Premium
Synthesis and Characterization of Copper Hexathiometadiphosphate Cu 2 P 2 S 6
Author(s) -
Kuhn Alexander,
Schoop Leslie M.,
Eger Roland,
Lotsch Bettina V.
Publication year - 2016
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201500810
Subject(s) - copper , crystallography , tetragonal crystal system , crystal structure , diamagnetism , band gap , tetrahedron , electronic structure , octahedron , oxidation state , chemistry , electronic band structure , materials science , metal , condensed matter physics , computational chemistry , physics , metallurgy , optoelectronics , quantum mechanics , magnetic field
Copper hexathiometadiphosphate, Cu 2 P 2 S 6 , was synthesized and characterized. Brick‐red copper hexathiometadiphosphate Cu 2 P 2 S 6 crystallizes in the tetragonal space group P 4 2 / mnm (no. 136) with a = b = 5.2565(7), c = 15.066(3) Å and V = 416.3(1) Å 3 in a novel structure type. This is the first hexathiometadiphosphate, whose crystal structure is based on a slightly distorted cubic closest packing of sulfur atoms. 1/3 of the tetrahedral voids are occupied by Cu and P in an ordered fashion, thus resulting in a layered structure. The structural motif of layers composed of corner‐sharing CuS 4 tetrahedra (comparable to red HgI 2 ) that are separated by [P 2 S 6 ] 2– anions orientated perpendicular to these layers, is rarely found in solid state chemistry. The compound is diamagnetic and shows negligible electronic conductivity. Electronic structure calculations and UV/Vis measurements point to a bandgap in the visible range and explain the red color of the compound. Additionally, the oxidation state +1 for Cu was confirmed by the electronic structure calculations. The thermal properties of Cu 2 P 2 S 6 were investigated by DTA.