Tl(V3S4)4 crystallizes in the triclinic P-1 space group. There are six inequivalent V sites. In the first V site, V(1) is bonded to one S(3), two equivalent S(2), and three equivalent S(7) atoms to form a mixture of edge, face, and corner-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 42-54°. In the second V site, V(2) is bonded to one S(4), two equivalent S(1), and three equivalent S(8) atoms to form a mixture of edge, face, and corner-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 41-55°. In the third V site, V(3) is bonded to one S(3), one S(5), two equivalent S(2), and two equivalent S(4) atoms to form a mixture of edge, face, and corner-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 42-51°. In the fourth V site, V(4) is bonded to one S(4), one S(6), two equivalent S(1), and two equivalent S(3) atoms to form a mixture of edge, face, and corner-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 41-51°. In the fifth V site, V(5) is bonded to one S(5), one S(7), two equivalent S(2), and two equivalent S(6) atoms to form a mixture of edge, face, and corner-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 42-54°. In the sixth V site, V(6) is bonded to one S(6), one S(8), two equivalent S(1), and two equivalent S(5) atoms to form a mixture of edge, face, and corner-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. Tl(1) is bonded in a 8-coordinate geometry to two equivalent Tl(1), two equivalent S(4), two equivalent S(5), and two equivalent S(8) atoms. There are eight inequivalent S sites. In the first S site, S(1) is bonded to two equivalent V(2), two equivalent V(4), and two equivalent V(6) atoms to form distorted face-sharing SV6 pentagonal pyramids. In the second S site, S(2) is bonded to two equivalent V(1), two equivalent V(3), and two equivalent V(5) atoms to form distorted SV6 pentagonal pyramids that share corners with two equivalent S(7)V4 trigonal pyramids, edges with three equivalent S(7)V4 trigonal pyramids, and faces with two equivalent S(2)V6 pentagonal pyramids. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to one V(1), one V(3), and two equivalent V(4) atoms. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to one V(2), one V(4), two equivalent V(3), and one Tl(1) atom. In the fifth S site, S(5) is bonded in a 5-coordinate geometry to one V(3), one V(5), two equivalent V(6), and one Tl(1) atom. In the sixth S site, S(6) is bonded in a rectangular see-saw-like geometry to one V(4), one V(6), and two equivalent V(5) atoms. In the seventh S site, S(7) is bonded to one V(5) and three equivalent V(1) atoms to form distorted SV4 trigonal pyramids that share corners with two equivalent S(2)V6 pentagonal pyramids, corners with two equivalent S(7)V4 trigonal pyramids, edges with three equivalent S(2)V6 pentagonal pyramids, and edges with two equivalent S(7)V4 trigonal pyramids. In the eighth S site, S(8) is bonded in a 4-coordinate geometry to one V(6), three equivalent V(2), and one Tl(1) atom.
Tl(V3S4)4 crystallizes in the triclinic P-1 space group. There are six inequivalent V sites. In the first V site, V(1) is bonded to one S(3), two equivalent S(2), and three equivalent S(7) atoms to form a mixture of edge, face, and corner-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 42-54°. The V(1)-S(3) bond length is 2.53 Å. Both V(1)-S(2) bond lengths are 2.46 Å. All V(1)-S(7) bond lengths are 2.33 Å. In the second V site, V(2) is bonded to one S(4), two equivalent S(1), and three equivalent S(8) atoms to form a mixture of edge, face, and corner-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 41-55°. The V(2)-S(4) bond length is 2.55 Å. Both V(2)-S(1) bond lengths are 2.45 Å. There are a spread of V(2)-S(8) bond distances ranging from 2.32-2.35 Å. In the third V site, V(3) is bonded to one S(3), one S(5), two equivalent S(2), and two equivalent S(4) atoms to form a mixture of edge, face, and corner-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 42-51°. The V(3)-S(3) bond length is 2.39 Å. The V(3)-S(5) bond length is 2.54 Å. There is one shorter (2.44 Å) and one longer (2.45 Å) V(3)-S(2) bond length. There is one shorter (2.38 Å) and one longer (2.39 Å) V(3)-S(4) bond length. In the fourth V site, V(4) is bonded to one S(4), one S(6), two equivalent S(1), and two equivalent S(3) atoms to form a mixture of edge, face, and corner-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 41-51°. The V(4)-S(4) bond length is 2.42 Å. The V(4)-S(6) bond length is 2.50 Å. Both V(4)-S(1) bond lengths are 2.46 Å. Both V(4)-S(3) bond lengths are 2.37 Å. In the fifth V site, V(5) is bonded to one S(5), one S(7), two equivalent S(2), and two equivalent S(6) atoms to form a mixture of edge, face, and corner-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 42-54°. The V(5)-S(5) bond length is 2.44 Å. The V(5)-S(7) bond length is 2.47 Å. Both V(5)-S(2) bond lengths are 2.47 Å. Both V(5)-S(6) bond lengths are 2.37 Å. In the sixth V site, V(6) is bonded to one S(6), one S(8), two equivalent S(1), and two equivalent S(5) atoms to form a mixture of edge, face, and corner-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. The V(6)-S(6) bond length is 2.42 Å. The V(6)-S(8) bond length is 2.52 Å. There is one shorter (2.44 Å) and one longer (2.45 Å) V(6)-S(1) bond length. Both V(6)-S(5) bond lengths are 2.39 Å. Tl(1) is bonded in a 8-coordinate geometry to two equivalent Tl(1), two equivalent S(4), two equivalent S(5), and two equivalent S(8) atoms. Both Tl(1)-Tl(1) bond lengths are 3.38 Å. Both Tl(1)-S(4) bond lengths are 3.22 Å. Both Tl(1)-S(5) bond lengths are 3.13 Å. Both Tl(1)-S(8) bond lengths are 3.19 Å. There are eight inequivalent S sites. In the first S site, S(1) is bonded to two equivalent V(2), two equivalent V(4), and two equivalent V(6) atoms to form distorted face-sharing SV6 pentagonal pyramids. In the second S site, S(2) is bonded to two equivalent V(1), two equivalent V(3), and two equivalent V(5) atoms to form distorted SV6 pentagonal pyramids that share corners with two equivalent S(7)V4 trigonal pyramids, edges with three equivalent S(7)V4 trigonal pyramids, and faces with two equivalent S(2)V6 pentagonal pyramids. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to one V(1), one V(3), and two equivalent V(4) atoms. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to one V(2), one V(4), two equivalent V(3), and one Tl(1) atom. In the fifth S site, S(5) is bonded in a 5-coordinate geometry to one V(3), one V(5), two equivalent V(6), and one Tl(1) atom. In the sixth S site, S(6) is bonded in a rectangular see-saw-like geometry to one V(4), one V(6), and two equivalent V(5) atoms. In the seventh S site, S(7) is bonded to one V(5) and three equivalent V(1) atoms to form distorted SV4 trigonal pyramids that share corners with two equivalent S(2)V6 pentagonal pyramids, corners with two equivalent S(7)V4 trigonal pyramids, edges with three equivalent S(2)V6 pentagonal pyramids, and edges with two equivalent S(7)V4 trigonal pyramids. In the eighth S site, S(8) is bonded in a 4-coordinate geometry to one V(6), three equivalent V(2), and one Tl(1) atom.