Tb3In5S12 crystallizes in the monoclinic P2_1/m space group. There are three inequivalent Tb sites. In the first Tb site, Tb(1) is bonded in a 8-coordinate geometry to one S(1), one S(7), two equivalent S(5), two equivalent S(6), and two equivalent S(9) atoms. In the second Tb site, Tb(2) is bonded in a 8-coordinate geometry to one S(10), one S(6), two equivalent S(3), two equivalent S(7), and two equivalent S(8) atoms. In the third Tb site, Tb(3) is bonded to one S(10), one S(5), two equivalent S(7), and three equivalent S(12) atoms to form distorted TbS7 pentagonal bipyramids that share  a cornercorner with one In(2)S6 octahedra, corners with two equivalent In(4)S6 octahedra, edges with two equivalent In(2)S6 octahedra, and edges with four equivalent Tb(3)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 38-52°. There are five inequivalent In sites. In the first In site, In(1) is bonded to one S(1), one S(3), two equivalent S(2), and two equivalent S(6) atoms to form distorted InS6 octahedra that share corners with two equivalent In(3)S6 octahedra, corners with three equivalent In(5)S4 tetrahedra, and edges with two equivalent In(1)S6 octahedra. The corner-sharing octahedral tilt angles are 50°. In the second In site, In(2) is bonded to one S(12), two equivalent S(5), and three equivalent S(11) atoms to form InS6 octahedra that share corners with three equivalent In(4)S6 octahedra,  a cornercorner with one Tb(3)S7 pentagonal bipyramid, edges with four equivalent In(2)S6 octahedra, and edges with two equivalent Tb(3)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 55-60°. In the third In site, In(3) is bonded to one S(4), one S(9), two equivalent S(1), and two equivalent S(8) atoms to form InS6 octahedra that share corners with two equivalent In(1)S6 octahedra, corners with two equivalent In(5)S4 tetrahedra, edges with two equivalent In(3)S6 octahedra, and edges with two equivalent In(4)S6 octahedra. The corner-sharing octahedral tilt angles are 50°. In the fourth In site, In(4) is bonded to one S(11), one S(8), two equivalent S(10), and two equivalent S(9) atoms to form InS6 octahedra that share corners with three equivalent In(2)S6 octahedra, corners with two equivalent Tb(3)S7 pentagonal bipyramids, edges with two equivalent In(3)S6 octahedra, and edges with two equivalent In(4)S6 octahedra. The corner-sharing octahedral tilt angles range from 55-60°. In the fifth In site, In(5) is bonded to one S(2), one S(3), and two equivalent S(4) atoms to form InS4 tetrahedra that share corners with two equivalent In(3)S6 octahedra, corners with three equivalent In(1)S6 octahedra, and corners with two equivalent In(5)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 57-73°. There are twelve inequivalent S sites. In the first S site, S(1) is bonded to one Tb(1), one In(1), and two equivalent In(3) atoms to form distorted STbIn3 trigonal pyramids that share corners with two equivalent S(8)Tb2In3 square pyramids, corners with two equivalent S(5)Tb3In2 square pyramids,  a cornercorner with one S(3)Tb2In2 tetrahedra,  a cornercorner with one S(7)Tb5 trigonal bipyramid, corners with two equivalent S(1)TbIn3 trigonal pyramids,  an edgeedge with one S(8)Tb2In3 square pyramid, edges with two equivalent S(9)Tb2In3 square pyramids, and edges with two equivalent S(6)Tb3In2 trigonal bipyramids. In the second S site, S(2) is bonded in a trigonal planar geometry to one In(5) and two equivalent In(1) atoms. In the third S site, S(3) is bonded to two equivalent Tb(2), one In(1), and one In(5) atom to form STb2In2 tetrahedra that share corners with two equivalent S(8)Tb2In3 square pyramids, corners with two equivalent S(3)Tb2In2 tetrahedra, corners with two equivalent S(7)Tb5 trigonal bipyramids,  a cornercorner with one S(1)TbIn3 trigonal pyramid, corners with two equivalent S(10)Tb2In2 trigonal pyramids,  an edgeedge with