TlV4FeS8 is Orthorhombic Perovskite-derived structured and crystallizes in the monoclinic C2/m space group. The structure consists of two 7440-28-0 atoms inside a V4FeS8 framework. In the V4FeS8 framework, there are two inequivalent V sites. In the first V site, V(1) is bonded to one S(4), two equivalent S(2), and three equivalent S(1) atoms to form distorted VS6 octahedra that share corners with two equivalent Fe(1)S6 octahedra, corners with four equivalent V(2)S6 octahedra, edges with four equivalent V(1)S6 octahedra, and  a faceface with one V(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 49-55°. In the second V site, V(2) is bonded to one S(4), two equivalent S(3), and three equivalent S(2) atoms to form distorted VS6 octahedra that share corners with four equivalent V(1)S6 octahedra, edges with two equivalent Fe(1)S6 octahedra, edges with four equivalent V(2)S6 octahedra, and  a faceface with one V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 49-55°. Fe(1) is bonded to two equivalent S(3) and four equivalent S(4) atoms to form FeS6 octahedra that share corners with four equivalent V(1)S6 octahedra, edges with two equivalent Fe(1)S6 octahedra, and edges with four equivalent V(2)S6 octahedra. The corner-sharing octahedral tilt angles are 50°. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to three equivalent V(1) atoms. In the second S site, S(2) is bonded in a 5-coordinate geometry to two equivalent V(1) and three equivalent V(2) atoms. In the third S site, S(3) is bonded in a 3-coordinate geometry to two equivalent V(2) and one Fe(1) atom. In the fourth S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to one V(1), one V(2), and two equivalent Fe(1) atoms.
TlV4FeS8 is Orthorhombic Perovskite-derived structured and crystallizes in the monoclinic C2/m space group. The structure consists of two 7440-28-0 atoms inside a V4FeS8 framework. In the V4FeS8 framework, there are two inequivalent V sites. In the first V site, V(1) is bonded to one S(4), two equivalent S(2), and three equivalent S(1) atoms to form distorted VS6 octahedra that share corners with two equivalent Fe(1)S6 octahedra, corners with four equivalent V(2)S6 octahedra, edges with four equivalent V(1)S6 octahedra, and  a faceface with one V(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 49-55°. The V(1)-S(4) bond length is 2.59 Å. Both V(1)-S(2) bond lengths are 2.50 Å. There is one shorter (2.28 Å) and two longer (2.33 Å) V(1)-S(1) bond lengths. In the second V site, V(2) is bonded to one S(4), two equivalent S(3), and three equivalent S(2) atoms to form distorted VS6 octahedra that share corners with four equivalent V(1)S6 octahedra, edges with two equivalent Fe(1)S6 octahedra, edges with four equivalent V(2)S6 octahedra, and  a faceface with one V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 49-55°. The V(2)-S(4) bond length is 2.22 Å. Both V(2)-S(3) bond lengths are 2.31 Å. There are two shorter (2.47 Å) and one longer (2.71 Å) V(2)-S(2) bond length. Fe(1) is bonded to two equivalent S(3) and four equivalent S(4) atoms to form FeS6 octahedra that share corners with four equivalent V(1)S6 octahedra, edges with two equivalent Fe(1)S6 octahedra, and edges with four equivalent V(2)S6 octahedra. The corner-sharing octahedral tilt angles are 50°. Both Fe(1)-S(3) bond lengths are 2.31 Å. All Fe(1)-S(4) bond lengths are 2.30 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to three equivalent V(1) atoms. In the second S site, S(2) is bonded in a 5-coordinate geometry to two equivalent V(1) and three equivalent V(2) atoms. In the third S site, S(3) is bonded in a 3-coordinate geometry to two equivalent V(2) and one Fe(1) atom. In the fourth S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to one V(1), one V(2), and two equivalent Fe(1) atoms.