Synthesis, crystal and electronic structure of the quaternary sulfides Ln2CuMS5 (Ln=La, Ce; M=Sb, Bi)

• Ln2CuSbS5 are complex quarternary phases crystallizing in their own structure type.
• Ln2CuSbS5 and Ce2CuBiS5 are new compound in the respective ternary phase diagrams.
• Ln2CuSbS5 on one side, and Ln2CuBiS5 on the other are not isotypic.

The series of quaternary sulfides with general formula Ln2CuMS5 (Ln=La, Ce; M=Sb, Bi) have been synthesized by solid-state reactions. Three representative members have been structurally characterized by single-crystal X-ray diffraction. La2CuSbS5 crystallizes in a new structure type (space group Ima2 (no. 46), Z=4, a=13.401(2) Å, b=7.592(1) Å, c=7.598(1) Å, V=773.1(3) Å3). The bismuth analogs of composition La2CuBiS5 and Ce2CuBiS5 crystallize with the La2CuInSe5 structure type (space group Pnma (no. 62), Z=4). Lattice parameters for La2CuBiS5: a=11.9213(5) Å, b=3.9967(2) Å, c=17.0537(8) Å, V=812.56(7) Å3; lattice parameters for Ce2CuBiS5: a=11.9179(15) Å, b=3.9596(5) Å, c=16.955(2) Å, V=800.13(17) Å3). The similarities and the differences between the two structures are discussed. Electronic structure calculations for La2CuSbS5 and La2CuBiS5 are also presented; they suggest semiconducting behavior with energy gaps exceeding 1.7 eV.

La2CuSbS5 crystallizes in a new structure type (space group Ima2 (no. 46). Its bismuth analog La2CuBiS5 crystallizes in the La2CuInSe5 structure type (space group Pnma (no. 62)). Z=4, a=11.9213(5) Å, b=3.9967(2) Å, c=17.0536(10) Å, V=813.53(10) Å3). The structures are based on rare-earth metal atoms coordinated by S atoms in a trigonal-prismatic and/or square-antiprismatic fashion, Cu-centered tetrahedra, and pnictogen atoms in pyramidal or distorted octahedral coordination.Figure optionsDownload as PowerPoint slide