In5(BiS4)3 crystallizes in the monoclinic C2/m space group. There are six inequivalent In sites. In the first In site, In(1) is bonded to two equivalent S(1) and four equivalent S(7) atoms to form InS6 octahedra that share corners with two equivalent In(6)S6 octahedra, edges with two equivalent In(1)S6 octahedra, and edges with four equivalent Bi(3)S5 square pyramids. The corner-sharing octahedral tilt angles are 53°. In the second In site, In(2) is bonded to two equivalent S(2) and four equivalent S(6) atoms to form a mixture of corner and edge-sharing InS6 octahedra. The corner-sharing octahedral tilt angles are 2°. In the third In site, In(3) is bonded to one S(4), two equivalent S(8), and three equivalent S(11) atoms to form a mixture of corner and edge-sharing InS6 octahedra. The corner-sharing octahedral tilt angles are 59°. In the fourth In site, In(4) is bonded to one S(6), one S(8), two equivalent S(10), and two equivalent S(2) atoms to form a mixture of corner and edge-sharing InS6 octahedra. The corner-sharing octahedral tilt angles range from 48-59°. In the fifth In site, In(5) is bonded to one S(12), one S(8), two equivalent S(3), and two equivalent S(4) atoms to form InS6 octahedra that share  a cornercorner with one In(4)S6 octahedra, corners with two equivalent Bi(3)S5 square pyramids, edges with two equivalent In(3)S6 octahedra, edges with two equivalent In(5)S6 octahedra, and  an edgeedge with one Bi(3)S5 square pyramid. The corner-sharing octahedral tilt angles are 48°. In the sixth In site, In(6) is bonded to one S(1), one S(10), two equivalent S(5), and two equivalent S(6) atoms to form InS6 octahedra that share  a cornercorner with one In(1)S6 octahedra, corners with two equivalent In(2)S6 octahedra, corners with two equivalent Bi(3)S5 square pyramids,  an edgeedge with one In(2)S6 octahedra, edges with two equivalent In(4)S6 octahedra, and edges with two equivalent In(6)S6 octahedra. The corner-sharing octahedral tilt angles range from 2-53°. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 4-coordinate geometry to one S(3), one S(9), and two equivalent S(12) atoms. In the second Bi site, Bi(2) is bonded in a 3-coordinate geometry to one S(5) and two equivalent S(9) atoms. In the third Bi site, Bi(3) is bonded to one S(7), two equivalent S(1), and two equivalent S(3) atoms to form BiS5 square pyramids that share corners with two equivalent In(5)S6 octahedra, corners with two equivalent In(6)S6 octahedra,  an edgeedge with one In(5)S6 octahedra, edges with two equivalent In(1)S6 octahedra, and edges with two equivalent Bi(3)S5 square pyramids. The corner-sharing octahedral tilt angles range from 20-59°. There are twelve inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one In(1), one In(6), and two equivalent Bi(3) atoms. In the second S site, S(2) is bonded in a distorted T-shaped geometry to one In(2) and two equivalent In(4) atoms. In the third S site, S(3) is bonded to two equivalent In(5), one Bi(1), and two equivalent Bi(3) atoms to form edge-sharing SIn2Bi3 trigonal bipyramids. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to one In(3) and two equivalent In(5) atoms. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to two equivalent In(6) and one Bi(2) atom. In the sixth S site, S(6) is bonded to one In(4), two equivalent In(2), and two equivalent In(6) atoms to form a mixture of corner and edge-sharing SIn5 square pyramids. In the seventh S site, S(7) is bonded in a distorted T-shaped geometry to two equivalent In(1) and one Bi(3) atom. In the eighth S site, S(8) is bonded in a rectangular see-saw-like geometry to one In(4), one In(5), and two equivalent In(3) atoms. In the ninth S site, S(9) is bonded in a trigonal non-coplanar geometry to one Bi(1) and two equivalent Bi(2) atoms. In the tenth S site, S(10) is bonded in a 3-coordinate geometry to one In(6) and two equivalent In(4) atoms. In the eleventh S site, S(11) is bonded in a 3-coordinate geometry to three equivalent In(3) atoms. In the twelfth S site, S(12) is bonded in a trigonal non-coplanar geometry to one In(5) and two equivalent Bi(1) atoms.
