CdBiS2Cl crystallizes in the orthorhombic Pnma space group. Cd(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent Cl(1) atoms to form CdS4Cl2 octahedra that share corners with two equivalent Cd(1)S4Cl2 octahedra, corners with four equivalent Bi(1)S5 square pyramids, edges with two equivalent Cd(1)S4Cl2 octahedra, and edges with three equivalent Bi(1)S5 square pyramids. The corner-sharing octahedral tilt angles are 47°. Bi(1) is bonded to two equivalent S(1) and three equivalent S(2) atoms to form BiS5 square pyramids that share corners with four equivalent Cd(1)S4Cl2 octahedra, edges with three equivalent Cd(1)S4Cl2 octahedra, and edges with four equivalent Bi(1)S5 square pyramids. The corner-sharing octahedral tilt angles range from 16-67°. There are two inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Cd(1) and two equivalent Bi(1) atoms. In the second S site, S(2) is bonded to two equivalent Cd(1) and three equivalent Bi(1) atoms to form edge-sharing SCd2Bi3 square pyramids. Cl(1) is bonded in an L-shaped geometry to two equivalent Cd(1) atoms.
CdBiS2Cl crystallizes in the orthorhombic Pnma space group. Cd(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent Cl(1) atoms to form CdS4Cl2 octahedra that share corners with two equivalent Cd(1)S4Cl2 octahedra, corners with four equivalent Bi(1)S5 square pyramids, edges with two equivalent Cd(1)S4Cl2 octahedra, and edges with three equivalent Bi(1)S5 square pyramids. The corner-sharing octahedral tilt angles are 47°. There is one shorter (2.63 Å) and one longer (2.65 Å) Cd(1)-S(1) bond length. Both Cd(1)-S(2) bond lengths are 2.84 Å. Both Cd(1)-Cl(1) bond lengths are 2.69 Å. Bi(1) is bonded to two equivalent S(1) and three equivalent S(2) atoms to form BiS5 square pyramids that share corners with four equivalent Cd(1)S4Cl2 octahedra, edges with three equivalent Cd(1)S4Cl2 octahedra, and edges with four equivalent Bi(1)S5 square pyramids. The corner-sharing octahedral tilt angles range from 16-67°. Both Bi(1)-S(1) bond lengths are 2.74 Å. There is one shorter (2.62 Å) and two longer (3.01 Å) Bi(1)-S(2) bond lengths. There are two inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Cd(1) and two equivalent Bi(1) atoms. In the second S site, S(2) is bonded to two equivalent Cd(1) and three equivalent Bi(1) atoms to form edge-sharing SCd2Bi3 square pyramids. Cl(1) is bonded in an L-shaped geometry to two equivalent Cd(1) atoms.