Materials Data on Zn(GaS2)2 by Materials Project

Abstract

ZnGa2S4 crystallizes in the monoclinic Cm space group. The structure is two-dimensional and consists of two ZnGa2S4 sheets oriented in the (0, 0, 1) direction. In one of the ZnGa2S4 sheets, Zn2+ is bonded to four S2- atoms to form ZnS4 tetrahedra that share corners with three equivalent GaS6 octahedra and corners with six equivalent ZnS4 tetrahedra. The corner-sharing octahedral tilt angles are 61°. There are a spread of Zn–S bond distances ranging from 2.25–2.59 Å. There are two inequivalent Ga3+ sites. In the first Ga3+ site, Ga3+ is bonded to six S2- atoms to form GaS6 octahedra that share corners with three equivalent ZnS4 tetrahedra, corners with three equivalent GaS4 tetrahedra, and edges with six equivalent GaS6 octahedra. There are three shorter (2.45 Å) and three longer (2.59 Å) Ga–S bond lengths. In the second Ga3+ site, Ga3+ is bonded to four S2- atoms to form GaS4 tetrahedra that share corners with three equivalent GaS6 octahedra and corners with six equivalent GaS4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. There are a spread of Ga–S bond distances ranging from 2.27–2.36 Å. There are four inequivalent S2- sites. In the first S2- site, S2- is bonded in a trigonal non-coplanar geometry to three equivalent Zn2+ atoms. In the second S2- site, S2- is bonded to one Zn2+ and three equivalent Ga3+ atoms to form corner-sharing SZnGa3 tetrahedra. In the third S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to four Ga3+ atoms. In the fourth S2- site, S2- is bonded in a trigonal non-coplanar geometry to three equivalent Ga3+ atoms. In one of the ZnGa2S4 sheets, Zn2+ is bonded to four S2- atoms to form ZnS4 tetrahedra that share corners with three equivalent GaS6 octahedra and corners with six equivalent ZnS4 tetrahedra. The corner-sharing octahedra tilt angles range from 61–62°. There are a spread of Zn–S bond distances ranging from 2.24–2.68 Å. There are two inequivalent Ga3+ sites. In the first Ga3+ site, Ga3+ is bonded to six S2- atoms to form GaS6 octahedra that share corners with three equivalent ZnS4 tetrahedra, corners with three equivalent GaS4 tetrahedra, and edges with six equivalent GaS6 octahedra. There are three shorter (2.45 Å) and three longer (2.59 Å) Ga–S bond lengths. In the second Ga3+ site, Ga3+ is bonded to four S2- atoms to form GaS4 tetrahedra that share corners with three equivalent GaS6 octahedra and corners with six equivalent GaS4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. There are one shorter (2.27 Å) and three longer (2.35 Å) Ga–S bond lengths. There are four inequivalent S2- sites. In the first S2- site, S2- is bonded in a trigonal non-coplanar geometry to three equivalent Zn2+ atoms. In the second S2- site, S2- is bonded to one Zn2+ and three equivalent Ga3+ atoms to form distorted corner-sharing SZnGa3 tetrahedra. In the third S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to four Ga3+ atoms. In the fourth S2- site, S2- is bonded in a trigonal non-coplanar geometry to three equivalent Ga3+ atoms.