DOE OSTI2020
Sr6Sb6S14(S3) crystallizes in the orthorhombic P2_12_12_1 space group. The structure is three-dimensional. there are six inequivalent Sr2+ sites. In the first Sr2+ site, Sr2+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Sr–S bond distances ranging from 3.01–3.27 Å. In the second Sr2+ site, Sr2+ is bonded in a 9-coordinate geometry to nine S2- atoms. There are a spread of Sr–S bond distances ranging from 3.05–3.60 Å. In the third Sr2+ site, Sr2+ is bonded to seven S2- atoms to form distorted SrS7 pentagonal bipyramids that share a cornercorner with one SbS5 square pyramid and edges with two equivalent SrS7 pentagonal bipyramids. There are a spread of Sr–S bond distances ranging from 3.02–3.32 Å. In the fourth Sr2+ site, Sr2+ is bonded to seven S2- atoms to form distorted SrS7 pentagonal bipyramids that share a cornercorner with one SbS5 square pyramid and edges with two equivalent SrS7 pentagonal bipyramids. There are a spread of Sr–S bond distances ranging from 3.03–3.19 Å. In the fifth Sr2+ site, Sr2+ is bonded in a 9-coordinate geometry to nine S2- atoms. There are a spread of Sr–S bond distances ranging from 3.04–3.31 Å. In the sixth Sr2+ site, Sr2+ is bonded in a 9-coordinate geometry to nine S2- atoms. There are a spread of Sr–S bond distances ranging from 3.03–3.32 Å. There are six inequivalent Sb+3.67+ sites. In the first Sb+3.67+ site, Sb+3.67+ is bonded in a distorted trigonal non-coplanar geometry to three S2- atoms. There are two shorter (2.47 Å) and one longer (2.53 Å) Sb–S bond lengths. In the second Sb+3.67+ site, Sb+3.67+ is bonded to five S2- atoms to form SbS5 square pyramids that share corners with two SrS7 pentagonal bipyramids. There are a spread of Sb–S bond distances ranging from 2.44–3.08 Å. In the third Sb+3.67+ site, Sb+3.67+ is bonded in a distorted rectangular see-saw-like geometry to four S2- atoms. There are a spread of Sb–S bond distances ranging from 2.47–3.17 Å. In the fourth Sb+3.67+ site, Sb+3.67+ is bonded in a 4-coordinate geometry to three S2- atoms. There are a spread of Sb–S bond distances ranging from 2.46–2.57 Å. In the fifth Sb+3.67+ site, Sb+3.67+ is bonded in a distorted rectangular see-saw-like geometry to four S2- atoms. There are a spread of Sb–S bond distances ranging from 2.47–2.87 Å. In the sixth Sb+3.67+ site, Sb+3.67+ is bonded in a distorted trigonal non-coplanar geometry to three S2- atoms. There are a spread of Sb–S bond distances ranging from 2.46–2.53 Å. There are seventeen inequivalent S2- sites. In the first S2- site, S2- is bonded in a 5-coordinate geometry to four Sr2+ and one S2- atom. The S–S bond length is 2.10 Å. In the second S2- site, S2- is bonded in a 6-coordinate geometry to four Sr2+ and two S2- atoms. The S–S bond length is 2.09 Å. In the third S2- site, S2- is bonded in a 5-coordinate geometry to four Sr2+ and one S2- atom. In the fourth S2- site, S2- is bonded to two Sr2+ and two Sb+3.67+ atoms to form distorted SSr2Sb2 trigonal pyramids that share a cornercorner with one SSr4Sb square pyramid, a cornercorner with one SSr4Sb trigonal bipyramid, corners with two equivalent SSr2Sb2 trigonal pyramids, and edges with three SSr4Sb trigonal bipyramids. In the fifth S2- site, S2- is bonded to four Sr2+ and one Sb+3.67+ atom to form distorted SSr4Sb trigonal bipyramids that share corners with four SSr4Sb trigonal bipyramids, an edgeedge with one SSr4Sb square pyramid, an edgeedge with one SSr4Sb trigonal bipyramid, and edges with two SSr2Sb2 trigonal pyramids. In the sixth S2- site, S2- is bonded to two Sr2+ and two Sb+3.67+ atoms to form SSr2Sb2 trigonal pyramids that share a cornercorner with one SSr4Sb square pyramid, a cornercorner with one SSr4Sb trigonal bipyramid, corners with two equivalent SSr2Sb2 trigonal pyramids, and edges with three SSr4Sb trigonal bipyramids. In the seventh S2- site, S2- is bonded in a 5-coordinate geometry to four Sr2+ and one Sb+3.67+ atom. In the eighth S2- site, S2- is bonded in a 3-coordinate geometry to one Sr2+ and two Sb+3.67+ atoms. In the ninth S2- site, S2- is bonded in a 3-coordinate geometry to one Sr2+ and two Sb+3.67+ atoms. In the tenth S2- site, S2- is bonded to four Sr2+ and one Sb+3.67+ atom to form distorted SSr4Sb trigonal bipyramids that share corners with four SSr4Sb trigonal bipyramids, corners with two SSr2Sb2 trigonal pyramids, edges with two equivalent SSr4Sb square pyramids, and an edgeedge with one SSr4Sb trigonal bipyramid. In the eleventh S2- site, S2- is bonded in a 4-coordinate geometry to one Sr2+ and two Sb+3.67+ atoms. In the twelfth S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to one Sr2+ and three Sb+3.67+ atoms. In the thirteenth S2- site, S2- is bonded to four Sr2+ and one Sb+3.67+ atom to form SSr4Sb square pyramids that share corners with two equivalent SSr4Sb trigonal bipyramids, corners with two SSr2Sb2 trigonal pyramids, and edges with four SSr4Sb trigonal bipyramids. In the fourteenth S2- site, S2- is bonded in a 3-coordinate geometry to three Sr2+ and one Sb+3.67+ atom. In the fifteenth S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to two Sr2+ and two Sb+3.67+ atoms. In the sixteenth S2- site, S2- is bonded to four Sr2+ and one Sb+3.67+ atom to form distorted SSr4Sb trigonal bipyramids that share corners with two equivalent SSr4Sb square pyramids, edges with four SSr4Sb trigonal bipyramids, and edges with two SSr2Sb2 trigonal pyramids. In the seventeenth S2- site, S2- is bonded to four Sr2+ and one Sb+3.67+ atom to form distorted SSr4Sb trigonal bipyramids that share corners with four SSr4Sb trigonal bipyramids, an edgeedge with one SSr4Sb square pyramid, edges with two equivalent SSr4Sb trigonal bipyramids, and edges with two SSr2Sb2 trigonal pyramids.