DOI: 10.17188/1281070
title: Materials Data on Cu6AgBi12PbS22 by Materials Project

description: AgCu6PbBi12S22 crystallizes in the monoclinic P2_1/m space group. The structure is three-dimensional. Ag1+ is bonded in a distorted rectangular see-saw-like geometry to four S2- atoms. There are two shorter (2.47 Å) and two longer (2.95 Å) Ag–S bond lengths. There are six inequivalent Cu1+ sites. In the first Cu1+ site, Cu1+ is bonded to four S2- atoms to form distorted CuS4 trigonal pyramids that share corners with five BiS6 octahedra, corners with four BiS5 square pyramids, corners with two equivalent CuS4 trigonal pyramids, and edges with three BiS6 octahedra. The corner-sharing octahedra tilt angles range from 2–90°. There are a spread of Cu–S bond distances ranging from 2.23–2.95 Å. In the second Cu1+ site, Cu1+ is bonded to four S2- atoms to form CuS4 tetrahedra that share corners with six BiS5 square pyramids, corners with two equivalent CuS4 tetrahedra, an edgeedge with one BiS5 square pyramid, and an edgeedge with one CuS4 tetrahedra. There are a spread of Cu–S bond distances ranging from 2.33–2.40 Å. In the third Cu1+ site, Cu1+ is bonded to four S2- atoms to form distorted CuS4 tetrahedra that share corners with six BiS5 square pyramids, corners with two equivalent CuS4 tetrahedra, an edgeedge with one BiS5 square pyramid, and an edgeedge with one CuS4 tetrahedra. There are a spread of Cu–S bond distances ranging from 2.29–2.42 Å. In the fourth Cu1+ site, Cu1+ is bonded in a 5-coordinate geometry to five S2- atoms. There are a spread of Cu–S bond distances ranging from 2.25–3.19 Å. In the fifth Cu1+ site, Cu1+ is bonded to four S2- atoms to form distorted CuS4 tetrahedra that share corners with four BiS6 octahedra, corners with two equivalent BiS5 square pyramids, and corners with two equivalent CuS4 tetrahedra. The corner-sharing octahedra tilt angles range from 52–67°. There are a spread of Cu–S bond distances ranging from 2.35–2.38 Å. In the sixth Cu1+ site, Cu1+ is bonded to four S2- atoms to form distorted CuS4 trigonal pyramids that share corners with three BiS6 octahedra, corners with two equivalent BiS5 square pyramids, and corners with two equivalent CuS4 trigonal pyramids. The corner-sharing octahedra tilt angles range from 2–81°. There are a spread of Cu–S bond distances ranging from 2.25–2.78 Å. Pb2+ is bonded in a 7-coordinate geometry to seven S2- atoms. There are a spread of Pb–S bond distances ranging from 3.08–3.22 Å. There are twelve inequivalent Bi+2.92+ sites. In the first Bi+2.92+ site, Bi+2.92+ is bonded in a 7-coordinate geometry to seven S2- atoms. There are a spread of Bi–S bond distances ranging from 2.74–3.24 Å. In the second Bi+2.92+ site, Bi+2.92+ is bonded to five S2- atoms to form BiS5 square pyramids that share corners with two equivalent CuS4 tetrahedra and edges with four equivalent BiS5 square pyramids. There are a spread of Bi–S bond distances ranging from 2.62–3.01 Å. In the third Bi+2.92+ site, Bi+2.92+ is bonded to five S2- atoms to form distorted BiS5 square pyramids that share corners with two equivalent BiS6 octahedra, corners with four CuS4 tetrahedra, corners with two equivalent CuS4 trigonal pyramids, edges with three BiS6 octahedra, and edges with two equivalent BiS5 square pyramids. The corner-sharing octahedral tilt angles are 9°. There are three shorter (2.68 Å) and two longer (3.09 Å) Bi–S bond lengths. In the fourth Bi+2.92+ site, Bi+2.92+ is bonded to six