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 to six S2- atoms to form distorted VS6 octahedra that share corners with three VS6 octahedra, 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 4–43°. There are a spread of V–S bond distances ranging from 2.38–2.86 Å. In the second 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 2.34–2.64 Å. In the third V+2.54+ site, V+2.54+ is bonded to five S2- atoms to form distorted VS5 trigonal bipyramids that share corners with two VS6 octahedra, a cornercorner with one VS6 pentagonal pyramid, a cornercorner with one VS5 trigonal bipyramid, and edges with two VS6 octahedra. The corner-sharing octahedra tilt angles range from 20–66°. There are a spread of V–S bond distances ranging from 2.32–2.41 Å. In the 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 2.36–2.55 Å. In the fifth 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, a cornercorner with one VS6 pentagonal pyramid, corners with two VS5 trigonal bipyramids, an edgeedge with one VS6 octahedra, an edgeedge with one VS6 pentagonal pyramid, and edges with two VS5 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 43–50°. There are a spread of V–S bond distances ranging from 2.34–2.76 Å. In the sixth V+2.54+ site, V+2.54+ is bonded to five S2- atoms to form VS5 trigonal bipyramids that share a cornercorner with one VS6 octahedra, corners with three VS5 trigonal bipyramids, edges with three VS6 octahedra, and an edgeedge with one VS6 pentagonal pyramid. The corner-sharing octahedral tilt angles are 72°. There are a spread of V–S bond distances ranging from 2.31–2.47 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 three VS6 octahedra, a cornercorner with one VS5 trigonal bipyramid, an edgeedge with one VS6 octahedra, an edgeedge with one VS6 pentagonal pyramid, and edges with two VS5 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 4–43°. There are a spread of V–S bond distances ranging from 2.35–2.76 Å. In the eighth V+2.54+ site, V+2.54+ is bonded to six S2- atoms to form distorted VS6 octahedra that share a cornercorner with one VS6 pentagonal pyramid, corners with two VS5 trigonal bipyramids, edges with three VS6 octahedra, an edgeedge with one VS6 pentagonal pyramid, and edges with two VS5 trigonal bipyramids. There are a spread of V–S bond distances ranging from 2.36–2.94 Å. In the ninth V+2.54+ site, V+2.54+ is bonded in a 7-coordinate geometry to seven S2- atoms. There are a spread of V–S bond distances ranging from 2.34–3.08 Å. In the tenth 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 2.35–2.57 Å. In the eleventh V+2.54+ site, V+2.54+ is bonded to five S2- atoms to form distorted VS5 trigonal bipyramids that share a cornercorner with one VS6 octahedra, a cornercorner with one VS5 trigonal bipyramid, edges with two VS6 octahedra, and a faceface with one VS6 pentagonal pyramid. The corner-sharing octahedral tilt angles are 27°. There are a spread of V–S bond distances ranging from 2.35–2.42 Å. In the twelfth V+2.54+ site, V+2.54+ is bonded to five S2- atoms to form distorted VS5 trigonal bipyramids that share a cornercorner with one VS6 octahedra, a cornercorner with one VS5 trigonal bipyramid, an edgeedge with one VS6 octahedra, and an edgeedge with one VS5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 53°. There are a spread of V–S bond distances ranging from 2.32–2.48 Å. In the thirteenth 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, edges with two VS6 octahedra, an edgeedge with one VS6 pentagonal pyramid, and an edgeedge with one VS5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 38–61°. There are a spread of V–S bond distances ranging from 2.32–2.49 Å. In the fourteenth V+2.54+ site, V+2.54+ is bonded to six S2- atoms to form distorted VS6 pentagonal pyramids that share corners with three VS6 octahedra, an edgeedge with one VS6 octahedra, edges with two VS5 trigonal bipyramids, and a faceface with one VS5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 2–38°. There are a spread of V–S bond distances ranging from 2.37–2.94 Å. In the fifteenth V+2.54+ site, V+2.54+ is bonded in a 4-coordinate geometry to six S2- atoms. There are a spread of V–S bond distances ranging from 2.29–3.19 Å. In the sixteenth 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 two VS6 pentagonal pyramids, an edgeedge with one VS6 octahedra, and edges with two VS5 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 7–42°. There are a spread of V–S bond distances ranging from 2.37–2.60 Å. In the seventeenth V+2.54+ site, V+2.54+ is bonded in a 7-coordinate geometry to seven S2- atoms. There are a spread of V–S bond distances ranging from 2.38–2.97 Å. In the eighteenth 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 2.34–2.93 Å. In the nineteenth 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 2.37–2.69 Å. In the