DOI: 10.17188/1199487
title: Materials Data on Tl4Bi2S5 by Materials Project

description: Tl4Bi2S5 crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. there are four inequivalent Tl1+ sites. In the first Tl1+ site, Tl1+ is bonded in a rectangular see-saw-like geometry to four S2- atoms. There are a spread of Tl–S bond distances ranging from 3.00–3.27 Å. In the second Tl1+ site, Tl1+ is bonded in a rectangular see-saw-like geometry to four S2- atoms. There are a spread of Tl–S bond distances ranging from 2.94–3.17 Å. In the third Tl1+ site, Tl1+ is bonded to five S2- atoms to form TlS5 square pyramids that share corners with four equivalent BiS6 octahedra, edges with four BiS6 octahedra, and edges with four TlS5 square pyramids. The corner-sharing octahedra tilt angles range from 12–13°. There are a spread of Tl–S bond distances ranging from 2.96–3.22 Å. In the fourth Tl1+ site, Tl1+ is bonded to five S2- atoms to form distorted TlS5 square pyramids that share corners with two equivalent BiS6 octahedra, edges with three BiS6 octahedra, and edges with four TlS5 square pyramids. The corner-sharing octahedral tilt angles are 14°. There are a spread of Tl–S bond distances ranging from 2.92–3.41 Å. There are two 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, corners with four equivalent TlS5 square pyramids, edges with four BiS6 octahedra, and edges with four TlS5 square pyramids. The corner-sharing octahedral tilt angles are 0°. There are a spread of Bi–S bond distances ranging from 2.69–3.11 Å. In the second Bi3+ site, Bi3+ is bonded to six S2- atoms to form BiS6 octahedra that share a cornercorner with one BiS6 octahedra, corners with two equivalent TlS5 square pyramids, edges with six BiS6 octahedra, and edges with three TlS5 square pyramids. The corner-sharing octahedral tilt angles are 0°. There are a spread of Bi–S bond distances ranging from 2.73–3.03 Å. There are five inequivalent S2- sites. In the first S2- site, S2- is bonded to three Tl1+ and three Bi3+ atoms to form STl3Bi3 octahedra that share corners with six STl2Bi4 octahedra and edges with ten STl3Bi3 octahedra. The corner-sharing octahedra tilt angles range from 3–14°. In the second S2- site, S2- is bonded to four Tl1+ and two equivalent Bi3+ atoms to form distorted STl4Bi2 octahedra that share corners with five STl2Bi4 octahedra and edges with ten STl3Bi3 octahedra. The corner-sharing octahedra tilt angles range from 4–15°. In the third S2- site, S2- is bonded to two equivalent Tl1+ and four Bi3+ atoms to form STl2Bi4 octahedra that share corners with four STl3Bi3 octahedra and edges with eleven STl2Bi4 octahedra. The corner-sharing octahedra tilt angles range from 3–9°. In the fourth S2- site, S2- is bonded to five Tl1+ and one Bi3+ atom to form STl5Bi octahedra that share corners with four STl2Bi4 octahedra and edges with nine STl3Bi3 octahedra. The corner-sharing octahedra tilt angles range from 9–15°. In the fifth S2- site, S2- is bonded to four Tl1+ and two equivalent Bi3+ atoms to form a mixture of corner and edge-sharing STl4Bi2 octahedra. The corner-sharing octahedra tilt angles range from 3–14°.