S2- atoms to form BiS6 octahedra that share corners with three BiS6 octahedra, corners with two equivalent CuS4 tetrahedra, and edges with seven BiS6 octahedra. The corner-sharing octahedral tilt angles are 1°. There are a spread of Bi–S bond distances ranging from 2.67–3.17 Å. In the fifth Bi+2.92+ site, Bi+2.92+ is bonded in a 7-coordinate geometry to seven S2- atoms. There are a spread of Bi–S bond distances ranging from 2.66–3.41 Å. In the sixth Bi+2.92+ site, Bi+2.92+ is bonded to six S2- atoms to form BiS6 octahedra that share a cornercorner with one BiS6 octahedra, corners with two equivalent CuS4 trigonal pyramids, edges with eight BiS6 octahedra, and an edgeedge with one CuS4 trigonal pyramid. The corner-sharing octahedral tilt angles are 1°. There are a spread of Bi–S bond distances ranging from 2.64–3.08 Å. In the seventh Bi+2.92+ site, Bi+2.92+ is bonded to six S2- atoms to form BiS6 octahedra that share corners with two equivalent BiS6 octahedra, corners with two equivalent CuS4 tetrahedra, and edges with seven BiS6 octahedra. The corner-sharing octahedral tilt angles are 6°. There are a spread of Bi–S bond distances ranging from 2.72–3.13 Å. In the eighth Bi+2.92+ site, Bi+2.92+ is bonded to six S2- atoms to form BiS6 octahedra that share corners with two equivalent BiS6 octahedra, corners with three CuS4 trigonal pyramids, edges with five BiS6 octahedra, and edges with two equivalent BiS5 square pyramids. The corner-sharing octahedral tilt angles are 1°. There are a spread of Bi–S bond distances ranging from 2.77–2.96 Å. In the ninth Bi+2.92+ site, Bi+2.92+ is bonded to six S2- atoms to form BiS6 octahedra that share corners with three BiS6 octahedra, corners with two equivalent BiS5 square pyramids, edges with nine BiS6 octahedra, an edgeedge with one BiS5 square pyramid, and edges with two equivalent CuS4 trigonal pyramids. The corner-sharing octahedra tilt angles range from 6–10°. There are a spread of Bi–S bond distances ranging from 2.76–3.07 Å. In the tenth Bi+2.92+ site, Bi+2.92+ is bonded to six S2- atoms to form BiS6 octahedra that share a cornercorner with one BiS6 octahedra, corners with three CuS4 trigonal pyramids, and edges with four BiS6 octahedra. The corner-sharing octahedral tilt angles are 10°. There are a spread of Bi–S bond distances ranging from 2.64–3.21 Å. In the eleventh Bi+2.92+ site, Bi+2.92+ is bonded to five S2- atoms to form distorted BiS5 square pyramids that share corners with four equivalent CuS4 tetrahedra, corners with two equivalent CuS4 trigonal pyramids, edges with four equivalent BiS5 square pyramids, and an edgeedge with one CuS4 tetrahedra. There are a spread of Bi–S bond distances ranging from 2.63–3.09 Å. In the twelfth Bi+2.92+ site, Bi+2.92+ is bonded to five S2- atoms to form BiS5 square pyramids that share corners with four equivalent CuS4 tetrahedra, corners with two equivalent CuS4 trigonal pyramids, edges with four equivalent BiS5 square pyramids, and an edgeedge with one CuS4 tetrahedra. There are a spread of Bi–S bond distances ranging from 2.63–3.10 Å. There are twenty-two inequivalent S2- sites. In the first S2- site, S2- is bonded in a 6-coordinate geometry to three Cu1+ and three Bi+2.92+ atoms. In the second S2- site, S2- is bonded in a 6-coordinate geometry to three equivalent Ag1+ and three Bi+2.92+ atoms. In the third S2- site, S2- is bonded in a distorted T-shaped geometry to three Bi+2.92+ atoms. In the fourth S2- site, S2- is bonded