TlV5S8 crystallizes in the monoclinic C2 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one S(1), two equivalent S(2), and three equivalent S(3) atoms to form a mixture of face, corner, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. In the second V site, V(2) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form a mixture of corner and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles are 48°. In the third V site, V(3) is bonded to one S(1), two equivalent S(3), and three equivalent S(4) atoms to form a mixture of face, corner, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. Tl(1) is bonded in a 4-coordinate geometry to four equivalent S(2) atoms. There are four inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one V(1), one V(3), and two equivalent V(2) atoms. In the second S site, S(2) is bonded in a 3-coordinate geometry to one V(2), two equivalent V(1), and two equivalent Tl(1) atoms. In the third S site, S(3) is bonded to two equivalent V(3) and three equivalent V(1) atoms to form distorted edge-sharing SV5 trigonal bipyramids. In the fourth S site, S(4) is bonded in a distorted T-shaped geometry to three equivalent V(3) atoms.
TlV5S8 crystallizes in the monoclinic C2 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one S(1), two equivalent S(2), and three equivalent S(3) atoms to form a mixture of face, corner, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. The V(1)-S(1) bond length is 2.38 Å. Both V(1)-S(2) bond lengths are 2.36 Å. There is one shorter (2.50 Å) and two longer (2.54 Å) V(1)-S(3) bond lengths. In the second V site, V(2) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form a mixture of corner and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles are 48°. Both V(2)-S(2) bond lengths are 2.44 Å. All V(2)-S(1) bond lengths are 2.41 Å. In the third V site, V(3) is bonded to one S(1), two equivalent S(3), and three equivalent S(4) atoms to form a mixture of face, corner, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. The V(3)-S(1) bond length is 2.52 Å. Both V(3)-S(3) bond lengths are 2.52 Å. There is one shorter (2.30 Å) and two longer (2.39 Å) V(3)-S(4) bond lengths. Tl(1) is bonded in a 4-coordinate geometry to four equivalent S(2) atoms. There are two shorter (3.22 Å) and two longer (3.24 Å) Tl(1)-S(2) bond lengths. There are four inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one V(1), one V(3), and two equivalent V(2) atoms. In the second S site, S(2) is bonded in a 3-coordinate geometry to one V(2), two equivalent V(1), and two equivalent Tl(1) atoms. In the third S site, S(3) is bonded to two equivalent V(3) and three equivalent V(1) atoms to form distorted edge-sharing SV5 trigonal bipyramids. In the fourth S site, S(4) is bonded in a distorted T-shaped geometry to three equivalent V(3) atoms.