DOE OSTI2020
Tl3(V3S4)8 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are twenty-four inequivalent V+2.54+ sites. In the first V+2.54+ site, V+2.54+ is bonded in a distorted see-saw-like geometry to four S2- atoms. There are a spread of V–S bond distances ranging from 2.29–2.34 Å. In the second V+2.54+ site, V+2.54+ is bonded in a 4-coordinate geometry to four S2- atoms. There are a spread of V–S bond distances ranging from 2.18–2.38 Å. In the third V+2.54+ site, V+2.54+ is bonded to six S2- atoms to form VS6 octahedra that share corners with three VS6 octahedra, corners with three VS5 trigonal bipyramids, an edgeedge with one VS5 trigonal bipyramid, and a faceface with one VS6 octahedra. The corner-sharing octahedra tilt angles range from 25–36°. There are a spread of V–S bond distances ranging from 2.37–2.63 Å. In the fourth V+2.54+ site, V+2.54+ is bonded to five S2- atoms to form VS5 trigonal bipyramids that share corners with four VS6 octahedra, corners with two VS5 trigonal bipyramids, an edgeedge with one VS6 octahedra, and a faceface with one VS6 octahedra. The corner-sharing octahedra tilt angles range from 49–60°. There are a spread of V–S bond distances ranging from 2.26–2.44 Å. In the fifth V+2.54+ site, V+2.54+ is bonded to six S2- atoms to form VS6 octahedra that share a cornercorner with one VS6 octahedra, corners with five VS5 trigonal bipyramids, edges with two VS6 octahedra, an edgeedge with one VS5 trigonal bipyramid, and a faceface with one VS6 octahedra. The corner-sharing octahedral tilt angles are 36°. There are a spread of V–S bond distances ranging from 2.35–2.71 Å. In the sixth V+2.54+ site, V+2.54+ is bonded to six S2- atoms to form distorted VS6 octahedra that share corners with two VS6 octahedra, corners with three VS5 trigonal bipyramids, edges with three VS6 octahedra, and edges with two VS5 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 25–42°. There are a spread of V–S bond distances ranging from 2.29–2.85 Å. In the seventh V+2.54+ site, V+2.54+ is bonded to six S2- atoms to form VS6 octahedra that share corners with two VS6 octahedra, corners with four VS5 trigonal bipyramids, an edgeedge with one VS6 octahedra, an edgeedge with one VS5 trigonal bipyramid, and a faceface with one VS5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 36–50°. There are a spread of V–S bond distances ranging from 2.34–2.56 Å. In the eighth V+2.54+ site, V+2.54+ is bonded to five S2- atoms to form VS5 trigonal bipyramids that share corners with four VS6 octahedra, corners with three VS5 trigonal bipyramids, and a faceface with one VS6 octahedra. The corner-sharing octahedra tilt angles range from 44–59°. There are a spread of V–S bond distances ranging from 2.25–2.44 Å. In the ninth V+2.54+ site, V+2.54+ is bonded to six S2- atoms to form distorted VS6 octahedra that share corners with three VS6 octahedra, corners with three VS5 trigonal bipyramids, an edgeedge with one VS5 trigonal bipyramid, faces with two VS6 octahedra, and a faceface with one VS5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 42–52°. There are a spread of V–S bond distances ranging from 2.32–2.84 Å. In the tenth V+2.54+ site, V+2.54+ is bonded to five S2- atoms to form distorted VS5 trigonal bipyramids that share corners with three VS6 octahedra, corners with two VS5 trigonal bipyramids, an edgeedge with one VS6 octahedra, an edgeedge with one VS5 trigonal bipyramid, and faces with two VS6 octahedra. The corner-sharing octahedra tilt angles range from 49–50°. There are a spread of V–S bond distances ranging from 2.29–2.43 Å. In the eleventh V+2.54+ site, V+2.54+ is bonded to five S2- atoms to form VS5 trigonal bipyramids that share corners with four VS6 octahedra, a cornercorner with one VS5 square pyramid, a cornercorner with one VS5 trigonal bipyramid, edges with three VS6 octahedra, and edges with two