in a 3-coordinate geometry to two equivalent Cu1+, two equivalent Pb2+, and one Bi+2.92+ atom. In the fifth S2- site, S2- is bonded to one Cu1+ and three Bi+2.92+ atoms to form distorted SCuBi3 tetrahedra that share corners with two equivalent SBi5 square pyramids, corners with two equivalent SCuBi3 tetrahedra, and edges with three equivalent SBi5 square pyramids. In the sixth S2- site, S2- is bonded in a 3-coordinate geometry to two equivalent Cu1+ and three equivalent Bi+2.92+ atoms. In the seventh S2- site, S2- is bonded in a 3-coordinate geometry to three Bi+2.92+ atoms. In the eighth S2- site, S2- is bonded to two Cu1+ and two equivalent Bi+2.92+ atoms to form a mixture of distorted edge and corner-sharing SCu2Bi2 trigonal pyramids. In the ninth S2- site, S2- is bonded to two equivalent Cu1+ and four Bi+2.92+ atoms to form distorted SCu2Bi4 octahedra that share a cornercorner with one SBi5Pb octahedra and edges with six SCu2Bi4 octahedra. The corner-sharing octahedral tilt angles are 6°. In the tenth S2- site, S2- is bonded to six Bi+2.92+ atoms to form SBi6 octahedra that share corners with two equivalent SCuBi5 octahedra and edges with seven SBi5Pb octahedra. The corner-sharing octahedral tilt angles are 2°. In the eleventh S2- site, S2- is bonded in a distorted trigonal non-coplanar geometry to one Cu1+ and two equivalent Bi+2.92+ atoms. In the twelfth S2- site, S2- is bonded to five Bi+2.92+ atoms to form distorted SBi5 square pyramids that share corners with two equivalent SCuBi3 tetrahedra, edges with four equivalent SBi5 square pyramids, and edges with three equivalent SCuBi3 tetrahedra. In the thirteenth S2- site, S2- is bonded to one Cu1+ and five Bi+2.92+ atoms to form SCuBi5 octahedra that share corners with two equivalent SBi6 octahedra, corners with two equivalent SCu2Bi2 trigonal pyramids, edges with seven SBi5Pb octahedra, and an edgeedge with one SCu2Bi2 trigonal pyramid. The corner-sharing octahedral tilt angles are 2°. In the fourteenth S2- site, S2- is bonded in a 6-coordinate geometry to three Cu1+, two equivalent Pb2+, and one Bi+2.92+ atom. In the fifteenth S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to one Ag1+, one Cu1+, and two equivalent Bi+2.92+ atoms. In the sixteenth S2- site, S2- is bonded in a 1-coordinate geometry to one Cu1+, two equivalent Pb2+, and two equivalent Bi+2.92+ atoms. In the seventeenth S2- site, S2- is bonded in a 6-coordinate geometry to one Cu1+ and five Bi+2.92+ atoms. In the eighteenth S2- site, S2- is bonded in a distorted trigonal non-coplanar geometry to three Bi+2.92+ atoms. In the nineteenth S2- site, S2- is bonded to one Pb2+ and five Bi+2.92+ atoms to form SBi5Pb octahedra that share a cornercorner with one SCu2Bi4 octahedra and edges with six SBi5Pb octahedra. The corner-sharing octahedral tilt angles are 6°. In the twentieth S2- site, S2- is bonded in a distorted trigonal non-coplanar geometry to one Cu1+ and four Bi+2.92+ atoms. In the twenty-first S2- site, S2- is bonded to two Cu1+ and two equivalent Bi+2.92+ atoms to form distorted SCu2Bi2 trigonal pyramids that share corners with two equivalent SCuBi5 octahedra, corners with two equivalent SCu2Bi2 trigonal pyramids, an edgeedge with one SCuBi5 octahedra, and an edgeedge with one SCu2Bi2 trigonal pyramid. The corner-sharing octahedral tilt angles are 14°. In the twenty-second S2- site, S2- is bonded in a 3-coordinate geometry to two equivalent Cu1+ and three equivalent Bi+2.92+ atoms.