one S(8)Tb2In3 square pyramid,  an edgeedge with one S(7)Tb5 trigonal bipyramid, and edges with two equivalent S(6)Tb3In2 trigonal bipyramids. In the fourth S site, S(4) is bonded in a trigonal non-coplanar geometry to one In(3) and two equivalent In(5) atoms. In the fifth S site, S(5) is bonded to one Tb(3), two equivalent Tb(1), and two equivalent In(2) atoms to form STb3In2 square pyramids that share corners with two equivalent S(9)Tb2In3 square pyramids, corners with two equivalent S(6)Tb3In2 trigonal bipyramids,  a cornercorner with one S(10)Tb2In2 trigonal pyramid,  a cornercorner with one S(12)Tb3In trigonal pyramid, corners with two equivalent S(1)TbIn3 trigonal pyramids,  an edgeedge with one S(9)Tb2In3 square pyramid, edges with two equivalent S(5)Tb3In2 square pyramids,  an edgeedge with one S(6)Tb3In2 trigonal bipyramid, edges with two equivalent S(7)Tb5 trigonal bipyramids, and edges with two equivalent S(12)Tb3In trigonal pyramids. In the sixth S site, S(6) is bonded to one Tb(2), two equivalent Tb(1), and two equivalent In(1) atoms to form distorted STb3In2 trigonal bipyramids that share corners with two equivalent S(8)Tb2In3 square pyramids, corners with two equivalent S(9)Tb2In3 square pyramids, corners with two equivalent S(5)Tb3In2 square pyramids,  a cornercorner with one S(10)Tb2In2 trigonal pyramid,  an edgeedge with one S(9)Tb2In3 square pyramid,  an edgeedge with one S(5)Tb3In2 square pyramid, edges with two equivalent S(3)Tb2In2 tetrahedra, edges with two equivalent S(6)Tb3In2 trigonal bipyramids, edges with two equivalent S(7)Tb5 trigonal bipyramids, and edges with two equivalent S(1)TbIn3 trigonal pyramids. In the seventh S site, S(7) is bonded to one Tb(1), two equivalent Tb(2), and two equivalent Tb(3) atoms to form distorted STb5 trigonal bipyramids that share corners with two equivalent S(8)Tb2In3 square pyramids, corners with two equivalent S(9)Tb2In3 square pyramids, corners with two equivalent S(3)Tb2In2 tetrahedra,  a cornercorner with one S(1)TbIn3 trigonal pyramid, corners with four equivalent S(12)Tb3In trigonal pyramids,  an edgeedge with one S(8)Tb2In3 square pyramid, edges with two equivalent S(5)Tb3In2 square pyramids,  an edgeedge with one S(3)Tb2In2 tetrahedra, edges with two equivalent S(6)Tb3In2 trigonal bipyramids, edges with two equivalent S(7)Tb5 trigonal bipyramids,  an edgeedge with one S(12)Tb3In trigonal pyramid, and edges with two equivalent S(10)Tb2In2 trigonal pyramids. In the eighth S site, S(8) is bonded to two equivalent Tb(2), one In(4), and two equivalent In(3) atoms to form STb2In3 square pyramids that share corners with two equivalent S(3)Tb2In2 tetrahedra, corners with two equivalent S(6)Tb3In2 trigonal bipyramids, corners with two equivalent S(7)Tb5 trigonal bipyramids, corners with two equivalent S(1)TbIn3 trigonal pyramids, edges with two equivalent S(8)Tb2In3 square pyramids, edges with two equivalent S(9)Tb2In3 square pyramids,  an edgeedge with one S(3)Tb2In2 tetrahedra,  an edgeedge with one S(7)Tb5 trigonal bipyramid,  an edgeedge with one S(1)TbIn3 trigonal pyramid, and edges with two equivalent S(10)Tb2In2 trigonal pyramids. In the ninth S site, S(9) is bonded to two equivalent Tb(1), one In(3), and two equivalent In(4) atoms to form STb2In3 square pyramids that share corners with two equivalent S(5)Tb3In2 square pyramids, corners with two equivalent S(6)Tb3In2 trigonal bipyramids, corners with two equivalent S(7)Tb5 trigonal bipyramids, corners with two equivalent S(10)Tb2In2 trigonal pyramids,  an edgeedge with one S(5)Tb3In2 square pyramid, edges with two equivalent S(8)Tb2In3 square pyramids, edges with two equivalent S(9)Tb2In3 square pyramids,  an edgeedge with one S(6)Tb3In2 trigonal bipyramid,  an edgeedge with one S(10)Tb2In2 trigonal pyramid, and edges with two equivalent S(1)TbIn3 trigonal pyramids. In the tenth S site, S(10) is