CRYSTAL STRUCTURE OF ND3CU0.45GA1.52S7 AND ND3AG0.45GA1.52S7
DOI:
https://doi.org/10.32782/pcsd-2024-2-1Keywords:
rare earth metals, chalcogenides, crystal structure, X-ray powder methodAbstract
Samples of stoichiometric compositions of Nd3Cu0.45Ga1.52S7 and Nd3Ag0.45Ga1.52S7, weighing one gram each, obtained by sintering elementary components of a high degree of purity in vacuum quartz containers (the synthesis was carried out in vacuumed quartz ampoules to a residual pressure of 1.33·10-2 Pa) at the maximum synthesis temperature 1100 °С. The synthesized alloys were homogenized by annealing at a temperature of 500 °С for 500 hours. Crystal structure of sulfides Nd3Cu0.45Ga1.52S7 (a = 9.9354(6) Å, c = 6.0566(6) Å, V = 517.8(1) Å3, RI = 0.0832, Rp = 0.2640) and Nd3Ag0.45Ga1.52S7 (a = 9.9233(5) Å, c = 6.0724(5) Å, V = 517.8(1) Å3, RI = 0.0867, Rp = 0.2547) was studied by X-ray powder method. The studied structures relate to the structural type La3CuSiS7 (space group P63,173; Pearson symbol hP24). The Nd3Cu0.45Ga1.52S7 and Nd3Ag0.45Ga1.52S7 chalcogenide phases were synthesized on the basis of Nd3Ga1.67S7 sulfide by partial replacement of gallium atoms in the site 2b (1/3 2/3 z) point system with monovalent copper and silver atoms, respectively. In these structures, Neodymium atoms occupy site 6c (x y z) and, together with Sulfur atoms, form trigonal prisms with one additional atom [Nd S13S23S3] (CN = 7). Trigonal prisms form "blocks" 3[Nd 7S]. In these "blocks" trigonal prisms are connected to each other by ribs. Gallium Ga atoms occupy site 2a (0 0 z) and have an octahedral environment (for the Nd3Ag0.45Ga1.52S7 structure). In the Nd3Cu0.45Ga1.52S7 structure, Ga atoms have a triangular environment, since they are located near one of the faces of the octahedron. Octahedra [Ga (site 2a) 6S] have common faces and form columns in the direction of the c axis. These octahedra with trigonal prisms are connected by eddes. Atoms of statistical mixtures R1 (0.52 Ga + 0.45 Cu) and R2 (0.52 Ga + 0.45 Ag) are in the center of the tetrahedron [R1(R2) S13S3] formed from Sulfur atoms and occupy the site 2b (1/3 2/3 z) (CN = 4).
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