BiInS3 crystallizes in the monoclinic P2_1/m space group. In(1) is bonded to three equivalent S(2) and three equivalent S(3) atoms to form InS6 octahedra that share corners with three equivalent Bi(1)S6 octahedra, edges with three equivalent Bi(1)S6 octahedra, and edges with six equivalent In(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 8-9°. Bi(1) is bonded to one S(3), two equivalent S(2), and three equivalent S(1) atoms to form BiS6 octahedra that share corners with three equivalent In(1)S6 octahedra, edges with three equivalent In(1)S6 octahedra, and edges with four equivalent Bi(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 8-9°. There are three inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to three equivalent Bi(1) atoms. In the second S site, S(2) is bonded to three equivalent In(1) and two equivalent Bi(1) atoms to form edge-sharing SIn3Bi2 square pyramids. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to three equivalent In(1) and one Bi(1) atom.
BiInS3 crystallizes in the monoclinic P2_1/m space group. In(1) is bonded to three equivalent S(2) and three equivalent S(3) atoms to form InS6 octahedra that share corners with three equivalent Bi(1)S6 octahedra, edges with three equivalent Bi(1)S6 octahedra, and edges with six equivalent In(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 8-9°. There is one shorter (2.62 Å) and two longer (2.72 Å) In(1)-S(2) bond lengths. All In(1)-S(3) bond lengths are 2.62 Å. Bi(1) is bonded to one S(3), two equivalent S(2), and three equivalent S(1) atoms to form BiS6 octahedra that share corners with three equivalent In(1)S6 octahedra, edges with three equivalent In(1)S6 octahedra, and edges with four equivalent Bi(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 8-9°. The Bi(1)-S(3) bond length is 2.95 Å. Both Bi(1)-S(2) bond lengths are 3.00 Å. There are two shorter (2.69 Å) and one longer (2.74 Å) Bi(1)-S(1) bond length. There are three inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to three equivalent Bi(1) atoms. In the second S site, S(2) is bonded to three equivalent In(1) and two equivalent Bi(1) atoms to form edge-sharing SIn3Bi2 square pyramids. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to three equivalent In(1) and one Bi(1) atom.