Materials Data on K4BaTi6S20O by Materials Project

Abstract

K4BaTi6S20O crystallizes in the hexagonal P6_322 space group. The structure is three-dimensional. there are two inequivalent K1+ sites. In the first K1+ site, K1+ is bonded to twelve S+1.40- atoms to form KS12 cuboctahedra that share corners with six equivalent TiS6O pentagonal bipyramids, edges with three equivalent BaS12 cuboctahedra, and faces with six equivalent TiS6O pentagonal bipyramids. There are six shorter (3.37 Å) and six longer (3.49 Å) K–S bond lengths. In the second K1+ site, K1+ is bonded in a 12-coordinate geometry to twelve S+1.40- atoms. There are a spread of K–S bond distances ranging from 3.28–3.82 Å. Ba2+ is bonded to twelve S+1.40- atoms to form BaS12 cuboctahedra that share corners with six equivalent TiS6O pentagonal bipyramids, edges with three equivalent KS12 cuboctahedra, and faces with six equivalent TiS6O pentagonal bipyramids. There are six shorter (3.39 Å) and six longer (3.47 Å) Ba–S bond lengths. Ti4+ is bonded to six S+1.40- and one O2- atom to form distorted TiS6O pentagonal bipyramids that share a cornercorner with one KS12 cuboctahedra, a cornercorner with one BaS12 cuboctahedra, a cornercorner with one TiS6O pentagonal bipyramid, a faceface with one KS12 cuboctahedra, a faceface with one BaS12 cuboctahedra, and faces with four equivalent TiS6O pentagonal bipyramids. There are a spread of Ti–S bond distances ranging from 2.37–2.55 Å. The Ti–O bond length is 2.30 Å. There are four inequivalent S+1.40- sites. In the first S+1.40- site, S+1.40- is bonded in a 6-coordinate geometry to three equivalent K1+ and three equivalent Ti4+ atoms. In the second S+1.40- site, S+1.40- is bonded in a 1-coordinate geometry to two equivalent K1+, one Ba2+, one Ti4+, and one S+1.40- atom. The S–S bond length is 2.07 Å. In the third S+1.40- site, S+1.40- is bonded in a 5-coordinate geometry to two K1+, one Ba2+, and three equivalent Ti4+ atoms. In the fourth S+1.40- site, S+1.40- is bonded in a 1-coordinate geometry to three K1+, one Ti4+, and one S+1.40- atom. O2- is bonded in an octahedral geometry to six equivalent Ti4+ atoms.