TlV6S8 crystallizes in the trigonal P-3 space group. V(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form a mixture of distorted edge, face, and corner-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 45-54°. Tl(1) is bonded in a 6-coordinate geometry to six equivalent S(2) atoms. There are two inequivalent S sites. In the first S site, S(2) is bonded in a 5-coordinate geometry to four equivalent V(1) and one Tl(1) atom. In the second S site, S(1) is bonded to six equivalent V(1) atoms to form distorted face-sharing SV6 pentagonal pyramids.
TlV6S8 crystallizes in the trigonal P-3 space group. V(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form a mixture of distorted edge, face, and corner-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 45-54°. Both V(1)-S(1) bond lengths are 2.48 Å. There are a spread of V(1)-S(2) bond distances ranging from 2.31-2.61 Å. Tl(1) is bonded in a 6-coordinate geometry to six equivalent S(2) atoms. All Tl(1)-S(2) bond lengths are 3.11 Å. There are two inequivalent S sites. In the first S site, S(2) is bonded in a 5-coordinate geometry to four equivalent V(1) and one Tl(1) atom. In the second S site, S(1) is bonded to six equivalent V(1) atoms to form distorted face-sharing SV6 pentagonal pyramids.