In5(BiS4)3 crystallizes in the monoclinic C2/m space group. There are six inequivalent In sites. In the first In site, In(1) is bonded to two equivalent S(1) and four equivalent S(7) atoms to form InS6 octahedra that share corners with two equivalent In(6)S6 octahedra, edges with two equivalent In(1)S6 octahedra, and edges with four equivalent Bi(3)S5 square pyramids. The corner-sharing octahedral tilt angles are 53°. Both In(1)-S(1) bond lengths are 2.66 Å. All In(1)-S(7) bond lengths are 2.68 Å. In the second In site, In(2) is bonded to two equivalent S(2) and four equivalent S(6) atoms to form a mixture of corner and edge-sharing InS6 octahedra. The corner-sharing octahedral tilt angles are 2°. Both In(2)-S(2) bond lengths are 2.54 Å. All In(2)-S(6) bond lengths are 2.75 Å. In the third In site, In(3) is bonded to one S(4), two equivalent S(8), and three equivalent S(11) atoms to form a mixture of corner and edge-sharing InS6 octahedra. The corner-sharing octahedral tilt angles are 59°. The In(3)-S(4) bond length is 2.61 Å. Both In(3)-S(8) bond lengths are 2.70 Å. There is one shorter (2.55 Å) and two longer (2.70 Å) In(3)-S(11) bond lengths. In the fourth In site, In(4) is bonded to one S(6), one S(8), two equivalent S(10), and two equivalent S(2) atoms to form a mixture of corner and edge-sharing InS6 octahedra. The corner-sharing octahedral tilt angles range from 48-59°. The In(4)-S(6) bond length is 2.66 Å. The In(4)-S(8) bond length is 2.60 Å. Both In(4)-S(10) bond lengths are 2.69 Å. Both In(4)-S(2) bond lengths are 2.67 Å. In the fifth In site, In(5) is bonded to one S(12), one S(8), two equivalent S(3), and two equivalent S(4) atoms to form InS6 octahedra that share  a cornercorner with one In(4)S6 octahedra, corners with two equivalent Bi(3)S5 square pyramids, edges with two equivalent In(3)S6 octahedra, edges with two equivalent In(5)S6 octahedra, and  an edgeedge with one Bi(3)S5 square pyramid. The corner-sharing octahedral tilt angles are 48°. The In(5)-S(12) bond length is 2.62 Å. The In(5)-S(8) bond length is 2.63 Å. Both In(5)-S(3) bond lengths are 2.84 Å. Both In(5)-S(4) bond lengths are 2.56 Å. In the sixth In site, In(6) is bonded to one S(1), one S(10), two equivalent S(5), and two equivalent S(6) atoms to form InS6 octahedra that share  a cornercorner with one In(1)S6 octahedra, corners with two equivalent In(2)S6 octahedra, corners with two equivalent Bi(3)S5 square pyramids,  an edgeedge with one In(2)S6 octahedra, edges with two equivalent In(4)S6 octahedra, and edges with two equivalent In(6)S6 octahedra. The corner-sharing octahedral tilt angles range from 2-53°. The In(6)-S(1) bond length is 2.62 Å. The In(6)-S(10) bond length is 2.53 Å. Both In(6)-S(5) bond lengths are 2.61 Å. Both In(6)-S(6) bond lengths are 2.86 Å. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 4-coordinate geometry to one S(3), one S(9), and two equivalent S(12) atoms. The Bi(1)-S(3) bond length is 2.94 Å. The Bi(1)-S(9) bond length is 2.82 Å. Both Bi(1)-S(12) bond lengths are 2.65 Å. In the second Bi site, Bi(2) is bonded in a 3-coordinate geometry to one S(5) and two equivalent S(9) atoms. The Bi(2)-S(5) bond length is 2.79 Å. Both Bi(2)-S(9) bond lengths are 2.67 Å. In the third Bi site, Bi(3) is bonded to one S(7), two equivalent S(1), and two equivalent S(3) atoms to form BiS5 square pyramids that share corners with two equivalent In(5)S6 octahedra, corners with two equivalent In(6)S6 octahedra,  an edgeedge with one In(5)S6 octahedra, edges with two equivalent In(1)S6 octahedra, and edges with two equivalent Bi(3)S5 square pyramids. The corner-sharing octahedral tilt angles range from 20-59°. The Bi(3)-S(7) bond length is 2.66 Å. Both Bi(3)-S(1) bond lengths are 2.81 Å. Both Bi(3)-S(3) bond lengths are 2.88 Å. There are twelve inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one In(1), one In(6), and two equivalent Bi(3) atoms. In the second S site, S(2) is bonded in a distorted T-shaped geometry to one In(2) and two equivalent In(4) atoms. In the third S site, S(3) is bonded to two equivalent In(5), one Bi(1), and two equivalent Bi(3) atoms to form edge-sharing SIn2Bi3 trigonal bipyramids. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to one In(3) and two equivalent In(5) atoms. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to two equivalent In(6) and one Bi(2) atom. In the sixth S site, S(6) is bonded to one In(4), two equivalent In(2), and two equivalent In(6) atoms to form a mixture of corner and edge-sharing SIn5 square pyramids. In the seventh S site, S(7) is bonded in a distorted T-shaped geometry to two equivalent In(1) and one Bi(3) atom. In the eighth S site, S(8) is bonded in a rectangular see-saw-like geometry to one In(4), one In(5), and two equivalent In(3) atoms. In the ninth S site, S(9) is bonded in a trigonal non-coplanar geometry to one Bi(1) and two equivalent Bi(2) atoms. In the tenth S site, S(10) is bonded in a 3-coordinate geometry to one In(6) and two equivalent In(4) atoms. In the eleventh S site, S(11) is bonded in a 3-coordinate geometry to three equivalent In(3) atoms. In the twelfth S site, S(12) is bonded in a trigonal non-coplanar geometry to one In(5) and two equivalent Bi(1) atoms.