VS5 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 2–63°. There are a spread of V–S bond distances ranging from 2.31–2.58 Å. In the twelfth V+2.54+ site, V+2.54+ is bonded to five S2- atoms to form VS5 trigonal bipyramids that share corners with three VS6 octahedra, a cornercorner with one VS5 square pyramid, corners with four VS5 trigonal bipyramids, edges with two VS6 octahedra, and an edgeedge with one VS5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 11–49°. There are a spread of V–S bond distances ranging from 2.25–2.47 Å. In the thirteenth V+2.54+ site, V+2.54+ is bonded in a 5-coordinate geometry to five S2- atoms. There are a spread of V–S bond distances ranging from 2.22–2.94 Å. In the fourteenth V+2.54+ site, V+2.54+ is bonded to six S2- atoms to form VS6 octahedra that share corners with two VS6 octahedra, a cornercorner with one VS5 square pyramid, corners with three VS5 trigonal bipyramids, edges with two VS6 octahedra, an edgeedge with one VS5 trigonal bipyramid, a faceface with one VS6 octahedra, and a faceface with one VS5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 22–34°. There are a spread of V–S bond distances ranging from 2.42–2.64 Å. In the fifteenth V+2.54+ site, V+2.54+ is bonded to five S2- atoms to form VS5 trigonal bipyramids that share corners with five VS6 octahedra, a cornercorner with one VS5 square pyramid, a cornercorner with one VS5 trigonal bipyramid, an edgeedge with one VS6 octahedra, and edges with two VS5 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 40–74°. There are a spread of V–S bond distances ranging from 2.31–2.50 Å. In the sixteenth V+2.54+ site, V+2.54+ is bonded in a 6-coordinate geometry to six S2- atoms. There are a spread of V–S bond distances ranging from 2.37–2.77 Å. In the seventeenth V+2.54+ site, V+2.54+ is bonded to five S2- atoms to form VS5 trigonal bipyramids that share corners with two VS6 octahedra, a cornercorner with one VS5 square pyramid, a cornercorner with one VS5 trigonal bipyramid, and a faceface with one VS6 octahedra. The corner-sharing octahedra tilt angles range from 45–46°. There are a spread of V–S bond distances ranging from 2.32–2.46 Å. In the eighteenth V+2.54+ site, V+2.54+ is bonded to six S2- atoms to form distorted VS6 octahedra that share corners with four VS6 octahedra, corners with two VS5 trigonal bipyramids, an edgeedge with one VS5 square pyramid, and a faceface with one VS5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 34–56°. There are a spread of V–S bond distances ranging from 2.28–2.92 Å. In the nineteenth V+2.54+ site, V+2.54+ is bonded to six S2- atoms to form VS6 octahedra that share corners with two VS6 octahedra, a cornercorner with one VS5 square pyramid, corners with four VS5 trigonal bipyramids, and a faceface with one VS6 octahedra. The corner-sharing octahedra tilt angles range from 56–58°. There are a spread of V–S bond distances ranging from 2.37–2.53 Å. In the twentieth V+2.54+ site, V+2.54+ is bonded to six S2- atoms to form VS6 octahedra that share corners with five VS6 octahedra, a cornercorner with one VS5 square pyramid, a cornercorner with one VS5 trigonal bipyramid, edges with three VS5 trigonal bipyramids, and a faceface with one VS5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 22–58°. There are a spread of V–S bond distances ranging from 2.34–2.59 Å. In the twenty-first V+2.54+ site, V+2.54+ is bonded to five S2- atoms to form distorted VS5 square pyramids that share corners with three VS6 octahedra, corners with four VS5 trigonal bipyramids, and an edgeedge with one VS6 octahedra. The corner-sharing octahedra tilt angles range from 45–59°. There are a spread of V–S bond distances ranging from 2.26–2.64 Å. In the twenty-second V+2.54+ site, V+2.54+ is bonded to five S2- atoms to form VS5 trigonal bipyramids that share corners with three VS6 