DOE OSTI2020
Ti4P8S29 crystallizes in the monoclinic Cc space group. The structure is two-dimensional and consists of two Ti4P8S29 sheets oriented in the (0, 1, 0) direction. there are four inequivalent Ti+3.50+ sites. In the first Ti+3.50+ site, Ti+3.50+ is bonded to six S+1.86- atoms to form distorted TiS6 octahedra that share edges with three PS4 tetrahedra. There are a spread of Ti–S bond distances ranging from 2.40–2.55 Å. In the second Ti+3.50+ site, Ti+3.50+ is bonded to six S+1.86- atoms to form TiS6 octahedra that share edges with three PS4 tetrahedra. There are a spread of Ti–S bond distances ranging from 2.41–2.53 Å. In the third Ti+3.50+ site, Ti+3.50+ is bonded to six S+1.86- atoms to form TiS6 octahedra that share edges with three PS4 tetrahedra. There are a spread of Ti–S bond distances ranging from 2.42–2.53 Å. In the fourth Ti+3.50+ site, Ti+3.50+ is bonded to six S+1.86- atoms to form distorted TiS6 octahedra that share edges with three PS4 tetrahedra. There are a spread of Ti–S bond distances ranging from 2.40–2.53 Å. There are eight inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four S+1.86- atoms to form PS4 tetrahedra that share an edgeedge with one TiS6 octahedra and an edgeedge with one PS4 tetrahedra. There are a spread of P–S bond distances ranging from 2.01–2.15 Å. In the second P5+ site, P5+ is bonded to four S+1.86- atoms to form PS4 tetrahedra that share edges with two TiS6 octahedra. There are three shorter (2.05 Å) and one longer (2.06 Å) P–S bond lengths. In the third P5+ site, P5+ is bonded to four S+1.86- atoms to form PS4 tetrahedra that share an edgeedge with one TiS6 octahedra and an edgeedge with one PS4 tetrahedra. There are a spread of P–S bond distances ranging from 2.01–2.37 Å. In the fourth P5+ site, P5+ is bonded to four S+1.86- atoms to form PS4 tetrahedra that share edges with two TiS6 octahedra. All P–S bond lengths are 2.05 Å. In the fifth P5+ site, P5+ is bonded to four S+1.86- atoms to form PS4 tetrahedra that share edges with two TiS6 octahedra. There are one shorter (2.05 Å) and three longer (2.06 Å) P–S bond lengths. In the sixth P5+ site, P5+ is bonded to four S+1.86- atoms to form PS4 tetrahedra that share an edgeedge with one TiS6 octahedra and an edgeedge with one PS4 tetrahedra. There are a spread of P–S bond distances ranging from 2.00–2.25 Å. In the seventh P5+ site, P5+ is bonded to four S+1.86- atoms to form PS4 tetrahedra that share edges with two TiS6 octahedra. There are three shorter (2.05 Å) and one longer (2.06 Å) P–S bond lengths. In the eighth P5+ site, P5+ is bonded to four S+1.86- atoms to form PS4 tetrahedra that share an edgeedge with one TiS6 octahedra and an edgeedge with one PS4 tetrahedra. There are a spread of P–S bond distances ranging from 2.01–2.14 Å. There are twenty-nine inequivalent S+1.86- sites. In the first S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom. In the second S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom. In the third S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom. In the fourth S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom. In the fifth S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom. In the sixth S+1.86- site, S+1.86- is bonded in an L-shaped geometry to two P5+ atoms. In the seventh S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom. In the eighth S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom. In the ninth S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom. In the tenth S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom. In the eleventh S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom. In the twelfth S+1.86- site, S+1.86- is bonded in an L-shaped geometry to two P5+ atoms. In the thirteenth S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom. In the fourteenth S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom. In the fifteenth S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom. In the sixteenth S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom. In the seventeenth S+1.86- site, S+1.86- is bonded in a 3-coordinate geometry to two P5+ and one S+1.86- atom. The S–S bond length is 1.92 Å. In the eighteenth S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom. In the nineteenth S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom. In the twentieth S+1.86- site, S+1.86- is bonded in a distorted single-bond geometry to one S+1.86- atom. In the twenty-first S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom. In the twenty-second S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom. In the twenty-third S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom. In the twenty-fourth S+1.86- site, S+1.86- is bonded in an L-shaped geometry to two P5+ atoms. In the twenty-fifth S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom. In the twenty-sixth S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom. In the twenty-seventh S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom. In the twenty-eighth S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom. In the twenty-ninth S+1.86- site, S+1.86- is bonded in an L-shaped geometry to one Ti+3.50+ and one P5+ atom.