DOI: 10.17188/1720105
title: Materials Data on Tl14Cu8(SbSe3)9 by Materials Project

description: Cu8Tl14(SbSe3)9 crystallizes in the monoclinic P2/m space group. The structure is three-dimensional. there are four inequivalent Cu+1.12+ sites. In the first Cu+1.12+ site, Cu+1.12+ is bonded to four Se2- atoms to form distorted CuSe4 trigonal pyramids that share corners with two SbSe6 octahedra, corners with two equivalent CuSe4 trigonal pyramids, edges with two equivalent SbSe6 octahedra, and edges with two equivalent CuSe4 tetrahedra. The corner-sharing octahedra tilt angles range from 5–65°. There are a spread of Cu–Se bond distances ranging from 2.43–2.78 Å. In the second Cu+1.12+ site, Cu+1.12+ is bonded to four Se2- atoms to form distorted CuSe4 tetrahedra that share a cornercorner with one SbSe6 octahedra, corners with two equivalent CuSe4 tetrahedra, edges with two equivalent SbSe6 octahedra, and edges with two equivalent CuSe4 trigonal pyramids. The corner-sharing octahedral tilt angles are 58°. There are a spread of Cu–Se bond distances ranging from 2.45–2.59 Å. In the third Cu+1.12+ site, Cu+1.12+ is bonded to four Se2- atoms to form distorted CuSe4 trigonal pyramids that share a cornercorner with one TlSe6 octahedra, a cornercorner with one SbSe6 octahedra, corners with two equivalent CuSe4 trigonal pyramids, edges with two equivalent SbSe6 octahedra, and edges with two equivalent CuSe4 tetrahedra. The corner-sharing octahedra tilt angles range from 4–63°. There are a spread of Cu–Se bond distances ranging from 2.45–2.56 Å. In the fourth Cu+1.12+ site, Cu+1.12+ is bonded to four Se2- atoms to form CuSe4 tetrahedra that share a cornercorner with one SbSe6 octahedra, corners with two equivalent TlSe5 square pyramids, corners with two equivalent CuSe4 tetrahedra, edges with two equivalent SbSe6 octahedra, and edges with two equivalent CuSe4 trigonal pyramids. The corner-sharing octahedral tilt angles are 59°. There are two shorter (2.47 Å) and two longer (2.53 Å) Cu–Se bond lengths. There are seven inequivalent Tl1+ sites. In the first Tl1+ site, Tl1+ is bonded in a 7-coordinate geometry to seven Se2- atoms. There are a spread of Tl–Se bond distances ranging from 3.20–3.61 Å. In the second Tl1+ site, Tl1+ is bonded in a 5-coordinate geometry to five Se2- atoms. There are a spread of Tl–Se bond distances ranging from 3.02–3.24 Å. In the third Tl1+ site, Tl1+ is bonded to five Se2- atoms to form distorted TlSe5 square pyramids that share corners with two equivalent SbSe6 octahedra, corners with two equivalent CuSe4 tetrahedra, an edgeedge with one SbSe6 octahedra, edges with two equivalent TlSe5 square pyramids, and edges with two equivalent SbSe5 square pyramids. The corner-sharing octahedral tilt angles are 5°. There are a spread of Tl–Se bond distances ranging from 2.97–3.16 Å. In the fourth Tl1+ site, Tl1+ is bonded to six Se2- atoms to form TlSe6 octahedra that share corners with two equivalent TlSe6 octahedra, corners with two equivalent SbSe6 octahedra, a cornercorner with one CuSe4 trigonal pyramid, edges with three equivalent TlSe6 octahedra, and edges with seven SbSe6 octahedra. The corner-sharing octahedra tilt angles range from 0–9°. There are a spread of Tl–Se bond distances ranging from 3.04–3.33 Å. In the fifth Tl1+ site, Tl1+ is bonded in a 7-coordinate geometry to seven Se2- atoms. There are a spread of Tl–Se bond distances ranging from 3.17–3.60 Å. In the sixth Tl1+ site, Tl1+ is bonded in a 7-coordinate geometry to seven Se2- atoms. There are a spread of Tl–Se bond distances ranging from 3.28–3.61 Å. In the seventh Tl1+ site, Tl1+ is bonded in a 5-coordinate geometry to seven Se2- atoms. There are a spread of Tl–Se bond distances ranging from 3.21–3.69 Å. There are five inequivalent Sb+3.44+ sites. In the first Sb+3.44+ site, Sb+3.44+ is bonded to five Se2- atoms to form SbSe5 square pyramids that share edges with two equivalent TlSe5 square pyramids and edges with two equivalent SbSe5 square pyramids. There are a spread of Sb–Se bond distances ranging from 2.61–2.99 Å. In the second Sb+3.44+ site, Sb+3.44+ is bonded to six Se2- atoms to form SbSe6 octahedra that share corners with two equivalent TlSe6 octahedra, corners with two equivalent TlSe5 square pyramids, corners with two CuSe4 trigonal pyramids, an edgeedge with one TlSe6 octahedra, edges with four