DOE OSTI2020
K4VP2S9 crystallizes in the orthorhombic Pna2_1 space group. The structure is three-dimensional. there are four inequivalent K1+ sites. In the first K1+ site, K1+ is bonded to eight S2- atoms to form distorted KS8 hexagonal bipyramids that share corners with seven KS8 hexagonal bipyramids, a cornercorner with one PS4 tetrahedra, corners with two equivalent VS5 trigonal bipyramids, edges with three PS4 tetrahedra, and an edgeedge with one VS5 trigonal bipyramid. There are a spread of K–S bond distances ranging from 3.20–3.60 Å. In the second K1+ site, K1+ is bonded to eight S2- atoms to form distorted KS8 hexagonal bipyramids that share corners with seven KS8 hexagonal bipyramids, a cornercorner with one PS4 tetrahedra, corners with two equivalent VS5 trigonal bipyramids, edges with three PS4 tetrahedra, and an edgeedge with one VS5 trigonal bipyramid. There are a spread of K–S bond distances ranging from 3.20–3.57 Å. In the third K1+ site, K1+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of K–S bond distances ranging from 3.30–3.67 Å. In the fourth K1+ site, K1+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of K–S bond distances ranging from 3.30–3.63 Å. V4+ is bonded to five S2- atoms to form distorted VS5 trigonal bipyramids that share corners with four KS8 hexagonal bipyramids, edges with two KS8 hexagonal bipyramids, and edges with two PS4 tetrahedra. There are one shorter (2.13 Å) and four longer (2.37 Å) V–S bond lengths. There are two 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 KS8 hexagonal bipyramid, edges with three KS8 hexagonal bipyramids, and an edgeedge with one VS5 trigonal bipyramid. There are a spread of P–S bond distances ranging from 2.01–2.12 Å. In the second P5+ site, P5+ is bonded to four S2- atoms to form PS4 tetrahedra that share a cornercorner with one KS8 hexagonal bipyramid, edges with three KS8 hexagonal bipyramids, and an edgeedge with one VS5 trigonal bipyramid. There are a spread of P–S bond distances ranging from 2.01–2.12 Å. There are nine inequivalent S2- sites. In the first S2- site, S2- is bonded in a distorted L-shaped geometry to three K1+, one V4+, and one P5+ atom. In the second S2- site, S2- is bonded in a 1-coordinate geometry to four K1+ and one P5+ atom. In the third S2- site, S2- is bonded in a 1-coordinate geometry to four K1+ and one P5+ atom. In the fourth S2- site, S2- is bonded in a distorted L-shaped geometry to three K1+, one V4+, and one P5+ atom. In the fifth S2- site, S2- is bonded in a 5-coordinate geometry to three K1+, one V4+, and one P5+ atom. In the sixth S2- site, S2- is bonded in a 5-coordinate geometry to three K1+, one V4+, and one P5+ atom. In the seventh S2- site, S2- is bonded in a distorted square pyramidal geometry to four K1+ and one V4+ atom. In the eighth S2- site, S2- is bonded in a 1-coordinate geometry to four K1+ and one P5+ atom. In the ninth S2- site, S2- is bonded in a 1-coordinate geometry to four K1+ and one P5+ atom.