DOE OSTI2020
Cs3Zr2P5S18 crystallizes in the monoclinic Cc space group. The structure is three-dimensional. there are three inequivalent Cs1+ sites. In the first Cs1+ site, Cs1+ is bonded in a 9-coordinate geometry to nine S2- atoms. There are a spread of Cs–S bond distances ranging from 3.65–4.05 Å. In the second Cs1+ site, Cs1+ is bonded in a 10-coordinate geometry to ten S2- atoms. There are a spread of Cs–S bond distances ranging from 3.60–4.16 Å. In the third Cs1+ site, Cs1+ is bonded in a 9-coordinate geometry to nine S2- atoms. There are a spread of Cs–S bond distances ranging from 3.58–4.16 Å. There are two inequivalent Zr4+ sites. In the first Zr4+ site, Zr4+ is bonded to seven S2- atoms to form ZrS7 pentagonal bipyramids that share a cornercorner with one PS4 tetrahedra and edges with three PS4 tetrahedra. There are a spread of Zr–S bond distances ranging from 2.62–2.76 Å. In the second Zr4+ site, Zr4+ is bonded to seven S2- atoms to form ZrS7 pentagonal bipyramids that share a cornercorner with one PS4 tetrahedra and edges with three PS4 tetrahedra. There are a spread of Zr–S bond distances ranging from 2.62–2.77 Å. There are five inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four S2- atoms to form PS4 tetrahedra that share a cornercorner with one PS4 tetrahedra and an edgeedge with one ZrS7 pentagonal bipyramid. There are a spread of P–S bond distances ranging from 1.98–2.18 Å. In the second P5+ site, P5+ is bonded to four S2- atoms to form PS4 tetrahedra that share a cornercorner with one ZrS7 pentagonal bipyramid, a cornercorner with one PS4 tetrahedra, and an edgeedge with one ZrS7 pentagonal bipyramid. There are a spread of P–S bond distances ranging from 2.03–2.14 Å. In the third P5+ site, P5+ is bonded to four S2- atoms to form PS4 tetrahedra that share edges with two ZrS7 pentagonal bipyramids. There are two shorter (2.05 Å) and two longer (2.06 Å) P–S bond lengths. In the fourth P5+ site, P5+ is bonded to four S2- atoms to form PS4 tetrahedra that share a cornercorner with one PS4 tetrahedra and an edgeedge with one ZrS7 pentagonal bipyramid. There are a spread of P–S bond distances ranging from 1.98–2.17 Å. In the fifth P5+ site, P5+ is bonded to four S2- atoms to form PS4 tetrahedra that share a cornercorner with one ZrS7 pentagonal bipyramid, a cornercorner with one PS4 tetrahedra, and an edgeedge with one ZrS7 pentagonal bipyramid. There are a spread of P–S bond distances ranging from 2.03–2.15 Å. There are eighteen inequivalent S2- sites. In the first S2- site, S2- is bonded in a distorted water-like geometry to two equivalent Cs1+ and two P5+ atoms. In the second S2- site, S2- is bonded in a distorted single-bond geometry to three Cs1+ and one P5+ atom. In the third S2- site, S2- is bonded in an L-shaped geometry to one Cs1+, one Zr4+, and one P5+ atom. In the fourth S2- site, S2- is bonded in a distorted L-shaped geometry to two Cs1+, one Zr4+, and one P5+ atom. In the fifth S2- site, S2- is bonded in a 2-coordinate geometry to two Cs1+, one Zr4+, and one P5+ atom. In the sixth S2- site, S2- is bonded in a distorted L-shaped geometry to two equivalent Cs1+, one Zr4+, and one P5+ atom. In the seventh S2- site, S2- is bonded in a distorted L-shaped geometry to two equivalent Cs1+, one Zr4+, and one P5+ atom. In the eighth S2- site, S2- is bonded in a distorted L-shaped geometry to two equivalent Cs1+, one Zr4+, and one P5+ atom. In the ninth S2- site, S2- is bonded in an L-shaped geometry to one Cs1+, one Zr4+, and one P5+ atom. In the tenth S2- site, S2- is bonded in a 2-coordinate geometry to one Cs1+, one Zr4+, and one P5+ atom. In the eleventh S2- site, S2- is bonded in a distorted L-shaped geometry to one Cs1+, one Zr4+, and one P5+ atom. In the twelfth S2- site, S2- is bonded in a distorted L-shaped geometry to one Cs1+, one Zr4+, and one P5+ atom. In the thirteenth S2- site, S2- is bonded in a distorted L-shaped geometry to one Cs1+, one Zr4+, and one P5+ atom. In the fourteenth S2- site, S2- is bonded in a 3-coordinate geometry to one Cs1+, one Zr4+, and one P5+ atom. In the fifteenth S2- site, S2- is bonded in a distorted L-shaped geometry to one Cs1+, one Zr4+, and one P5+ atom. In the sixteenth S2- site, S2- is bonded in a 2-coordinate geometry to one Cs1+, one Zr4+, and one P5+ atom. In the seventeenth S2- site, S2- is bonded in a distorted water-like geometry to one Cs1+ and two P5+ atoms. In the eighteenth S2- site, S2- is bonded in a 1-coordinate geometry to three Cs1+ and one P5+ atom.