Materials Data on Cs3Cu2(BiS2)5 by Materials Project

Abstract

Cs3Bi5Cu2S10 crystallizes in the orthorhombic Pnnm space group. The structure is three-dimensional. there are two inequivalent Cs1+ sites. In the first Cs1+ site, Cs1+ is bonded in a 6-coordinate geometry to six S2- atoms. There are four shorter (3.44 Å) and two longer (3.46 Å) Cs–S bond lengths. In the second Cs1+ site, Cs1+ is bonded in a 7-coordinate geometry to seven S2- atoms. There are a spread of Cs–S bond distances ranging from 3.48–3.80 Å. Cu1+ is bonded to four S2- atoms to form CuS4 tetrahedra that share a cornercorner with one BiS6 octahedra, corners with two equivalent CuS4 tetrahedra, and edges with four BiS6 octahedra. The corner-sharing octahedral tilt angles are 13°. There are a spread of Cu–S bond distances ranging from 2.34–2.69 Å. There are three inequivalent Bi3+ sites. In the first Bi3+ site, Bi3+ is bonded to six S2- atoms to form BiS6 octahedra that share a cornercorner with one BiS6 octahedra, edges with six BiS6 octahedra, and edges with two equivalent CuS4 tetrahedra. The corner-sharing octahedral tilt angles are 41°. There are a spread of Bi–S bond distances ranging from 2.68–3.08 Å. In the second Bi3+ site, Bi3+ is bonded to six S2- atoms to form distorted BiS6 octahedra that share corners with three BiS6 octahedra, edges with five BiS6 octahedra, and edges with two equivalent CuS4 tetrahedra. The corner-sharing octahedra tilt angles range from 8–41°. There are a spread of Bi–S bond distances ranging from 2.65–3.24 Å. In the third Bi3+ site, Bi3+ is bonded to six S2- atoms to form BiS6 octahedra that share corners with four equivalent BiS6 octahedra, corners with two equivalent CuS4 tetrahedra, and edges with eight BiS6 octahedra. The corner-sharing octahedral tilt angles are 8°. There are two shorter (2.85 Å) and four longer (2.90 Å) Bi–S bond lengths. There are five inequivalent S2- sites. In the first S2- site, S2- is bonded to three Cs1+, one Cu1+, and two equivalent Bi3+ atoms to form distorted SCs3CuBi2 octahedra that share corners with seven SCs3CuBi2 octahedra, corners with two equivalent SCs2Bi3 square pyramids, edges with three SCs3CuBi2 octahedra, edges with two equivalent SCs2Bi3 square pyramids, and a faceface with one SCs2CuBi3 octahedra. The corner-sharing octahedra tilt angles range from 0–74°. In the second S2- site, S2- is bonded to two equivalent Cs1+, one Cu1+, and three Bi3+ atoms to form distorted SCs2CuBi3 octahedra that share corners with three SCs3CuBi2 octahedra, corners with two equivalent SCs2Bi3 square pyramids, edges with six SCs2CuBi3 octahedra, an edgeedge with one SCs2Bi3 square pyramid, and a faceface with one SCs3CuBi2 octahedra. The corner-sharing octahedra tilt angles range from 0–74°. In the third S2- site, S2- is bonded to one Cs1+ and five Bi3+ atoms to form SCsBi5 octahedra that share corners with six SCs3CuBi2 octahedra, edges with eight SCs3CuBi2 octahedra, and edges with two equivalent SCs2Bi3 square pyramids. The corner-sharing octahedra tilt angles range from 0–46°. In the fourth S2- site, S2- is bonded to two equivalent Cs1+ and three Bi3+ atoms to form SCs2Bi3 square pyramids that share corners with four SCs3CuBi2 octahedra, corners with two equivalent SCs2Bi3 square pyramids, edges with five SCs3CuBi2 octahedra, and edges with three equivalent SCs2Bi3 square pyramids. The corner-sharing octahedra tilt angles range from 6–69°. In the fifth S2- site, S2- is bonded in a 6-coordinate geometry to two equivalent Cs1+, two equivalent Cu1+, and two Bi3+ atoms.