DOI: 10.17188/1355019
title: Materials Data on Na4Zn3S5 by Materials Project

description: Na4Zn3S5 crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. there are four inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded to five S2- atoms to form distorted NaS5 trigonal bipyramids that share corners with two equivalent NaS6 octahedra, corners with two equivalent NaS5 square pyramids, corners with three ZnS4 tetrahedra, an edgeedge with one NaS6 octahedra, edges with four ZnS4 tetrahedra, and edges with two equivalent NaS5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 32°. There are a spread of Na–S bond distances ranging from 2.69–2.81 Å. In the second Na1+ site, Na1+ is bonded to five S2- atoms to form NaS5 square pyramids that share corners with three equivalent NaS6 octahedra, corners with four ZnS4 tetrahedra, corners with two equivalent NaS5 trigonal bipyramids, edges with four equivalent NaS5 square pyramids, and edges with four ZnS4 tetrahedra. The corner-sharing octahedra tilt angles range from 33–54°. There are three shorter (2.95 Å) and two longer (3.01 Å) Na–S bond lengths. In the third Na1+ site, Na1+ is bonded to six S2- atoms to form NaS6 octahedra that share corners with three equivalent NaS5 square pyramids, corners with five ZnS4 tetrahedra, corners with two equivalent NaS5 trigonal bipyramids, edges with four equivalent NaS6 octahedra, edges with five ZnS4 tetrahedra, and an edgeedge with one NaS5 trigonal bipyramid. There are a spread of Na–S bond distances ranging from 2.89–3.12 Å. In the fourth Na1+ site, Na1+ is bonded in a 5-coordinate geometry to five S2- atoms. There are a spread of Na–S bond distances ranging from 2.78–2.95 Å. There are three inequivalent Zn2+ sites. In the first Zn2+ site, Zn2+ is bonded to four S2- atoms to form ZnS4 tetrahedra that share a cornercorner with one NaS6 octahedra, corners with two equivalent NaS5 square pyramids, corners with six ZnS4 tetrahedra, a cornercorner with one NaS5 trigonal bipyramid, edges with two equivalent NaS6 octahedra, and edges with three equivalent NaS5 square pyramids. The corner-sharing octahedral tilt angles are 15°. There are one shorter (2.39 Å) and three longer (2.40 Å) Zn–S bond lengths. In the second Zn2+ site, Zn2+ is bonded to four S2- atoms to form ZnS4 tetrahedra that share corners with two equivalent NaS6 octahedra, corners with two equivalent NaS5 square pyramids, corners with six ZnS4 tetrahedra, corners with two equivalent NaS5 trigonal bipyramids, an edgeedge with one NaS5 square pyramid, and edges with two equivalent NaS5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 48°. There are a spread of Zn–S bond distances ranging from 2.32–2.49 Å. In the third Zn2+ site, Zn2+ is bonded to four S2- atoms to form ZnS4 tetrahedra that share corners with two equivalent NaS6 octahedra, corners with six ZnS4 tetrahedra, edges with three equivalent NaS6 octahedra, and edges with two equivalent NaS5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 18°. There are a spread of Zn–S bond distances ranging from 2.35–2.48 Å. There are five inequivalent S2- sites. In the first S2- site, S2- is bonded in a 6-coordinate geometry to four Na1+ and two Zn2+ atoms. In the second S2- site, S2- is bonded in a 7-coordinate geometry to five Na1+ and two equivalent Zn2+ atoms. In the third S2- site, S2- is bonded in a 8-coordinate geometry to six Na1+ and two Zn2+ atoms. In the fourth S2- site, S2- is bonded to three equivalent Na1+ and three Zn2+ atoms to form a mixture of distorted corner and edge-sharing SNa3Zn3 octahedra. The corner-sharing octahedral tilt angles are 72°. In the fifth S2- site, S2- is bonded to three Na1+ and three Zn2+ atoms to form a mixture of distorted corner and edge-sharing SNa3Zn3 octahedra. The corner-sharing octahedral tilt angles are 72°.