TlIn3S5 crystallizes in the monoclinic C2/m space group. Tl(1) is bonded in a 4-coordinate geometry to two equivalent S(3) and two equivalent S(4) atoms. There are four inequivalent In sites. In the first In site, In(1) is bonded to one S(1), two equivalent S(2), and three equivalent S(3) atoms to form a mixture of corner and edge-sharing InS6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. In the second In site, In(2) is bonded in a 6-coordinate geometry to one S(1), one S(4), two equivalent S(2), and two equivalent S(5) atoms. In the third In site, In(3) is bonded to two equivalent S(2) and four equivalent S(4) atoms to form a mixture of corner and edge-sharing InS6 octahedra. The corner-sharing octahedral tilt angles are 55°. In the fourth In site, In(4) is bonded to two equivalent S(5) and four equivalent S(1) atoms to form a mixture of corner and edge-sharing InS6 octahedra. The corner-sharing octahedral tilt angles are 48°. There are five inequivalent S sites. In the first S site, S(1) is bonded to one In(1), one In(2), and two equivalent In(4) atoms to form a mixture of corner and edge-sharing SIn4 trigonal pyramids. In the second S site, S(2) is bonded in a 5-coordinate geometry to one In(3), two equivalent In(1), and two equivalent In(2) atoms. In the third S site, S(3) is bonded in a 5-coordinate geometry to two equivalent Tl(1) and three equivalent In(1) atoms. In the fourth S site, S(4) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Tl(1), one In(2), and two equivalent In(3) atoms. In the fifth S site, S(5) is bonded in a distorted T-shaped geometry to one In(4) and two equivalent In(2) atoms.
TlIn3S5 crystallizes in the monoclinic C2/m space group. Tl(1) is bonded in a 4-coordinate geometry to two equivalent S(3) and two equivalent S(4) atoms. Both Tl(1)-S(3) bond lengths are 3.15 Å. Both Tl(1)-S(4) bond lengths are 3.28 Å. There are four inequivalent In sites. In the first In site, In(1) is bonded to one S(1), two equivalent S(2), and three equivalent S(3) atoms to form a mixture of corner and edge-sharing InS6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. The In(1)-S(1) bond length is 2.73 Å. Both In(1)-S(2) bond lengths are 2.62 Å. There is one shorter (2.56 Å) and two longer (2.65 Å) In(1)-S(3) bond lengths. In the second In site, In(2) is bonded in a 6-coordinate geometry to one S(1), one S(4), two equivalent S(2), and two equivalent S(5) atoms. The In(2)-S(1) bond length is 2.57 Å. The In(2)-S(4) bond length is 2.48 Å. Both In(2)-S(2) bond lengths are 3.10 Å. Both In(2)-S(5) bond lengths are 2.53 Å. In the third In site, In(3) is bonded to two equivalent S(2) and four equivalent S(4) atoms to form a mixture of corner and edge-sharing InS6 octahedra. The corner-sharing octahedral tilt angles are 55°. Both In(3)-S(2) bond lengths are 2.55 Å. All In(3)-S(4) bond lengths are 2.69 Å. In the fourth In site, In(4) is bonded to two equivalent S(5) and four equivalent S(1) atoms to form a mixture of corner and edge-sharing InS6 octahedra. The corner-sharing octahedral tilt angles are 48°. Both In(4)-S(5) bond lengths are 2.73 Å. All In(4)-S(1) bond lengths are 2.60 Å. There are five inequivalent S sites. In the first S site, S(1) is bonded to one In(1), one In(2), and two equivalent In(4) atoms to form a mixture of corner and edge-sharing SIn4 trigonal pyramids. In the second S site, S(2) is bonded in a 5-coordinate geometry to one In(3), two equivalent In(1), and two equivalent In(2) atoms. In the third S site, S(3) is bonded in a 5-coordinate geometry to two equivalent Tl(1) and three equivalent In(1) atoms. In the fourth S site, S(4) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Tl(1), one In(2), and two equivalent In(3) atoms. In the fifth S site, S(5) is bonded in a distorted T-shaped geometry to one In(4) and two equivalent In(2) atoms.