Abstract: | Ba3P3I2 and Ba5P5I3: Stepwise Oxidation of Barium Phosphide with Iodine The novel compounds Ba3P3I2 and Ba5P5I3 were obtained by the reaction of barium phosphide with iodine. The air and moisture sensitive compounds crystallize in new structure types: Ba3P3I2 (oP32; Pnma; a = 1719.5(4) pm; b = 462.4(2) pm; c = 1427.2(4) pm; Z = 4; R(F)N′ = 0.067 (N′(hkl) = 2667), Ba5P5I3 (mC52; C2/m; a = 4266.4(13) pm; b = 456.3(2) pm; c = 943.1(3) pm; ß = 92.20(3)°; Z = 4; R(F)N′ = 0.040 (N′(hkl) = 3909). Both can be described as double salts of a hypothetic Zintl Phase ('Ba2P3' or 'Ba7P10') and a halide (BaI2). Characteristic structural features are P3 and P4 chains, corresponding to Ba3P3]I2 and Ba10P3]2P4]I6, respectively. The bonding characteristics will be interpreted on the basis of the structure and the physical properties. |