Materials Data on K4Mn(AsS4)2 by Materials Project

Abstract

K4Mn(AsS4)2 crystallizes in the monoclinic P2/c space group. The structure is three-dimensional. there are five inequivalent K1+ sites. In the first K1+ site, K1+ is bonded to six S2- atoms to form distorted KS6 octahedra that share corners with four equivalent MnS6 octahedra, corners with two equivalent AsS4 tetrahedra, edges with two equivalent KS6 octahedra, and edges with two equivalent AsS4 tetrahedra. The corner-sharing octahedra tilt angles range from 5–16°. There are a spread of K–S bond distances ranging from 3.28–3.66 Å. In the second 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 3.16–3.62 Å. In the third K1+ site, K1+ is bonded in a 7-coordinate geometry to seven S2- atoms. There are a spread of K–S bond distances ranging from 3.17–3.70 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 3.15–3.76 Å. In the fifth K1+ site, K1+ is bonded to six S2- atoms to form distorted KS6 octahedra that share corners with two equivalent AsS4 tetrahedra, edges with two equivalent KS6 octahedra, edges with two equivalent MnS6 octahedra, and edges with two equivalent AsS4 tetrahedra. There are a spread of K–S bond distances ranging from 3.20–3.30 Å. Mn2+ is bonded to six S2- atoms to form MnS6 octahedra that share corners with two equivalent KS6 octahedra, an edgeedge with one KS6 octahedra, an edgeedge with one MnS6 octahedra, and edges with three AsS4 tetrahedra. The corner-sharing octahedra tilt angles range from 5–16°. There are a spread of Mn–S bond distances ranging from 2.55–2.79 Å. There are two inequivalent As5+ sites. In the first As5+ site, As5+ is bonded to four S2- atoms to form AsS4 tetrahedra that share a cornercorner with one KS6 octahedra, an edgeedge with one KS6 octahedra, and edges with two equivalent MnS6 octahedra. The corner-sharing octahedral tilt angles are 82°. There are a spread of As–S bond distances ranging from 2.16–2.22 Å. In the second As5+ site, As5+ is bonded to four S2- atoms to form AsS4 tetrahedra that share a cornercorner with one KS6 octahedra, an edgeedge with one KS6 octahedra, and an edgeedge with one MnS6 octahedra. The corner-sharing octahedral tilt angles are 82°. There are a spread of As–S bond distances ranging from 2.17–2.22 Å. There are eight inequivalent S2- sites. In the first S2- site, S2- is bonded in a 2-coordinate geometry to three K1+, one Mn2+, and one As5+ atom. In the second S2- site, S2- is bonded to four K1+ and one As5+ atom to form distorted SK4As trigonal bipyramids that share a cornercorner with one SK4MnAs octahedra, corners with two SK4As trigonal bipyramids, an edgeedge with one SK4MnAs octahedra, and edges with two SK4As trigonal bipyramids. The corner-sharing octahedral tilt angles are 61°. In the third S2- site, S2- is bonded in a 6-coordinate geometry to three K1+, two equivalent Mn2+, and one As5+ atom. In the fourth S2- site, S2- is bonded in a 6-coordinate geometry to four K1+, one Mn2+, and one As5+ atom. In the fifth S2- site, S2- is bonded to four K1+ and one As5+ atom to form distorted SK4As trigonal bipyramids that share corners with two equivalent SK4MnAs octahedra, a cornercorner with one SK4As trigonal bipyramid, an edgeedge with one SK4MnAs octahedra, and edges with two SK4As trigonal bipyramids. The corner-sharing octahedra tilt angles range from 36–65°. In the sixth S2- site, S2- is bonded in a 5-coordinate geometry to four K1+ and one As5+ atom. In the seventh S2- site, S2- is bonded to four K1+, one Mn2+, and one As5+ atom to form distorted SK4MnAs octahedra that share corners with three SK4As trigonal bipyramids, an edgeedge with one SK4MnAs octahedra, and edges with two SK4As trigonal bipyramids. In the eighth S2- site, S2- is bonded in a 2-coordinate geometry to three K1+, one Mn2+, and one As5+ atom.