DOE OSTI2020
Sb17S27 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are seventeen inequivalent Sb+3.18+ sites. In the first Sb+3.18+ site, Sb+3.18+ is bonded to five S2- atoms to form distorted SbS5 square pyramids that share corners with seven SbS6 octahedra, edges with four SbS6 octahedra, and an edgeedge with one SbS5 square pyramid. The corner-sharing octahedra tilt angles range from 3–88°. There are a spread of Sb–S bond distances ranging from 2.49–3.00 Å. In the second Sb+3.18+ site, Sb+3.18+ is bonded to five S2- atoms to form SbS5 square pyramids that share a cornercorner with one SbS6 octahedra and edges with four SbS5 square pyramids. The corner-sharing octahedral tilt angles are 69°. There are a spread of Sb–S bond distances ranging from 2.48–2.94 Å. In the third Sb+3.18+ site, Sb+3.18+ is bonded to six S2- atoms to form distorted SbS6 octahedra that share corners with two SbS6 octahedra, corners with three SbS5 square pyramids, edges with four SbS6 octahedra, and edges with two SbS5 square pyramids. The corner-sharing octahedra tilt angles range from 5–11°. There are a spread of Sb–S bond distances ranging from 2.46–3.16 Å. In the fourth Sb+3.18+ site, Sb+3.18+ is bonded to five S2- atoms to form SbS5 square pyramids that share corners with two SbS6 octahedra and edges with four SbS5 square pyramids. The corner-sharing octahedra tilt angles range from 69–70°. There are a spread of Sb–S bond distances ranging from 2.46–2.81 Å. In the fifth Sb+3.18+ site, Sb+3.18+ is bonded to six S2- atoms to form SbS6 octahedra that share corners with three SbS6 octahedra, corners with two equivalent SbS5 square pyramids, edges with seven SbS6 octahedra, and an edgeedge with one SbS5 square pyramid. The corner-sharing octahedra tilt angles range from 3–4°. There are a spread of Sb–S bond distances ranging from 2.60–3.08 Å. In the sixth Sb+3.18+ site, Sb+3.18+ is bonded to five S2- atoms to form SbS5 square pyramids that share a cornercorner with one SbS6 octahedra and edges with four SbS5 square pyramids. The corner-sharing octahedral tilt angles are 70°. There are a spread of Sb–S bond distances ranging from 2.47–2.92 Å. In the seventh Sb+3.18+ site, Sb+3.18+ is bonded to five S2- atoms to form distorted SbS5 square pyramids that share corners with seven SbS6 octahedra, edges with four SbS6 octahedra, and an edgeedge with one SbS5 square pyramid. The corner-sharing octahedra tilt angles range from 3–88°. There are a spread of Sb–S bond distances ranging from 2.48–2.99 Å. In the eighth Sb+3.18+ site, Sb+3.18+ is bonded to six S2- atoms to form distorted SbS6 octahedra that share corners with two SbS6 octahedra, corners with three SbS5 square pyramids, edges with four SbS6 octahedra, and edges with two SbS5 square pyramids. The corner-sharing octahedra tilt angles range from 4–12°. There are a spread of Sb–S bond distances ranging from 2.46–3.17 Å. In the ninth Sb+3.18+ site, Sb+3.18+ is bonded to six S2- atoms to form distorted SbS6 octahedra that share corners with two SbS6 octahedra, corners with four SbS5 square pyramids, and edges with five SbS6 octahedra. The corner-sharing octahedral tilt angles are 3°. There are a spread of Sb–S bond distances ranging from 2.49–3.14 Å. In the tenth Sb+3.18+ site, Sb+3.18+ is bonded to six S2- atoms to form distorted SbS6 octahedra that share corners with two SbS6 octahedra, corners with four SbS5 square pyramids, and edges with eight SbS6 octahedra. The corner-sharing octahedra tilt angles range from 3–4°. There are a spread of Sb–S bond distances ranging from 2.59–3.20 Å. In the eleventh Sb+3.18+ site, Sb+3.18+ is bonded to five S2- atoms to form SbS5 square pyramids that share corners with two SbS6 octahedra and edges with four SbS5 square pyramids. The corner-sharing octahedral tilt angles are 69°. There are a spread of Sb–S bond distances ranging from 2.46–2.82 Å. In the twelfth Sb+3.18+ site, Sb+3.18+ is bonded to six S2- atoms to form SbS6 octahedra that share corners with four SbS6 octahedra, edges with seven SbS6 octahedra, and edges with two SbS5 square pyramids. The corner-sharing octahedra tilt angles range from 4–12°. There are a spread of Sb–S bond distances ranging from 2.60–3.16 Å. In the thirteenth Sb+3.18+ site, Sb+3.18+ is bonded to five S2- atoms to form SbS5 square pyramids that share corners with two SbS6 octahedra and edges with four SbS5 square pyramids. The corner-sharing octahedra tilt angles range from 67–68°. There are a spread of Sb–S bond distances ranging from 2.47–2.92 Å. In the fourteenth Sb+3.18+ site, Sb+3.18+ is bonded to six S2- atoms to form distorted SbS6 octahedra that share corners with three SbS6 