Materials Data on Al2ZnS4 by Materials Project

ZnAl2S4 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. Zn2+ is bonded to six S2- atoms to form ZnS6 octahedra that share corners with four equivalent ZnS6 octahedra, corners with four equivalent AlS6 octahedra, corners with four equivalent AlS4 tetrahedra, edges with two equivalent AlS6 octahedra, and an edgeedge with one AlS4 tetrahedra. The corner-sharing octahedra tilt angles range from 49–51°. There are a spread of Zn–S bond distances ranging from 2.54–2.65 Å. There are two inequivalent Al3+ sites. In the first Al3+ site, Al3+ is bonded to four S2- atoms to form AlS4 tetrahedra that share corners with two equivalent AlS6 octahedra, corners with four equivalent ZnS6 octahedra, an edgeedge with one ZnS6 octahedra, and edges with two equivalent AlS6 octahedra. The corner-sharing octahedra tilt angles range from 60–67°. There are three shorter (2.25 Å) and one longer (2.27 Å) Al–S bond lengths. In the second Al3+ site, Al3+ is bonded to six S2- atoms to form AlS6 octahedra that share corners with four equivalent ZnS6 octahedra, corners with two equivalent AlS4 tetrahedra, edges with two equivalent ZnS6 octahedra, edges with two equivalent AlS6 octahedra, and edges with two equivalent AlS4 tetrahedra. The corner-sharing octahedra tilt angles range from 49–51°. There are a spread of Al–S bond distances ranging from 2.44–2.46 Å. There are three inequivalent S2- sites. In the first S2- site, S2- is bonded to one Zn2+ and three Al3+ atoms to form distorted corner-sharing SAl3Zn tetrahedra. In the second S2- site, S2- is bonded in a rectangular see-saw-like geometry to one Zn2+ and three Al3+ atoms. In the third S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to two equivalent Zn2+ and two Al3+ atoms.