bonded to one Tb(2), one Tb(3), and two equivalent In(4) atoms to form STb2In2 trigonal pyramids that share  a cornercorner with one S(5)Tb3In2 square pyramid, corners with two equivalent S(9)Tb2In3 square pyramids, corners with two equivalent S(3)Tb2In2 tetrahedra,  a cornercorner with one S(6)Tb3In2 trigonal bipyramid, corners with two equivalent S(10)Tb2In2 trigonal pyramids, corners with three equivalent S(12)Tb3In trigonal pyramids,  an edgeedge with one S(9)Tb2In3 square pyramid, edges with two equivalent S(8)Tb2In3 square pyramids, and edges with two equivalent S(7)Tb5 trigonal bipyramids. In the eleventh S site, S(11) is bonded in a rectangular see-saw-like geometry to one In(4) and three equivalent In(2) atoms. In the twelfth S site, S(12) is bonded to three equivalent Tb(3) and one In(2) atom to form distorted STb3In trigonal pyramids that share  a cornercorner with one S(5)Tb3In2 square pyramid, corners with four equivalent S(7)Tb5 trigonal bipyramids, corners with two equivalent S(12)Tb3In trigonal pyramids, corners with three equivalent S(10)Tb2In2 trigonal pyramids, edges with two equivalent S(5)Tb3In2 square pyramids,  an edgeedge with one S(7)Tb5 trigonal bipyramid, and edges with two equivalent S(12)Tb3In trigonal pyramids.
Tb3In5S12 crystallizes in the monoclinic P2_1/m space group. There are three inequivalent Tb sites. In the first Tb site, Tb(1) is bonded in a 8-coordinate geometry to one S(1), one S(7), two equivalent S(5), two equivalent S(6), and two equivalent S(9) atoms. The Tb(1)-S(1) bond length is 3.07 Å. The Tb(1)-S(7) bond length is 2.89 Å. Both Tb(1)-S(5) bond lengths are 2.94 Å. Both Tb(1)-S(6) bond lengths are 2.77 Å. Both Tb(1)-S(9) bond lengths are 2.92 Å. In the second Tb site, Tb(2) is bonded in a 8-coordinate geometry to one S(10), one S(6), two equivalent S(3), two equivalent S(7), and two equivalent S(8) atoms. The Tb(2)-S(10) bond length is 2.87 Å. The Tb(2)-S(6) bond length is 2.84 Å. Both Tb(2)-S(3) bond lengths are 2.83 Å. Both Tb(2)-S(7) bond lengths are 2.84 Å. Both Tb(2)-S(8) bond lengths are 2.98 Å. In the third Tb site, Tb(3) is bonded to one S(10), one S(5), two equivalent S(7), and three equivalent S(12) atoms to form distorted TbS7 pentagonal bipyramids that share  a cornercorner with one In(2)S6 octahedra, corners with two equivalent In(4)S6 octahedra, edges with two equivalent In(2)S6 octahedra, and edges with four equivalent Tb(3)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 38-52°. The Tb(3)-S(10) bond length is 2.74 Å. The Tb(3)-S(5) bond length is 2.84 Å. Both Tb(3)-S(7) bond lengths are 2.84 Å. There are two shorter (2.72 Å) and one longer (2.79 Å) Tb(3)-S(12) bond length. There are five inequivalent In sites. In the first In site, In(1) is bonded to one S(1), one S(3), two equivalent S(2), and two equivalent S(6) atoms to form distorted InS6 octahedra that share corners with two equivalent In(3)S6 octahedra, corners with three equivalent In(5)S4 tetrahedra, and edges with two equivalent In(1)S6 octahedra. The corner-sharing octahedral tilt angles are 50°. The In(1)-S(1) bond length is 2.56 Å. The In(1)-S(3) bond length is 2.60 Å. Both In(1)-S(2) bond lengths are 2.53 Å. Both In(1)-S(6) bond lengths are 2.84 Å. In the second In site, In(2) is bonded to one S(12), two equivalent S(5), and three equivalent S(11) atoms to form InS6 octahedra that share corners with three equivalent In(4)S6 octahedra,  a cornercorner with one Tb(3)S7 pentagonal bipyramid, edges with four equivalent In(2)S6 octahedra, and edges with two equivalent Tb(3)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 55-60°. The In(2)-S(12) bond length is 2.54 Å. Both In(2)-S(5) bond lengths are 2.72 Å. There is one shorter (2.62 Å) and two longer (2.65 Å) In(2)-S(11) bond lengths. In the third In site, In(3) is bonded to one S(4), one S(9), two equivalent S(1), and two