TlIn5S8 crystallizes in the monoclinic Cm space group. Tl(1) is bonded in a 2-coordinate geometry to two equivalent S(6) atoms. There are five inequivalent In sites. In the first In site, In(1) is bonded to one S(3), one S(6), two equivalent S(1), and two equivalent S(5) atoms to form InS6 octahedra that share corners with two equivalent In(5)S6 octahedra,  a cornercorner with one In(4)S4 tetrahedra, corners with two equivalent In(3)S4 tetrahedra, edges with two equivalent In(1)S6 octahedra, and edges with two equivalent In(2)S6 octahedra. The corner-sharing octahedral tilt angles are 48°. In the second In site, In(2) is bonded to one S(4), one S(5), two equivalent S(2), and two equivalent S(6) atoms to form InS6 octahedra that share corners with two equivalent In(5)S6 octahedra,  a cornercorner with one In(3)S4 tetrahedra, corners with two equivalent In(4)S4 tetrahedra, edges with two equivalent In(1)S6 octahedra, and edges with two equivalent In(2)S6 octahedra. The corner-sharing octahedral tilt angles are 47°. In the third In site, In(3) is bonded to one S(1), one S(4), and two equivalent S(7) atoms to form distorted InS4 tetrahedra that share  a cornercorner with one In(2)S6 octahedra, corners with two equivalent In(1)S6 octahedra, corners with two equivalent In(3)S4 tetrahedra, and edges with two equivalent In(5)S6 octahedra. The corner-sharing octahedral tilt angles range from 62-87°. In the fourth In site, In(4) is bonded to one S(2), one S(3), and two equivalent S(8) atoms to form distorted InS4 tetrahedra that share  a cornercorner with one In(1)S6 octahedra, corners with two equivalent In(2)S6 octahedra, corners with two equivalent In(4)S4 tetrahedra, and edges with two equivalent In(5)S6 octahedra. The corner-sharing octahedral tilt angles range from 64-84°. In the fifth In site, In(5) is bonded to one S(7), one S(8), two equivalent S(3), and two equivalent S(4) atoms to form InS6 octahedra that share corners with two equivalent In(1)S6 octahedra, corners with two equivalent In(2)S6 octahedra, edges with two equivalent In(5)S6 octahedra, edges with two equivalent In(3)S4 tetrahedra, and edges with two equivalent In(4)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-48°. There are eight inequivalent S sites. In the first S site, S(1) is bonded in a distorted trigonal non-coplanar geometry to one In(3) and two equivalent In(1) atoms. In the second S site, S(2) is bonded in a distorted trigonal non-coplanar geometry to one In(4) and two equivalent In(2) atoms. In the third S site, S(3) is bonded to one In(1), one In(4), and two equivalent In(5) atoms to form a mixture of edge and corner-sharing SIn4 trigonal pyramids. In the fourth S site, S(4) is bonded to one In(2), one In(3), and two equivalent In(5) atoms to form a mixture of edge and corner-sharing SIn4 trigonal pyramids. In the fifth S site, S(5) is bonded in a distorted T-shaped geometry to one In(2) and two equivalent In(1) atoms. In the sixth S site, S(6) is bonded in a 3-coordinate geometry to two equivalent Tl(1), one In(1), and two equivalent In(2) atoms. In the seventh S site, S(7) is bonded in a distorted T-shaped geometry to one In(5) and two equivalent In(3) atoms. In the eighth S site, S(8) is bonded in a distorted T-shaped geometry to one In(5) and two equivalent In(4) atoms.