twentieth 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 2.37–2.56 Å. In the twenty-first V+2.54+ site, V+2.54+ is bonded to six S2- atoms to form VS6 octahedra that share corners with two VS6 pentagonal pyramids, corners with three VS5 trigonal bipyramids, edges with two VS6 octahedra, and an edgeedge with one VS5 trigonal bipyramid. There are a spread of V–S bond distances ranging from 2.31–2.61 Å. In the twenty-second 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, a cornercorner with one VS6 pentagonal 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 7–50°. There are a spread of V–S bond distances ranging from 2.37–2.86 Å. In the twenty-third V+2.54+ site, V+2.54+ is bonded to six S2- atoms to form distorted VS6 pentagonal pyramids that share corners with four VS6 octahedra, corners with two VS5 trigonal bipyramids, and edges with two VS6 octahedra. The corner-sharing octahedra tilt angles range from 11–61°. There are a spread of V–S bond distances ranging from 2.38–2.60 Å. In the twenty-fourth 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 VS6 pentagonal pyramid, corners with two VS5 trigonal bipyramids, and edges with three VS6 octahedra. The corner-sharing octahedra tilt angles range from 25–80°. There are a spread of V–S bond distances ranging from 2.32–2.46 Å. There are three inequivalent Tl1+ sites. In the first Tl1+ site, Tl1+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Tl–S bond distances ranging from 2.86–3.33 Å. In the second Tl1+ site, Tl1+ is bonded in a 9-coordinate geometry to nine S2- atoms. There are a spread of Tl–S bond distances ranging from 2.92–3.37 Å. In the third Tl1+ site, Tl1+ is bonded in a 9-coordinate geometry to nine S2- atoms. There are a spread of Tl–S bond distances ranging from 2.99–3.51 Å. There are thirty-two inequivalent S2- sites. In the first S2- site, S2- is bonded in a 6-coordinate geometry to five V+2.54+ and one Tl1+ atom. In the second S2- site, S2- is bonded in a 3-coordinate geometry to four V+2.54+ and one Tl1+ atom. In the third S2- site, S2- is bonded in a 5-coordinate geometry to five 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 to four V+2.54+ and one Tl1+ atom to form a mixture of distorted edge and corner-sharing STlV4 trigonal bipyramids. In the seventh S2- site, S2- is bonded in a 5-coordinate geometry to four V+2.54+ and one Tl1+ atom. In the eighth S2- site, S2- is bonded in a 5-coordinate geometry to four V+2.54+ and one Tl1+ atom. In the ninth S2- site, S2- is bonded to five V+2.54+ and one Tl1+ atom to form distorted edge-sharing STlV5 trigonal bipyramids. In the tenth S2- site, S2- is bonded in a 4-coordinate geometry to five V+2.54+ and one Tl1+ atom. In the eleventh S2- site, S2- is bonded in a 4-coordinate geometry to three 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 to five V+2.54+ atoms to form distorted SV5 trigonal bipyramids that share a cornercorner with one STlV4 trigonal bipyramid and an edgeedge with one STlV5 trigonal bipyramid. In the fourteenth S2- site, S2- is bonded in a 6-coordinate geometry to five V+2.54+ and one Tl1+ atom. In the fifteenth S2- site, S2- is bonded in a 6-coordinate geometry to four V+2.54+ and two Tl1+ atoms. In the sixteenth S2- site, S2- is bonded in a 4-coordinate geometry to five V+2.54+ and one Tl1+ atom. In the seventeenth S2- site, S2- is bonded in a 5-coordinate geometry to four V+2.54+ and one Tl1+ atom. In the eighteenth S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to four V+2.54+ and one Tl1+ atom. In the nineteenth S2- site, S2- is bonded in a 5-coordinate geometry to four 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 5-coordinate geometry to five V+2.54+ atoms. In the twenty-second S2- site, S2- is bonded in a 7-coordinate geometry to five V+2.54+ and two Tl1+ atoms. In the twenty-third S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.54+ and one Tl1+ atom. In the twenty-fourth S2- site, S2- is bonded in a 3-coordinate geometry to four V+2.54+ and two Tl1+ atoms. In the twenty-fifth S2- site, S2- is bonded in a 6-coordinate geometry to five V+2.54+ and one Tl1+ atom. In the twenty-sixth S2- site, S2- is bonded in a 5-coordinate geometry to four V+2.54+ and one Tl1+ atom. In the twenty-seventh S2- site, S2- is bonded in a 6-coordinate geometry to five V+2.54+ and one Tl1+ atom. In the twenty-eighth S2- site, S2- is bonded to five V+2.54+ atoms to form distorted edge-sharing SV5 trigonal bipyramids. In the twenty-ninth S2- site, S2- is bonded in a 5-coordinate geometry to five V+2.54+ atoms. In the thirtieth S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.54+ and one Tl1+ atom. In the thirty-first S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to four V+2.54+ and one Tl1+ atom. In the thirty-second S2- site, S2- is bonded in a 5-coordinate geometry to four V+2.54+ and one Tl1+ atom.