DOE OSTI2020
Ti2Tl3P5S18 crystallizes in the monoclinic Cc space group. The structure is three-dimensional. there are two inequivalent Ti4+ sites. In the first Ti4+ site, Ti4+ is bonded to six S2- atoms to form TiS6 octahedra that share edges with three PS4 tetrahedra. There are a spread of Ti–S bond distances ranging from 2.43–2.48 Å. In the second Ti4+ site, Ti4+ is bonded to six S2- atoms to form TiS6 octahedra that share edges with three PS4 tetrahedra. There are a spread of Ti–S bond distances ranging from 2.43–2.47 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 3.20–3.74 Å. In the second 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 3.24–3.74 Å. In the third 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 3.22–3.86 Å. There are five inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four S2- atoms to form PS4 tetrahedra that share edges with two TiS6 octahedra. All P–S bond lengths are 2.05 Å. In the second P5+ site, P5+ is bonded to four S2- atoms to form PS4 tetrahedra that share a cornercorner with one PS4 tetrahedra and an edgeedge with one TiS6 octahedra. There are a spread of P–S bond distances ranging from 1.97–2.15 Å. In the third P5+ site, P5+ is bonded to four S2- atoms to form PS4 tetrahedra that share a cornercorner with one PS4 tetrahedra and an edgeedge with one TiS6 octahedra. There are a spread of P–S bond distances ranging from 1.96–2.16 Å. In the fourth P5+ site, P5+ is bonded to four S2- atoms to form PS4 tetrahedra that share a cornercorner with one PS4 tetrahedra and an edgeedge with one TiS6 octahedra. There are a spread of P–S bond distances ranging from 1.98–2.14 Å. In the fifth P5+ site, P5+ is bonded to four S2- atoms to form PS4 tetrahedra that share a cornercorner with one PS4 tetrahedra and an edgeedge with one TiS6 octahedra. There are a spread of P–S bond distances ranging from 1.98–2.14 Å. There are eighteen inequivalent S2- sites. In the first S2- site, S2- is bonded in a distorted L-shaped geometry to one Ti4+, one Tl1+, and one P5+ atom. In the second S2- site, S2- is bonded in a distorted L-shaped geometry to one Ti4+, one Tl1+, and one P5+ atom. In the third S2- site, S2- is bonded in a distorted single-bond geometry to three Tl1+ and one P5+ atom. In the fourth S2- site, S2- is bonded in a distorted single-bond geometry to three Tl1+ and one P5+ atom. In the fifth S2- site, S2- is bonded in a distorted single-bond geometry to two Tl1+ and one P5+ atom. In the sixth S2- site, S2- is bonded in a distorted single-bond geometry to three Tl1+ and one P5+ atom. In the seventh S2- site, S2- is bonded in an L-shaped geometry to one Ti4+, one Tl1+, and one P5+ atom. In the eighth S2- site, S2- is bonded in an L-shaped geometry to one Ti4+, one Tl1+, and one P5+ atom. In the ninth S2- site, S2- is bonded in an L-shaped geometry to one Ti4+ and one P5+ atom. In the tenth S2- site, S2- is bonded in an L-shaped geometry to one Ti4+, one Tl1+, and one P5+ atom. In the eleventh S2- site, S2- is bonded in a distorted L-shaped geometry to one Ti4+, one Tl1+, and one P5+ atom. In the twelfth S2- site, S2- is bonded in a distorted L-shaped geometry to one Ti4+, one Tl1+, and one P5+ atom. In the thirteenth S2- site, S2- is bonded in a distorted L-shaped geometry to one Ti4+, one Tl1+, and one P5+ atom. In the fourteenth S2- site, S2- is bonded in a distorted L-shaped geometry to one Ti4+, one Tl1+, and one P5+ atom. In the fifteenth S2- site, S2- is bonded in a water-like geometry to one Tl1+ and two P5+ atoms. In the sixteenth S2- site, S2- is bonded in a water-like geometry to one Tl1+ and two P5+ atoms. In the seventeenth S2- site, S2- is bonded in a distorted L-shaped geometry to one Ti4+, one Tl1+, and one P5+ atom. In the eighteenth S2- site, S2- is bonded in a distorted L-shaped geometry to one Ti4+, one Tl1+, and one P5+ atom.