DOE OSTI2020
Na3GaS3 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. there are six inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded in a 4-coordinate geometry to four S2- atoms. There are a spread of Na–S bond distances ranging from 2.77–3.10 Å. In the second Na1+ site, Na1+ is bonded to five S2- atoms to form distorted NaS5 trigonal bipyramids that share corners with five GaS4 tetrahedra, corners with two equivalent NaS5 trigonal bipyramids, corners with two equivalent NaS4 trigonal pyramids, an edgeedge with one NaS6 octahedra, an edgeedge with one GaS4 tetrahedra, and an edgeedge with one NaS4 trigonal pyramid. There are a spread of Na–S bond distances ranging from 2.78–3.17 Å. In the third 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 2.78–3.25 Å. In the fourth Na1+ site, Na1+ is bonded in a 6-coordinate geometry to six S2- atoms. There are a spread of Na–S bond distances ranging from 2.81–3.44 Å. In the fifth Na1+ site, Na1+ is bonded to six S2- atoms to form distorted NaS6 octahedra that share corners with four GaS4 tetrahedra, corners with three equivalent NaS4 trigonal pyramids, edges with two equivalent NaS6 octahedra, edges with two GaS4 tetrahedra, and an edgeedge with one NaS5 trigonal bipyramid. There are a spread of Na–S bond distances ranging from 2.84–3.29 Å. In the sixth Na1+ site, Na1+ is bonded to four S2- atoms to form distorted NaS4 trigonal pyramids that share corners with three equivalent NaS6 octahedra, corners with three GaS4 tetrahedra, corners with two equivalent NaS5 trigonal bipyramids, an edgeedge with one GaS4 tetrahedra, and an edgeedge with one NaS5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 52–95°. There are a spread of Na–S bond distances ranging from 2.82–2.92 Å. There are two inequivalent Ga3+ sites. In the first Ga3+ site, Ga3+ is bonded to four S2- atoms to form GaS4 tetrahedra that share corners with two equivalent NaS6 octahedra, corners with two equivalent NaS5 trigonal bipyramids, corners with two equivalent NaS4 trigonal pyramids, an edgeedge with one NaS6 octahedra, an edgeedge with one GaS4 tetrahedra, an edgeedge with one NaS5 trigonal bipyramid, and an edgeedge with one NaS4 trigonal pyramid. The corner-sharing octahedra tilt angles range from 2–50°. There are a spread of Ga–S bond distances ranging from 2.25–2.37 Å. In the second Ga3+ site, Ga3+ is bonded to four S2- atoms to form GaS4 tetrahedra that share corners with two equivalent NaS6 octahedra, corners with three equivalent NaS5 trigonal bipyramids, a cornercorner with one NaS4 trigonal pyramid, an edgeedge with one NaS6 octahedra, and an edgeedge with one GaS4 tetrahedra. The corner-sharing octahedra tilt angles range from 28–53°. There are a spread of Ga–S bond distances ranging from 2.24–2.37 Å. There are six inequivalent S2- sites. In the first S2- site, S2- is bonded in a 7-coordinate geometry to six Na1+ and one Ga3+ atom. In the second S2- site, S2- is bonded to six Na1+ and one Ga3+ atom to form distorted SNa6Ga pentagonal bipyramids that share corners with two equivalent SNa5Ga pentagonal pyramids, edges with two equivalent SNa6Ga pentagonal bipyramids, and edges with two equivalent SNa5Ga pentagonal pyramids. In the third S2- site, S2- is bonded in a 5-coordinate geometry to three Na1+ and two equivalent Ga3+ atoms. In the fourth S2- site, S2- is bonded in a 6-coordinate geometry to four Na1+ and two equivalent Ga3+ atoms. In the fifth S2- site, S2- is bonded to five Na1+ and one Ga3+ atom to form distorted SNa5Ga pentagonal pyramids that share corners with two equivalent SNa6Ga pentagonal bipyramids, edges with two equivalent SNa6Ga pentagonal bipyramids, and edges with two equivalent SNa5Ga pentagonal pyramids. In the sixth S2- site, S2- is bonded in a 7-coordinate geometry to six Na1+ and one Ga3+ atom.