TlIn5S8 crystallizes in the monoclinic Cm space group. Tl(1) is bonded in a 2-coordinate geometry to two equivalent S(6) atoms. Both Tl(1)-S(6) bond lengths are 3.24 Å. There are five inequivalent In sites. In the first In site, In(1) is bonded to one S(3), one S(6), two equivalent S(1), and two equivalent S(5) atoms to form InS6 octahedra that share corners with two equivalent In(5)S6 octahedra,  a cornercorner with one In(4)S4 tetrahedra, corners with two equivalent In(3)S4 tetrahedra, edges with two equivalent In(1)S6 octahedra, and edges with two equivalent In(2)S6 octahedra. The corner-sharing octahedral tilt angles are 48°. The In(1)-S(3) bond length is 2.76 Å. The In(1)-S(6) bond length is 2.61 Å. Both In(1)-S(1) bond lengths are 2.70 Å. Both In(1)-S(5) bond lengths are 2.59 Å. In the second In site, In(2) is bonded to one S(4), one S(5), two equivalent S(2), and two equivalent S(6) atoms to form InS6 octahedra that share corners with two equivalent In(5)S6 octahedra,  a cornercorner with one In(3)S4 tetrahedra, corners with two equivalent In(4)S4 tetrahedra, edges with two equivalent In(1)S6 octahedra, and edges with two equivalent In(2)S6 octahedra. The corner-sharing octahedral tilt angles are 47°. The In(2)-S(4) bond length is 2.78 Å. The In(2)-S(5) bond length is 2.55 Å. Both In(2)-S(2) bond lengths are 2.68 Å. Both In(2)-S(6) bond lengths are 2.63 Å. In the third In site, In(3) is bonded to one S(1), one S(4), and two equivalent S(7) atoms to form distorted InS4 tetrahedra that share  a cornercorner with one In(2)S6 octahedra, corners with two equivalent In(1)S6 octahedra, corners with two equivalent In(3)S4 tetrahedra, and edges with two equivalent In(5)S6 octahedra. The corner-sharing octahedral tilt angles range from 62-87°. The In(3)-S(1) bond length is 2.44 Å. The In(3)-S(4) bond length is 2.53 Å. Both In(3)-S(7) bond lengths are 2.54 Å. In the fourth In site, In(4) is bonded to one S(2), one S(3), and two equivalent S(8) atoms to form distorted InS4 tetrahedra that share  a cornercorner with one In(1)S6 octahedra, corners with two equivalent In(2)S6 octahedra, corners with two equivalent In(4)S4 tetrahedra, and edges with two equivalent In(5)S6 octahedra. The corner-sharing octahedral tilt angles range from 64-84°. The In(4)-S(2) bond length is 2.45 Å. The In(4)-S(3) bond length is 2.53 Å. Both In(4)-S(8) bond lengths are 2.53 Å. In the fifth In site, In(5) is bonded to one S(7), one S(8), two equivalent S(3), and two equivalent S(4) atoms to form InS6 octahedra that share corners with two equivalent In(1)S6 octahedra, corners with two equivalent In(2)S6 octahedra, edges with two equivalent In(5)S6 octahedra, edges with two equivalent In(3)S4 tetrahedra, and edges with two equivalent In(4)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-48°. The In(5)-S(7) bond length is 2.64 Å. The In(5)-S(8) bond length is 2.64 Å. Both In(5)-S(3) bond lengths are 2.62 Å. Both In(5)-S(4) bond lengths are 2.65 Å. There are eight inequivalent S sites. In the first S site, S(1) is bonded in a distorted trigonal non-coplanar geometry to one In(3) and two equivalent In(1) atoms. In the second S site, S(2) is bonded in a distorted trigonal non-coplanar geometry to one In(4) and two equivalent In(2) atoms. In the third S site, S(3) is bonded to one In(1), one In(4), and two equivalent In(5) atoms to form a mixture of edge and corner-sharing SIn4 trigonal pyramids. In the fourth S site, S(4) is bonded to one In(2), one In(3), and two equivalent In(5) atoms to form a mixture of edge and corner-sharing SIn4 trigonal pyramids. In the fifth S site, S(5) is bonded in a distorted T-shaped geometry to one In(2) and two equivalent In(1) atoms. In the sixth S site, S(6) is bonded in a 3-coordinate geometry to two equivalent Tl(1), one In(1), and two equivalent In(2) atoms. In the seventh S site, S(7) is bonded in a distorted T-shaped geometry to one In(5) and two equivalent In(3) atoms. In the eighth S site, S(8) is bonded in a distorted T-shaped geometry to one In(5) and two equivalent In(4) atoms.