Materials Data on Tl4S3 by Materials Project

Tl4S3 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. there are four inequivalent Tl+1.50+ sites. In the first Tl+1.50+ site, Tl+1.50+ is bonded to four S2- atoms to form TlS4 tetrahedra that share corners with two equivalent TlS4 tetrahedra, corners with five equivalent TlS5 trigonal bipyramids, and an edgeedge with one TlS5 trigonal bipyramid. There are a spread of Tl–S bond distances ranging from 2.53–2.62 Å. In the second Tl+1.50+ site, Tl+1.50+ is bonded to five S2- atoms to form TlS5 trigonal bipyramids that share corners with five equivalent TlS4 tetrahedra, an edgeedge with one TlS4 tetrahedra, and edges with two equivalent TlS5 trigonal bipyramids. There are a spread of Tl–S bond distances ranging from 3.01–3.31 Å. In the third Tl+1.50+ site, Tl+1.50+ is bonded in a rectangular see-saw-like geometry to four S2- atoms. There are a spread of Tl–S bond distances ranging from 2.92–3.40 Å. In the fourth Tl+1.50+ site, Tl+1.50+ is bonded in a rectangular see-saw-like geometry to four S2- atoms. There are a spread of Tl–S bond distances ranging from 2.99–3.36 Å. There are three inequivalent S2- sites. In the first S2- site, S2- is bonded in a 5-coordinate geometry to five Tl+1.50+ atoms. In the second S2- site, S2- is bonded to six Tl+1.50+ atoms to form a mixture of distorted edge and corner-sharing STl6 octahedra. The corner-sharing octahedral tilt angles are 9°. In the third S2- site, S2- is bonded to six Tl+1.50+ atoms to form distorted edge-sharing STl6 octahedra.