DOE OSTI2020
Tl(V3S4)4 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are twelve inequivalent V+2.58+ sites. In the first V+2.58+ site, V+2.58+ is bonded to six S2- atoms to form a mixture of face, edge, and corner-sharing VS6 octahedra. The corner-sharing octahedra tilt angles range from 44–53°. There are a spread of V–S bond distances ranging from 2.32–2.54 Å. In the second V+2.58+ site, V+2.58+ is bonded to six S2- atoms to form a mixture of face, edge, and corner-sharing VS6 octahedra. The corner-sharing octahedra tilt angles range from 43–53°. There are a spread of V–S bond distances ranging from 2.33–2.55 Å. In the third V+2.58+ site, V+2.58+ is bonded to six S2- atoms to form a mixture of face, edge, and corner-sharing VS6 octahedra. The corner-sharing octahedra tilt angles range from 43–53°. There are a spread of V–S bond distances ranging from 2.32–2.53 Å. In the fourth V+2.58+ site, V+2.58+ is bonded to six S2- atoms to form a mixture of face, edge, and corner-sharing VS6 octahedra. The corner-sharing octahedra tilt angles range from 44–53°. There are a spread of V–S bond distances ranging from 2.33–2.55 Å. In the fifth V+2.58+ site, V+2.58+ is bonded to six S2- atoms to form a mixture of face, edge, and corner-sharing VS6 octahedra. The corner-sharing octahedra tilt angles range from 43–53°. There are a spread of V–S bond distances ranging from 2.33–2.55 Å. In the sixth V+2.58+ site, V+2.58+ is bonded to six S2- atoms to form a mixture of face, edge, and corner-sharing VS6 octahedra. The corner-sharing octahedra tilt angles range from 44–53°. There are a spread of V–S bond distances ranging from 2.33–2.53 Å. In the seventh V+2.58+ site, V+2.58+ is bonded to six S2- atoms to form a mixture of face, edge, and corner-sharing VS6 octahedra. The corner-sharing octahedra tilt angles range from 43–53°. There are a spread of V–S bond distances ranging from 2.33–2.55 Å. In the eighth V+2.58+ site, V+2.58+ is bonded to six S2- atoms to form a mixture of face, edge, and corner-sharing VS6 octahedra. The corner-sharing octahedra tilt angles range from 44–53°. There are a spread of V–S bond distances ranging from 2.33–2.54 Å. In the ninth V+2.58+ site, V+2.58+ is bonded to six S2- atoms to form a mixture of face, edge, and corner-sharing VS6 octahedra. The corner-sharing octahedra tilt angles range from 44–53°. There are a spread of V–S bond distances ranging from 2.33–2.55 Å. In the tenth V+2.58+ site, V+2.58+ is bonded to six S2- atoms to form a mixture of face, edge, and corner-sharing VS6 octahedra. The corner-sharing octahedra tilt angles range from 44–53°. There are a spread of V–S bond distances ranging from 2.33–2.54 Å. In the eleventh V+2.58+ site, V+2.58+ is bonded to six S2- atoms to form a mixture of face, edge, and corner-sharing VS6 octahedra. The corner-sharing octahedra tilt angles range from 44–53°. There are a spread of V–S bond distances ranging from 2.33–2.54 Å. In the twelfth V+2.58+ site, V+2.58+ is bonded to six S2- atoms to form a mixture of face, edge, and corner-sharing VS6 octahedra. The corner-sharing octahedra tilt angles range from 43–53°. There are a spread of V–S bond distances ranging from 2.33–2.55 Å. Tl1+ is bonded in a 6-coordinate geometry to six S2- atoms. There are three shorter (3.03 Å) and three longer (3.19 Å) Tl–S bond lengths. There are sixteen inequivalent S2- sites. In the first S2- site, S2- is bonded to six V+2.58+ atoms to form distorted face-sharing SV6 pentagonal pyramids. In the second S2- site, S2- is bonded to six V+2.58+ atoms to form distorted face-sharing SV6 pentagonal pyramids. In the third S2- site, S2- is bonded to six V+2.58+ atoms to form distorted face-sharing SV6 pentagonal pyramids. In the fourth S2- site, S2- is bonded to six V+2.58+ atoms to form distorted face-sharing SV6 pentagonal pyramids. In the fifth S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.58+ atoms. In the sixth S2- site, S2- is bonded in a 5-coordinate geometry to four V+2.58+ and one Tl1+ atom. In the seventh S2- site, S2- is bonded in a 5-coordinate geometry to four V+2.58+ and one Tl1+ atom. In the eighth S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.58+ atoms. In the ninth S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.58+ atoms. In the tenth S2- site, S2- is bonded in a 5-coordinate geometry to four V+2.58+ and one Tl1+ atom. In the eleventh S2- site, S2- is bonded in a 5-coordinate geometry to four V+2.58+ and one Tl1+ atom. In the twelfth S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.58+ atoms. In the thirteenth S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.58+ atoms. In the fourteenth S2- site, S2- is bonded in a 5-coordinate geometry to four V+2.58+ and one Tl1+ atom. In the fifteenth S2- site, S2- is bonded in a 5-coordinate geometry to four V+2.58+ and one Tl1+ atom. In the sixteenth S2- site, S2- is bonded in a 4-coordinate geometry to four V+2.58+ atoms.