Materials Data on Cu6PS5Br by Materials Project

Abstract

Cu6PS5Br crystallizes in the monoclinic Cc space group. The structure is three-dimensional. there are six inequivalent Cu1+ sites. In the first Cu1+ site, Cu1+ is bonded in a distorted trigonal planar geometry to three S2- atoms. There are one shorter (2.26 Å) and two longer (2.28 Å) Cu–S bond lengths. In the second Cu1+ site, Cu1+ is bonded to three S2- and one Br1- atom to form CuS3Br tetrahedra that share corners with two equivalent PS4 tetrahedra and corners with six CuS3Br tetrahedra. There are a spread of Cu–S bond distances ranging from 2.29–2.34 Å. The Cu–Br bond length is 2.61 Å. In the third Cu1+ site, Cu1+ is bonded in a distorted trigonal planar geometry to three S2- atoms. All Cu–S bond lengths are 2.27 Å. In the fourth Cu1+ site, Cu1+ is bonded in a distorted trigonal planar geometry to three S2- atoms. There are one shorter (2.26 Å) and two longer (2.27 Å) Cu–S bond lengths. In the fifth Cu1+ site, Cu1+ is bonded to three S2- and one Br1- atom to form CuS3Br tetrahedra that share corners with two equivalent PS4 tetrahedra and corners with six CuS3Br tetrahedra. There are a spread of Cu–S bond distances ranging from 2.28–2.32 Å. The Cu–Br bond length is 2.73 Å. In the sixth Cu1+ site, Cu1+ is bonded to three S2- and one Br1- atom to form CuS3Br tetrahedra that share corners with two equivalent PS4 tetrahedra and corners with six CuS3Br tetrahedra. There are a spread of Cu–S bond distances ranging from 2.30–2.36 Å. The Cu–Br bond length is 2.60 Å. P5+ is bonded to four S2- atoms to form PS4 tetrahedra that share corners with six CuS3Br tetrahedra. There are two shorter (2.07 Å) and two longer (2.08 Å) P–S bond lengths. There are five inequivalent S2- sites. In the first S2- site, S2- is bonded to three Cu1+ and one P5+ atom to form SCu3P tetrahedra that share corners with three equivalent SCu6 octahedra and corners with six SCu3P tetrahedra. The corner-sharing octahedra tilt angles range from 45–69°. In the second S2- site, S2- is bonded to six Cu1+ atoms to form distorted corner-sharing SCu6 octahedra. In the third S2- site, S2- is bonded to three Cu1+ and one P5+ atom to form SCu3P tetrahedra that share corners with three equivalent SCu6 octahedra and corners with six SCu3P tetrahedra. The corner-sharing octahedra tilt angles range from 58–62°. In the fourth S2- site, S2- is bonded to three Cu1+ and one P5+ atom to form SCu3P tetrahedra that share corners with three equivalent SCu6 octahedra and corners with six SCu3P tetrahedra. The corner-sharing octahedra tilt angles range from 44–68°. In the fifth S2- site, S2- is bonded to three Cu1+ and one P5+ atom to form SCu3P tetrahedra that share corners with three equivalent SCu6 octahedra and corners with six SCu3P tetrahedra. The corner-sharing octahedra tilt angles range from 45–65°. Br1- is bonded in a distorted trigonal planar geometry to three Cu1+ atoms.