Materials Data on Cu4(BiS2)5 by Materials Project

Abstract

Cu4Bi5S10 crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. there are two inequivalent Cu+1.25+ sites. In the first Cu+1.25+ site, Cu+1.25+ is bonded to four S2- atoms to form a mixture of edge and corner-sharing CuS4 tetrahedra. There are three shorter (2.31 Å) and one longer (2.36 Å) Cu–S bond lengths. In the second Cu+1.25+ site, Cu+1.25+ is bonded to four S2- atoms to form CuS4 tetrahedra that share corners with three equivalent BiS6 octahedra, corners with two equivalent CuS4 tetrahedra, and edges with two equivalent CuS4 tetrahedra. The corner-sharing octahedra tilt angles range from 1–75°. There are a spread of Cu–S bond distances ranging from 2.28–2.47 Å. There are three inequivalent Bi3+ sites. In the first Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to seven S2- atoms. There are a spread of Bi–S bond distances ranging from 2.64–3.37 Å. In the second Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to seven S2- atoms. There are a spread of Bi–S bond distances ranging from 2.67–3.55 Å. In the third Bi3+ site, Bi3+ is bonded to six S2- atoms to form BiS6 octahedra that share corners with six equivalent CuS4 tetrahedra and edges with two equivalent BiS6 octahedra. All Bi–S bond lengths are 2.83 Å. There are five inequivalent S2- sites. In the first S2- site, S2- is bonded to two equivalent Cu+1.25+ and two equivalent Bi3+ atoms to form a mixture of distorted edge and corner-sharing SCu2Bi2 trigonal pyramids. In the second S2- site, S2- is bonded in a 6-coordinate geometry to three equivalent Cu+1.25+ and three Bi3+ atoms. In the third S2- site, S2- is bonded in a 3-coordinate geometry to two equivalent Cu+1.25+ and three equivalent Bi3+ atoms. In the fourth S2- site, S2- is bonded in a 3-coordinate geometry to one Cu+1.25+ and four Bi3+ atoms. In the fifth S2- site, S2- is bonded in a 3-coordinate geometry to five Bi3+ atoms.