prepared through solid state reactions using alkali metal halide flux at high temperatures. The structure of these compounds have been analyzed by single crystal X-ray diffraction methods. These thiophosphates have various structural type from 0-dimensional to 1-dimensional depending on connecting modes of CrS6 octahedra and stoichiometries. In these phases, the anionic unit [Cr2(PS4)2S4n-] is stabilized through the electrostatic interactions with alkali metal cation and these units form inorganic clusters or chains. The 0-dimensional chromium thiophosphate cluster, Cs2CrPS6 crystallizes in the space group P21/n of the monoclinic system with four formula units in a cell of dimensions a = 6.49624(17), b = 12.6508(4), c = 9.9810(3) Å, β = 98.2793(8)˚ and V = 811.72(4) Å3. The 1-dimsnional chromium thiophosphate, CsCrPS5 crystallizes in the space group P21/c of the monoclinic system with four formula units in a cell of dimensions a = 6.49624(17), b = 12.6508(4), c = 9.9810(3) Å, β = 98.2793(8)˚ and V = 811.72(4) Å3. The 1-dimsnional chromium thiophosphate, Rb3Cr2P3S12 crystallizes in the space group P21/c of the monoclinic system with four formula units in a cell of dimensions a = 9.3028(4), b = 12.9607(5), c = 19.0313(3) Å, β = 105.903(2)˚ and V= 2206.80(15) Å3. The 1-dimsnional chromium thiophosphate, Cs3Cr2P3S12 crystallizes in the space group P21/c of the monoclinic system with four formula units in a cell of dimensions a = 15.2811(16), b = 13.2192(15), c = 11.4613(14) Å, β = 91.045(3)˚ and V = 2314.8(5) Å3.
In the socond stage of this work, the thiophosphates mentioned above have been dissolved in polar solvents such as NMF and DMF to solubilize anionic clusters or chains. Counter cations such as NH4Cl and PPh4Cl have been added to the solution to stabilize the inorganic (polymer) anions. As a result, various form of metal clusters have been isolated as single crystals and their structures have been analysed with X-ray diffraction data. The metal sulfide clusters and thiophosphate clusters, α-CrS6(C3H4N)3, ß-CrS6(C3H4N)3,Cr2P2S8(NMF)4 and Cr2P2S12(C2H4N)2(
PPh)2(H2O)2 have been prepared through solution state reactions using polar solvents at room temperatures. α-CrS6(C3H4N)3 crystallizes in the space group Pbca of the orthorhombic system in with eight formula units in a cell of dimensions a = 10.1965(6), b = 17.5659(8), c = 20.4441(10) Å and V = 3661.8(3)Å3. β-CrS6(C3H4N)3 crystallizes in the space group P of the triclinic system in with two formula units in a cell of dimensions a = 9.1600(9), b = 9.7945(12), c = 12.6611(12) Å, α = 74.707(5)˚, β = 68.540(3)˚, γ = 85.319(4)˚ and V = 1019.60(19)Å3. α and β CrS6(C3H4N)3 have isostructural building unit but have different space group and unitcell parameters. Cr2P2S8(NMF)4 crystallizes in the space group P21/n of the monoclinic system in with two formula units in a cell of dimensions a = 10.0443(5), b = 12.0554(8), c = 10.8131(6) Å, β = 103.6969(16)˚, γ = 85.319(4)˚ and V = 1272.09(12)Å3. Cr2P2S12(C2H4N)2(PPh)2(H2O)2 crystallizes in the space group P of the triclinic system in with two formula units in a cell of dimensions a = 11.5464(9), b = 11.9169(7), c = 12.8596(8) Å, α = 71.2840(16)˚, β = 63.9762(15)˚, γ = 73.7930(15)˚ and V = 1485.60(17)Å3. The anionic unit [Cr2(PS4)2S4n-] is maintained in Cr2P2S12(C2H4N)2(PPh)2(H2O)2 while Cr2P2S8(N
MF)4 cluster and [CrS69-] unit in CrS6(C3H4N)3 cluster are reconstructed from discrete [Cr2(PS4)2S4n-] unit.