equivalent S(8) atoms to form InS6 octahedra that share corners with two equivalent In(1)S6 octahedra, corners with two equivalent In(5)S4 tetrahedra, edges with two equivalent In(3)S6 octahedra, and edges with two equivalent In(4)S6 octahedra. The corner-sharing octahedral tilt angles are 50°. The In(3)-S(4) bond length is 2.62 Å. The In(3)-S(9) bond length is 2.62 Å. Both In(3)-S(1) bond lengths are 2.56 Å. Both In(3)-S(8) bond lengths are 2.74 Å. In the fourth In site, In(4) is bonded to one S(11), one S(8), two equivalent S(10), and two equivalent S(9) atoms to form InS6 octahedra that share corners with three equivalent In(2)S6 octahedra, corners with two equivalent Tb(3)S7 pentagonal bipyramids, edges with two equivalent In(3)S6 octahedra, and edges with two equivalent In(4)S6 octahedra. The corner-sharing octahedral tilt angles range from 55-60°. The In(4)-S(11) bond length is 2.63 Å. The In(4)-S(8) bond length is 2.63 Å. Both In(4)-S(10) bond lengths are 2.54 Å. Both In(4)-S(9) bond lengths are 2.73 Å. In the fifth In site, In(5) is bonded to one S(2), one S(3), and two equivalent S(4) atoms to form InS4 tetrahedra that share corners with two equivalent In(3)S6 octahedra, corners with three equivalent In(1)S6 octahedra, and corners with two equivalent In(5)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 57-73°. The In(5)-S(2) bond length is 2.46 Å. The In(5)-S(3) bond length is 2.49 Å. Both In(5)-S(4) bond lengths are 2.48 Å. There are twelve inequivalent S sites. In the first S site, S(1) is bonded to one Tb(1), one In(1), and two equivalent In(3) atoms to form distorted STbIn3 trigonal pyramids that share corners with two equivalent S(8)Tb2In3 square pyramids, corners with two equivalent S(5)Tb3In2 square pyramids,  a cornercorner with one S(3)Tb2In2 tetrahedra,  a cornercorner with one S(7)Tb5 trigonal bipyramid, corners with two equivalent S(1)TbIn3 trigonal pyramids,  an edgeedge with one S(8)Tb2In3 square pyramid, edges with two equivalent S(9)Tb2In3 square pyramids, and edges with two equivalent S(6)Tb3In2 trigonal bipyramids. In the second S site, S(2) is bonded in a trigonal planar geometry to one In(5) and two equivalent In(1) atoms. In the third S site, S(3) is bonded to two equivalent Tb(2), one In(1), and one In(5) atom to form STb2In2 tetrahedra that share corners with two equivalent S(8)Tb2In3 square pyramids, corners with two equivalent S(3)Tb2In2 tetrahedra, corners with two equivalent S(7)Tb5 trigonal bipyramids,  a cornercorner with one S(1)TbIn3 trigonal pyramid, corners with two equivalent S(10)Tb2In2 trigonal pyramids,  an edgeedge with one S(8)Tb2In3 square pyramid,  an edgeedge with one S(7)Tb5 trigonal bipyramid, and edges with two equivalent S(6)Tb3In2 trigonal bipyramids. In the fourth S site, S(4) is bonded in a trigonal non-coplanar geometry to one In(3) and two equivalent In(5) atoms. In the fifth S site, S(5) is bonded to one Tb(3), two equivalent Tb(1), and two equivalent In(2) atoms to form STb3In2 square pyramids that share corners with two equivalent S(9)Tb2In3 square pyramids, corners with two equivalent S(6)Tb3In2 trigonal bipyramids,  a cornercorner with one S(10)Tb2In2 trigonal pyramid,  a cornercorner with one S(12)Tb3In trigonal pyramid, corners with two equivalent S(1)TbIn3 trigonal pyramids,  an edgeedge with one S(9)Tb2In3 square pyramid, edges with two equivalent S(5)Tb3In2 square pyramids,  an edgeedge with one S(6)Tb3In2 trigonal bipyramid, edges with two equivalent S(7)Tb5 trigonal bipyramids, and edges with two equivalent S(12)Tb3In trigonal pyramids. In the sixth S site, S(6) is bonded to one Tb(2), two equivalent Tb(1), and two equivalent In(1) atoms to form distorted STb3In2 trigonal bipyramids that share corners with two equivalent S(8)Tb2In3 square pyramids, corners with two equivalent S(9)Tb2In3 square pyramids, corners with two equivalent