Materials Data on Hf(TlS)4 by Materials Project

Hf(TlS)4 is Orthorhombic Perovskite-like structured and crystallizes in the triclinic P-1 space group. The structure is three-dimensional. there are three inequivalent Hf4+ sites. In the first Hf4+ site, Hf4+ is bonded to six S2- atoms to form HfS6 octahedra that share corners with two TlS5 square pyramids, edges with two HfS6 octahedra, and edges with five TlS5 square pyramids. There are a spread of Hf–S bond distances ranging from 2.52–2.63 Å. In the second Hf4+ site, Hf4+ is bonded to six S2- atoms to form HfS6 octahedra that share corners with three TlS5 square pyramids, edges with two HfS6 octahedra, and edges with three TlS5 square pyramids. There are a spread of Hf–S bond distances ranging from 2.51–2.66 Å. In the third Hf4+ site, Hf4+ is bonded to six S2- atoms to form HfS6 octahedra that share corners with two equivalent TlS5 square pyramids, edges with two equivalent HfS6 octahedra, and edges with two equivalent TlS5 square pyramids. There are two shorter (2.57 Å) and four longer (2.59 Å) Hf–S bond lengths. There are ten inequivalent Tl1+ sites. In the first Tl1+ site, Tl1+ is bonded to five S2- atoms to form distorted TlS5 square pyramids that share corners with two equivalent HfS6 octahedra, edges with three HfS6 octahedra, and an edgeedge with one TlS5 square pyramid. The corner-sharing octahedra tilt angles range from 15–19°. There are a spread of Tl–S bond distances ranging from 2.88–3.41 Å. In the second Tl1+ site, Tl1+ is bonded to five S2- atoms to form distorted TlS5 square pyramids that share corners with two HfS6 octahedra, corners with two equivalent TlS5 square pyramids, edges with three HfS6 octahedra, and edges with two TlS5 square pyramids. The corner-sharing octahedra tilt angles range from 7–8°. There are a spread of Tl–S bond distances ranging from 2.96–3.45 Å. In the third Tl1+ site, Tl1+ is bonded in a distorted rectangular see-saw-like geometry to four S2- atoms. There are a spread of Tl–S bond distances ranging from 2.89–3.25 Å. In the fourth Tl1+ site, Tl1+ is bonded in a 5-coordinate geometry to five S2- atoms. There are a spread of Tl–S bond distances ranging from 2.92–3.50 Å. In the fifth Tl1+ site, Tl1+ is bonded in a 4-coordinate geometry to four S2- atoms. There are a spread of Tl–S bond distances ranging from 2.92–3.46 Å. In the sixth Tl1+ site, Tl1+ is bonded in a distorted rectangular see-saw-like geometry to four S2- atoms. There are a spread of Tl–S bond distances ranging from 2.92–3.49 Å. In the seventh Tl1+ site, Tl1+ is bonded to five S2- atoms to form distorted TlS5 square pyramids that share corners with two HfS6 octahedra, corners with two equivalent TlS5 square pyramids, edges with three HfS6 octahedra, and edges with two TlS5 square pyramids. The corner-sharing octahedra tilt angles range from 12–16°. There are a spread of Tl–S bond distances ranging from 2.88–3.37 Å. In the eighth Tl1+ site, Tl1+ is bonded in a distorted rectangular see-saw-like geometry to four S2- atoms. There are a spread of Tl–S bond distances ranging from 2.89–3.28 Å. In the ninth Tl1+ site, Tl1+ is bonded in a distorted rectangular see-saw-like geometry to four S2- atoms. There are a spread of Tl–S bond distances ranging from 2.89–3.45 Å. In the tenth Tl1+ site, Tl1+ is bonded in a 5-coordinate geometry to five S2- atoms. There are a spread of Tl–S bond distances ranging from 2.93–3.43 Å. There are ten inequivalent S2- sites. In the first S2- site, S2- is bonded in a 6-coordinate geometry to one Hf4+ and five Tl1+ atoms. In the second S2- site, S2- is bonded in a 6-coordinate geometry to two equivalent Hf4+ and four Tl1+ atoms. In the third S2- site, S2- is bonded in a 6-coordinate geometry to two Hf4+ and four Tl1+ atoms. In the fourth S2- site, S2- is bonded to two Hf4+ and four Tl1+ atoms to form distorted corner-sharing SHf2Tl4 octahedra. The corner-sharing octahedral tilt angles are 0°. In the fifth S2- site, S2- is bonded in a 6-coordinate geometry to one Hf4+ and five Tl1+ atoms. In the sixth S2- site, S2- is bonded in a 6-coordinate geometry to two Hf4+ and four Tl1+ atoms. In the seventh S2- site, S2- is bonded in a 6-coordinate geometry to one Hf4+ and five Tl1+ atoms. In the eighth S2- site, S2- is bonded in a 6-coordinate geometry to one Hf4+ and five Tl1+ atoms. In the ninth S2- site, S2- is bonded in a 6-coordinate geometry to one Hf4+ and five Tl1+ atoms. In the tenth S2- site, S2- is bonded in a 6-coordinate geometry to two Hf4+ and four Tl1+ atoms.