octahedra, corners with two VS5 trigonal bipyramids, and edges with two VS6 octahedra. The corner-sharing octahedra tilt angles range from 36–45°. There are a spread of V–S bond distances ranging from 2.21–2.49 Å. In the twenty-third V+2.54+ site, V+2.54+ is bonded in a 4-coordinate geometry to four S2- atoms. There are a spread of V–S bond distances ranging from 2.25–2.48 Å. In the twenty-fourth V+2.54+ site, V+2.54+ is bonded in a 6-coordinate geometry to six S2- atoms. There are a spread of V–S bond distances ranging from 2.39–2.66 Å. There are three inequivalent Tl1+ sites. In the first Tl1+ site, Tl1+ is bonded in a 3-coordinate geometry to three S2- atoms. There are one shorter (2.82 Å) and two longer (3.14 Å) Tl–S bond lengths. In the second Tl1+ site, Tl1+ is bonded in a 6-coordinate geometry to six S2- atoms. There are a spread of Tl–S bond distances ranging from 2.94–3.27 Å. In the third Tl1+ site, Tl1+ is bonded in a 7-coordinate geometry to seven S2- atoms. There are a spread of Tl–S bond distances ranging from 2.85–3.46 Å. There are thirty-two inequivalent S2- sites. In the first S2- site, S2- is bonded in a distorted pentagonal planar geometry to five V+2.54+ atoms. In the second S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.54+ atoms. In the third S2- site, S2- is bonded in a distorted see-saw-like geometry to four V+2.54+ atoms. In the fourth S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.54+ atoms. In the fifth S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.54+ atoms. In the sixth S2- site, S2- is bonded in a 3-coordinate geometry to three V+2.54+ and one Tl1+ atom. In the seventh S2- site, S2- is bonded in a 3-coordinate geometry to three V+2.54+ and one Tl1+ atom. In the eighth S2- site, S2- is bonded in a 4-coordinate geometry to three V+2.54+ and one Tl1+ atom. In the ninth S2- site, S2- is bonded in a 5-coordinate geometry to four V+2.54+ and one Tl1+ atom. In the tenth S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.54+ atoms. In the eleventh S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.54+ and one Tl1+ atom. In the twelfth S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.54+ atoms. In the thirteenth S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.54+ atoms. In the fourteenth S2- site, S2- is bonded in a 4-coordinate geometry to three V+2.54+ and one Tl1+ atom. In the fifteenth S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.54+ and one Tl1+ atom. In the sixteenth S2- site, S2- is bonded in a 6-coordinate geometry to five V+2.54+ and one Tl1+ atom. In the seventeenth S2- site, S2- is bonded in a 6-coordinate geometry to five V+2.54+ and one Tl1+ atom. In the eighteenth S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.54+ and one Tl1+ atom. In the nineteenth S2- site, S2- is bonded in a 4-coordinate geometry to three V+2.54+ and one Tl1+ atom. In the twentieth S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.54+ atoms. In the twenty-first S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.54+ atoms. In the twenty-second S2- site, S2- is bonded in a 1-coordinate geometry to four V+2.54+ and one Tl1+ atom. In the twenty-third S2- site, S2- is bonded in a 5-coordinate geometry to five V+2.54+ atoms. In the twenty-fourth S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.54+ and one Tl1+ atom. In the twenty-fifth S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.54+ atoms. In the twenty-sixth S2- site, S2- is bonded in a 4-coordinate geometry to three V+2.54+ and one Tl1+ atom. In the twenty-seventh S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.54+ atoms. In the twenty-eighth S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.54+ and one Tl1+ atom. In the twenty-ninth S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.54+ atoms. In the thirtieth S2- site, S2- is bonded in a 5-coordinate geometry t