DOI: 10.17188/1199646
title: Materials Data on KNa22C2S9ClO42 by Materials Project

description: KNa22C2S9O42Cl crystallizes in the hexagonal P6_3/m space group. The structure is three-dimensional. K1+ is bonded to twelve O2- atoms to form KO12 cuboctahedra that share corners with six equivalent NaO6 octahedra, edges with six equivalent SO4 tetrahedra, and faces with two equivalent NaO6 octahedra. The corner-sharing octahedral tilt angles are 43°. There are six shorter (2.96 Å) and six longer (3.19 Å) K–O bond lengths. There are six inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded to six O2- atoms to form NaO6 octahedra that share corners with two equivalent KO12 cuboctahedra, corners with four equivalent SO4 tetrahedra, and edges with two equivalent NaO6 octahedra. There are a spread of Na–O bond distances ranging from 2.32–2.52 Å. In the second Na1+ site, Na1+ is bonded to six O2- atoms to form distorted NaO6 octahedra that share corners with three equivalent NaO6 octahedra, corners with three SO4 tetrahedra, an edgeedge with one NaO6 octahedra, and an edgeedge with one SO4 tetrahedra. The corner-sharing octahedra tilt angles range from 54–75°. There are a spread of Na–O bond distances ranging from 2.33–2.64 Å. In the third Na1+ site, Na1+ is bonded in a 7-coordinate geometry to six O2- and one Cl1- atom. There are three shorter (2.45 Å) and three longer (2.72 Å) Na–O bond lengths. The Na–Cl bond length is 2.69 Å. In the fourth Na1+ site, Na1+ is bonded to six O2- atoms to form NaO6 octahedra that share corners with six SO4 tetrahedra, a faceface with one KO12 cuboctahedra, and a faceface with one NaO6 octahedra. There are three shorter (2.40 Å) and three longer (2.47 Å) Na–O bond lengths. In the fifth Na1+ site, Na1+ is bonded in a 5-coordinate geometry to four O2- and one Cl1- atom. There are a spread of Na–O bond distances ranging from 2.29–2.53 Å. The Na–Cl bond length is 2.93 Å. In the sixth Na1+ site, Na1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Na–O bond distances ranging from 2.38–2.64 Å. C4+ is bonded in a trigonal planar geometry to three equivalent O2- atoms. All C–O bond lengths are 1.30 Å. There are two inequivalent S6+ sites. In the first S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with four NaO6 octahedra and edges with two equivalent NaO6 octahedra. The corner-sharing octahedral tilt angles are 45°. There are a spread of S–O bond distances ranging from 1.49–1.51 Å. In the second S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with five NaO6 octahedra and an edgeedge with one KO12 cuboctahedra. The corner-sharing octahedra tilt angles range from 42–61°. There is two shorter (1.49 Å) and two longer (1.50 Å) S–O bond length. There are eight inequivalent O2- sites. In the first O2- site, O2- is bonded in a 4-coordinate geometry to three Na1+ and one S6+ atom. In the second O2- site, O2- is bonded to four Na1+ and one C4+ atom to form distorted ONa4C trigonal bipyramids that share a cornercorner with one ONa3S tetrahedra, a cornercorner with one ONa4C trigonal bipyramid, and edges with two equivalent ONa4C trigonal bipyramids. In the third O2- site, O2- is bonded in a 4-coordinate geometry to three Na1+ and one S6+ atom. In the fourth O2- site, O2- is bonded in a 1-coordinate geometry to one K1+, three Na1+, and one S6+ atom. In the fifth O2- site, O2- is bonded to three Na1+ and one S6+ atom to form distorted ONa3S tetrahedra that share a cornercorner with one ClNa5 trigonal bipyramid and corners with two equivalent ONa4C trigonal bipyramids. In the sixth O2- site, O2- is bonded in a 1-coordinate geometry to one K1+, two Na1+, and one S6+ atom. In the seventh O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Na1+ and one S6+ atom. In the eighth O2- site, O2- is bonded in a 1-coordinate geometry to three Na1+ and one S6+ atom. Cl1- is bonded to five Na1+ atoms to form ClNa5 trigonal bipyramids that share corners with three equivalent ONa3S tetrahedra.