octahedra, corners with three SbS5 square pyramids, and edges with six SbS6 octahedra. The corner-sharing octahedra tilt angles range from 4–5°. There are a spread of Sb–S bond distances ranging from 2.44–3.17 Å. In the fifteenth Sb+3.18+ site, Sb+3.18+ is bonded to five S2- atoms to form SbS5 square pyramids that share corners with two SbS6 octahedra and edges with four SbS5 square pyramids. The corner-sharing octahedra tilt angles range from 70–71°. There are a spread of Sb–S bond distances ranging from 2.48–2.77 Å. In the sixteenth Sb+3.18+ site, Sb+3.18+ is bonded to six S2- atoms to form SbS6 octahedra that share corners with three SbS6 octahedra, corners with two equivalent SbS5 square pyramids, edges with seven SbS6 octahedra, and an edgeedge with one SbS5 square pyramid. The corner-sharing octahedra tilt angles range from 3–5°. There are a spread of Sb–S bond distances ranging from 2.62–3.07 Å. In the seventeenth Sb+3.18+ site, Sb+3.18+ is bonded to six S2- atoms to form distorted SbS6 octahedra that share corners with three SbS6 octahedra, corners with three SbS5 square pyramids, and edges with six SbS6 octahedra. The corner-sharing octahedra tilt angles range from 3–5°. There are a spread of Sb–S bond distances ranging from 2.46–3.17 Å. There are twenty-seven inequivalent S2- sites. In the first S2- site, S2- is bonded in a water-like geometry to two Sb+3.18+ atoms. In the second S2- site, S2- is bonded in an L-shaped geometry to two Sb+3.18+ atoms. In the third S2- site, S2- is bonded in a distorted trigonal non-coplanar geometry to three Sb+3.18+ atoms. In the fourth S2- site, S2- is bonded to five Sb+3.18+ atoms to form distorted SSb5 square pyramids that share corners with two SSb6 octahedra, edges with two SSb6 octahedra, and an edgeedge with one SSb5 square pyramid. The corner-sharing octahedral tilt angles are 9°. In the fifth S2- site, S2- is bonded in a 3-coordinate geometry to three Sb+3.18+ atoms. In the sixth S2- site, S2- is bonded in a 3-coordinate geometry to three Sb+3.18+ atoms. In the seventh S2- site, S2- is bonded in a 3-coordinate geometry to three Sb+3.18+ atoms. In the eighth S2- site, S2- is bonded in a water-like geometry to two Sb+3.18+ atoms. In the ninth S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to four Sb+3.18+ atoms. In the tenth S2- site, S2- is bonded to five Sb+3.18+ atoms to form distorted SSb5 square pyramids that share corners with two SSb6 octahedra, edges with two SSb6 octahedra, and an edgeedge with one SSb5 square pyramid. The corner-sharing octahedral tilt angles are 3°. In the eleventh S2- site, S2- is bonded in a 3-coordinate geometry to three Sb+3.18+ atoms. In the twelfth S2- site, S2- is bonded in a distorted trigonal non-coplanar geometry to three Sb+3.18+ atoms. In the thirteenth S2- site, S2- is bonded in a distorted trigonal non-coplanar geometry to three Sb+3.18+ atoms. In the fourteenth S2- site, S2- is bonded in a 3-coordinate geometry to three Sb+3.18+ atoms. In the fifteenth S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to four Sb+3.18+ atoms. In the sixteenth S2- site, S2- is bonded to five Sb+3.18+ atoms to form distorted SSb5 square pyramids that share edges with two SSb6 octahedra and edges with two SSb5 square pyramids. In the seventeenth S2- site, S2- is bonded in a square co-planar geometry to four Sb+3.18+ atoms. In the eighteenth S2- site, S2- is bonded in a 3-coordinate geometry to three Sb+3.18+ atoms. In the nineteenth S2- site, S2- is bonded in a 3-coordinate geometry to three Sb+3.18+ atoms. In the twentieth S2- site, S2- is bonded in a 3-coordinate geometry to three Sb+3.18+ atoms. In the twenty-first S2- site, S2- is bonded in a distorted trigonal non-coplanar geometry to three Sb+3.18+ atoms. In the twenty-second S2- site, S2- is bonded in a rectangular see-saw-like geometry to four Sb+3.18+ atoms. In the twenty-third S2- site, S2- is bonded in a distorted trigonal non-coplanar geometry to three Sb+3.18+ atoms. In the twenty-fourth S2- site, S2- is bonded in a distorted trigonal non-coplanar geometry to three Sb+3.18+ atoms. In the twenty-fifth S2- site, S2- is bonded to six Sb+3.18+ atoms to form distorted SSb6 octahedra that share corners with two SSb5 square pyramids, an edgeedge with one SSb6 octahedra, and edges with three SSb5 square pyramids. In the twenty-sixth S2- site, S2- is bonded in a distorted trigonal non-coplanar geometry to three Sb+3.18+ atoms. In the twenty-seventh S2- site, S2- is bonded to six Sb+3.18+ atoms to form distorted SSb6 octahedra that share corners with two SSb5 square pyramids, an edgeedge with one SSb6 octahedra, and edges with three SSb5 square pyramids.