SbSe6 octahedra, an edgeedge with one TlSe5 square pyramid, and edges with two equivalent CuSe4 tetrahedra. The corner-sharing octahedral tilt angles are 9°. There are a spread of Sb–Se bond distances ranging from 2.86–2.95 Å. In the third Sb+3.44+ site, Sb+3.44+ is bonded to six Se2- atoms to form SbSe6 octahedra that share corners with three SbSe6 octahedra, a cornercorner with one CuSe4 tetrahedra, edges with three SbSe6 octahedra, edges with four equivalent TlSe6 octahedra, and edges with two equivalent CuSe4 trigonal pyramids. The corner-sharing octahedra tilt angles range from 0–13°. There are a spread of Sb–Se bond distances ranging from 2.82–3.08 Å. In the fourth Sb+3.44+ site, Sb+3.44+ is bonded to six Se2- atoms to form SbSe6 octahedra that share corners with two equivalent CuSe4 trigonal pyramids, edges with two equivalent SbSe6 octahedra, and edges with four equivalent CuSe4 tetrahedra. There are four shorter (2.88 Å) and two longer (2.93 Å) Sb–Se bond lengths. In the fifth Sb+3.44+ site, Sb+3.44+ is bonded to six Se2- atoms to form SbSe6 octahedra that share corners with two equivalent SbSe6 octahedra, a cornercorner with one CuSe4 tetrahedra, edges with two equivalent TlSe6 octahedra, edges with five SbSe6 octahedra, and edges with two equivalent CuSe4 trigonal pyramids. The corner-sharing octahedral tilt angles are 13°. There are a spread of Sb–Se bond distances ranging from 2.76–3.25 Å. There are fourteen inequivalent Se2- sites. In the first Se2- site, Se2- is bonded to one Cu+1.12+, three Tl1+, and two equivalent Sb+3.44+ atoms to form a mixture of corner and edge-sharing SeTl3CuSb2 octahedra. The corner-sharing octahedra tilt angles range from 7–8°. In the second Se2- site, Se2- is bonded in a 6-coordinate geometry to three Cu+1.12+, two equivalent Tl1+, and one Sb+3.44+ atom. In the third Se2- site, Se2- is bonded to one Cu+1.12+, three Tl1+, and two equivalent Sb+3.44+ atoms to form SeTl3CuSb2 octahedra that share corners with two equivalent SeTl3Sb3 octahedra and edges with five SeTl3CuSb2 octahedra. The corner-sharing octahedral tilt angles are 1°. In the fourth Se2- site, Se2- is bonded to one Cu+1.12+, three Tl1+, and two equivalent Sb+3.44+ atoms to form SeTl3CuSb2 octahedra that share corners with two equivalent SeTl3CuSb2 octahedra, edges with three equivalent SeTl3CuSb2 octahedra, and edges with two equivalent SeTl3Sb2 square pyramids. The corner-sharing octahedral tilt angles are 0°. In the fifth Se2- site, Se2- is bonded to three Tl1+ and two equivalent Sb+3.44+ atoms to form SeTl3Sb2 square pyramids that share edges with two equivalent SeTl3CuSb2 octahedra and edges with two equivalent SeTl3Sb2 square pyramids. In the sixth Se2- site, Se2- is bonded to two Tl1+ and four Sb+3.44+ atoms to form SeTl2Sb4 octahedra that share corners with five SeTl2CuSb3 octahedra and edges with eight SeTl2Sb4 octahedra. The corner-sharing octahedra tilt angles range from 5–8°. In the seventh Se2- site, Se2- is bonded to four equivalent Tl1+ and two equivalent Sb+3.44+ atoms to form SeTl4Sb2 octahedra that share corners with four equivalent SeTl3Sb3 octahedra and edges with twelve SeTl2Sb4 octahedra. The corner-sharing octahedral tilt angles are 7°. In the eighth Se2- site, Se2- is bonded to three Tl1+ and three Sb+3.44+ atoms to form SeTl3Sb3 octahedra that share corners with four SeTl4Sb2 octahedra and edges with ten SeTl3CuSb2 octahedra. The corner-sharing octahedra tilt angles range from 1–7°. In the ninth Se2- site, Se2- is bonded in a 7-coordinate geometry to six Tl1+ and one Sb+3.44+ atom. In the tenth Se2- site, Se2- is bonded in a 7-coordinate geometry to five Tl1+ and two equivalent Sb+3.44+ atoms. In the eleventh Se2- site, Se2- is bonded in a 6-coordinate geometry to three Cu+1.12+, four equivalent Tl1+, and one Sb+3.44+ atom. In the twelfth Se2- site, Se2- is bonded in a 4-coordinate geometry to three Cu+1.12+, two equivalent Tl1+, and one Sb+3.44+ atom. In the thirteenth Se2- site, Se2- is bonded in a 4-coordinate geometry to three Cu+1.12+, four Tl1+, and one Sb+3.44+ atom. In the fourteenth Se2- site, Se2- is bonded to one Cu+1.12+, two equivalent Tl1+, and three Sb+3.44+ atoms to form SeTl2CuSb3 octahedra that share corners with two equivalent SeTl2Sb4 octahedra and edges with seven SeTl3CuSb2 octahedra. The corner-sharing octahedral tilt angles are 5°.