TlIn5S7 crystallizes in the monoclinic P2_1/m space group. Tl(1) is bonded in a 4-coordinate geometry to two equivalent S(1) and two equivalent S(6) atoms. There are five inequivalent In sites. In the first In site, In(1) is bonded to one S(6), two equivalent S(3), and three equivalent S(4) atoms to form edge-sharing InS6 octahedra. In the second In site, In(2) is bonded to one S(5), two equivalent S(7), and three equivalent S(2) atoms to form a mixture of corner and edge-sharing InS6 octahedra. The corner-sharing octahedral tilt angles are 3°. In the third In site, In(3) is bonded in a 3-coordinate geometry to one S(3) and two equivalent S(6) atoms. In the fourth In site, In(4) is bonded to one S(7), two equivalent S(2), and three equivalent S(1) atoms to form a mixture of corner and edge-sharing InS6 octahedra. The corner-sharing octahedral tilt angles are 3°. In the fifth In site, In(5) is bonded in a 3-coordinate geometry to one S(4) and two equivalent S(5) atoms. There are seven inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Tl(1) and three equivalent In(4) atoms to form distorted STl2In3 trigonal bipyramids that share corners with two equivalent S(6)Tl2In3 square pyramids, corners with four equivalent S(2)In5 square pyramids,  an edgeedge with one S(2)In5 square pyramid,  an edgeedge with one S(6)Tl2In3 square pyramid, and edges with four equivalent S(1)Tl2In3 trigonal bipyramids. In the second S site, S(2) is bonded to two equivalent In(4) and three equivalent In(2) atoms to form SIn5 square pyramids that share corners with four equivalent S(1)Tl2In3 trigonal bipyramids, edges with four equivalent S(2)In5 square pyramids, and  an edgeedge with one S(1)Tl2In3 trigonal bipyramid. In the third S site, S(3) is bonded in a 3-coordinate geometry to one In(3) and two equivalent In(1) atoms. In the fourth S site, S(4) is bonded in a rectangular see-saw-like geometry to one In(5) and three equivalent In(1) atoms. In the fifth S site, S(5) is bonded in a trigonal non-coplanar geometry to one In(2) and two equivalent In(5) atoms. In the sixth S site, S(6) is bonded to two equivalent Tl(1), one In(1), and two equivalent In(3) atoms to form a mixture of distorted corner and edge-sharing STl2In3 square pyramids. In the seventh S site, S(7) is bonded in a distorted T-shaped geometry to one In(4) and two equivalent In(2) atoms.
TlIn5S7 crystallizes in the monoclinic P2_1/m space group. Tl(1) is bonded in a 4-coordinate geometry to two equivalent S(1) and two equivalent S(6) atoms. Both Tl(1)-S(1) bond lengths are 3.12 Å. Both Tl(1)-S(6) bond lengths are 3.16 Å. There are five inequivalent In sites. In the first In site, In(1) is bonded to one S(6), two equivalent S(3), and three equivalent S(4) atoms to form edge-sharing InS6 octahedra. The In(1)-S(6) bond length is 2.61 Å. Both In(1)-S(3) bond lengths are 2.65 Å. There is one shorter (2.65 Å) and two longer (2.70 Å) In(1)-S(4) bond lengths. In the second In site, In(2) is bonded to one S(5), two equivalent S(7), and three equivalent S(2) atoms to form a mixture of corner and edge-sharing InS6 octahedra. The corner-sharing octahedral tilt angles are 3°. The In(2)-S(5) bond length is 2.63 Å. Both In(2)-S(7) bond lengths are 2.58 Å. There is one shorter (2.65 Å) and two longer (2.78 Å) In(2)-S(2) bond lengths. In the third In site, In(3) is bonded in a 3-coordinate geometry to one S(3) and two equivalent S(6) atoms. The In(3)-S(3) bond length is 2.54 Å. Both In(3)-S(6) bond lengths are 2.58 Å. In the fourth In site, In(4) is bonded to one S(7), two equivalent S(2), and three equivalent S(1) atoms to form a mixture of corner and edge-sharing InS6 octahedra. The corner-sharing octahedral tilt angles are 3°. The In(4)-S(7) bond length is 2.53 Å. Both In(4)-S(2) bond lengths are 2.82 Å. There is one shorter (2.53 Å) and two longer (2.62 Å) In(4)-S(1) bond lengths. In the fifth In site, In(5) is bonded in a 3-coordinate geometry to one S(4) and two equivalent S(5) atoms. The In(5)-S(4) bond length is 2.65 Å. Both In(5)-S(5) bond lengths are 2.55 Å. There are seven inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Tl(1) and three equivalent In(4) atoms to form distorted STl2In3 trigonal bipyramids that share corners with two equivalent S(6)Tl2In3 square pyramids, corners with four equivalent S(2)In5 square pyramids,  an edgeedge with one S(2)In5 square pyramid,  an edgeedge with one S(6)Tl2In3 square pyramid, and edges with four equivalent S(1)Tl2In3 trigonal bipyramids. In the second S site, S(2) is bonded to two equivalent In(4) and three equivalent In(2) atoms to form SIn5 square pyramids that share corners with four equivalent S(1)Tl2In3 trigonal bipyramids, edges with four equivalent S(2)In5 square pyramids, and  an edgeedge with one S(1)Tl2In3 trigonal bipyramid. In the third S site, S(3) is bonded in a 3-coordinate geometry to one In(3) and two equivalent In(1) atoms. In the fourth S site, S(4) is bonded in a rectangular see-saw-like geometry to one In(5) and three equivalent In(1) atoms. In the fifth S site, S(5) is bonded in a trigonal non-coplanar geometry to one In(2) and two equivalent In(5) atoms. In the sixth S site, S(6) is bonded to two equivalent Tl(1), one In(1), and two equivalent In(3) atoms to form a mixture of distorted corner and edge-sharing STl2In3 square pyramids. In the seventh S site, S(7) is bonded in a distorted T-shaped geometry to one In(4) and two equivalent In(2) atoms.