Materials Data on Al12ZnS19 by Materials Project

Abstract

ZnAl12S19 is beta indium sulfide-derived structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Zn2+ is bonded in a 6-coordinate geometry to six equivalent S2- atoms. All Zn–S bond lengths are 3.22 Å. There are five inequivalent Al3+ sites. In the first Al3+ site, Al3+ is bonded to six S2- atoms to form AlS6 octahedra that share corners with two equivalent AlS6 octahedra, corners with three equivalent AlS4 tetrahedra, a cornercorner with one AlS5 trigonal bipyramid, and edges with five AlS6 octahedra. The corner-sharing octahedral tilt angles are 55°. There are a spread of Al–S bond distances ranging from 2.33–2.51 Å. In the second Al3+ site, Al3+ is bonded to four S2- atoms to form corner-sharing AlS4 tetrahedra. The corner-sharing octahedra tilt angles range from 54–58°. There are one shorter (2.28 Å) and three longer (2.31 Å) Al–S bond lengths. In the third Al3+ site, Al3+ is bonded to six S2- atoms to form AlS6 octahedra that share corners with six equivalent AlS6 octahedra, corners with three equivalent AlS5 trigonal bipyramids, and a faceface with one AlS6 octahedra. The corner-sharing octahedral tilt angles are 55°. There are three shorter (2.37 Å) and three longer (2.46 Å) Al–S bond lengths. In the fourth Al3+ site, Al3+ is bonded to six equivalent S2- atoms to form AlS6 octahedra that share corners with six equivalent AlS4 tetrahedra and edges with six equivalent AlS6 octahedra. All Al–S bond lengths are 2.42 Å. In the fifth Al3+ site, Al3+ is bonded to five S2- atoms to form corner-sharing AlS5 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 42–60°. There are three shorter (2.25 Å) and two longer (2.65 Å) Al–S bond lengths. There are five inequivalent S2- sites. In the first S2- site, S2- is bonded in a 3-coordinate geometry to three Al3+ atoms. In the second S2- site, S2- is bonded in a 3-coordinate geometry to one Zn2+ and three Al3+ atoms. In the third S2- site, S2- is bonded in a rectangular see-saw-like geometry to four Al3+ atoms. In the fourth S2- site, S2- is bonded to four Al3+ atoms to form a mixture of distorted edge and corner-sharing SAl4 tetrahedra. In the fifth S2- site, S2- is bonded to four Al3+ atoms to form a mixture of distorted edge and corner-sharing SAl4 trigonal pyramids.