S(5)Tb3In2 square pyramids,  a cornercorner with one S(10)Tb2In2 trigonal pyramid,  an edgeedge with one S(9)Tb2In3 square pyramid,  an edgeedge with one S(5)Tb3In2 square pyramid, edges with two equivalent S(3)Tb2In2 tetrahedra, edges with two equivalent S(6)Tb3In2 trigonal bipyramids, edges with two equivalent S(7)Tb5 trigonal bipyramids, and edges with two equivalent S(1)TbIn3 trigonal pyramids. In the seventh S site, S(7) is bonded to one Tb(1), two equivalent Tb(2), and two equivalent Tb(3) atoms to form distorted STb5 trigonal bipyramids that share corners with two equivalent S(8)Tb2In3 square pyramids, corners with two equivalent S(9)Tb2In3 square pyramids, corners with two equivalent S(3)Tb2In2 tetrahedra,  a cornercorner with one S(1)TbIn3 trigonal pyramid, corners with four equivalent S(12)Tb3In trigonal pyramids,  an edgeedge with one S(8)Tb2In3 square pyramid, edges with two equivalent S(5)Tb3In2 square pyramids,  an edgeedge with one S(3)Tb2In2 tetrahedra, edges with two equivalent S(6)Tb3In2 trigonal bipyramids, edges with two equivalent S(7)Tb5 trigonal bipyramids,  an edgeedge with one S(12)Tb3In trigonal pyramid, and edges with two equivalent S(10)Tb2In2 trigonal pyramids. In the eighth S site, S(8) is bonded to two equivalent Tb(2), one In(4), and two equivalent In(3) atoms to form STb2In3 square pyramids that share corners with two equivalent S(3)Tb2In2 tetrahedra, corners with two equivalent S(6)Tb3In2 trigonal bipyramids, corners with two equivalent S(7)Tb5 trigonal bipyramids, corners with two equivalent S(1)TbIn3 trigonal pyramids, edges with two equivalent S(8)Tb2In3 square pyramids, edges with two equivalent S(9)Tb2In3 square pyramids,  an edgeedge with one S(3)Tb2In2 tetrahedra,  an edgeedge with one S(7)Tb5 trigonal bipyramid,  an edgeedge with one S(1)TbIn3 trigonal pyramid, and edges with two equivalent S(10)Tb2In2 trigonal pyramids. In the ninth S site, S(9) is bonded to two equivalent Tb(1), one In(3), and two equivalent In(4) atoms to form STb2In3 square pyramids that share corners with two equivalent S(5)Tb3In2 square pyramids, corners with two equivalent S(6)Tb3In2 trigonal bipyramids, corners with two equivalent S(7)Tb5 trigonal bipyramids, corners with two equivalent S(10)Tb2In2 trigonal pyramids,  an edgeedge with one S(5)Tb3In2 square pyramid, edges with two equivalent S(8)Tb2In3 square pyramids, edges with two equivalent S(9)Tb2In3 square pyramids,  an edgeedge with one S(6)Tb3In2 trigonal bipyramid,  an edgeedge with one S(10)Tb2In2 trigonal pyramid, and edges with two equivalent S(1)TbIn3 trigonal pyramids. In the tenth S site, S(10) is bonded to one Tb(2), one Tb(3), and two equivalent In(4) atoms to form STb2In2 trigonal pyramids that share  a cornercorner with one S(5)Tb3In2 square pyramid, corners with two equivalent S(9)Tb2In3 square pyramids, corners with two equivalent S(3)Tb2In2 tetrahedra,  a cornercorner with one S(6)Tb3In2 trigonal bipyramid, corners with two equivalent S(10)Tb2In2 trigonal pyramids, corners with three equivalent S(12)Tb3In trigonal pyramids,  an edgeedge with one S(9)Tb2In3 square pyramid, edges with two equivalent S(8)Tb2In3 square pyramids, and edges with two equivalent S(7)Tb5 trigonal bipyramids. In the eleventh S site, S(11) is bonded in a rectangular see-saw-like geometry to one In(4) and three equivalent In(2) atoms. In the twelfth S site, S(12) is bonded to three equivalent Tb(3) and one In(2) atom to form distorted STb3In trigonal pyramids that share  a cornercorner with one S(5)Tb3In2 square pyramid, corners with four equivalent S(7)Tb5 trigonal bipyramids, corners with two equivalent S(12)Tb3In trigonal pyramids, corners with three equivalent S(10)Tb2In2 trigonal pyramids, edges with two equivalent S(5)Tb3In2 square pyramids,  an edgeedge with one S(7)Tb5 trigonal bipyramid, and edges with two equivalent S(12)Tb3In trigonal pyramids.