MnBiS2Cl crystallizes in the orthorhombic Pnma space group. Mn(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent Cl(1) atoms to form MnS4Cl2 octahedra that share corners with two equivalent Mn(1)S4Cl2 octahedra, corners with four equivalent Bi(1)S5 square pyramids, edges with two equivalent Mn(1)S4Cl2 octahedra, and edges with three equivalent Bi(1)S5 square pyramids. The corner-sharing octahedral tilt angles are 41°. 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 Mn(1)S4Cl2 octahedra, edges with three equivalent Mn(1)S4Cl2 octahedra, and edges with four equivalent Bi(1)S5 square pyramids. The corner-sharing octahedral tilt angles range from 16-68°. There are two inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to two equivalent Mn(1) and two equivalent Bi(1) atoms. In the second S site, S(2) is bonded to two equivalent Mn(1) and three equivalent Bi(1) atoms to form distorted edge-sharing SMn2Bi3 square pyramids. Cl(1) is bonded in a water-like geometry to two equivalent Mn(1) atoms.
MnBiS2Cl crystallizes in the orthorhombic Pnma space group. Mn(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent Cl(1) atoms to form MnS4Cl2 octahedra that share corners with two equivalent Mn(1)S4Cl2 octahedra, corners with four equivalent Bi(1)S5 square pyramids, edges with two equivalent Mn(1)S4Cl2 octahedra, and edges with three equivalent Bi(1)S5 square pyramids. The corner-sharing octahedral tilt angles are 41°. Both Mn(1)-S(1) bond lengths are 2.54 Å. Both Mn(1)-S(2) bond lengths are 2.66 Å. Both Mn(1)-Cl(1) bond lengths are 2.57 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 Mn(1)S4Cl2 octahedra, edges with three equivalent Mn(1)S4Cl2 octahedra, and edges with four equivalent Bi(1)S5 square pyramids. The corner-sharing octahedral tilt angles range from 16-68°. Both Bi(1)-S(1) bond lengths are 2.71 Å. There is one shorter (2.62 Å) and two longer (3.03 Å) Bi(1)-S(2) bond lengths. There are two inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to two equivalent Mn(1) and two equivalent Bi(1) atoms. In the second S site, S(2) is bonded to two equivalent Mn(1) and three equivalent Bi(1) atoms to form distorted edge-sharing SMn2Bi3 square pyramids. Cl(1) is bonded in a water-like geometry to two equivalent Mn(1) atoms.