MnBiS2Br crystallizes in the monoclinic C2/m space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form MnS6 octahedra that share corners with two equivalent Mn(2)S2Br4 octahedra, corners with four equivalent Bi(1)S5 square pyramids, edges with two equivalent Mn(1)S6 octahedra, and edges with six equivalent Bi(1)S5 square pyramids. The corner-sharing octahedral tilt angles are 42°. In the second Mn site, Mn(2) is bonded to two equivalent S(2) and four equivalent Br(1) atoms to form MnS2Br4 octahedra that share corners with two equivalent Mn(1)S6 octahedra, corners with four equivalent Bi(1)S5 square pyramids, and edges with two equivalent Mn(2)S2Br4 octahedra. The corner-sharing octahedral tilt angles are 42°. Bi(1) is bonded to two equivalent S(2) and three equivalent S(1) atoms to form distorted BiS5 square pyramids that share corners with two equivalent Mn(2)S2Br4 octahedra, corners with two equivalent Mn(1)S6 octahedra, edges with three equivalent Mn(1)S6 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 to two equivalent Mn(1) and three equivalent Bi(1) atoms to form a mixture of distorted edge and corner-sharing SMn2Bi3 square pyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Mn(1), one Mn(2), and two equivalent Bi(1) atoms. Br(1) is bonded in an L-shaped geometry to two equivalent Mn(2) atoms.
MnBiS2Br crystallizes in the monoclinic C2/m space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form MnS6 octahedra that share corners with two equivalent Mn(2)S2Br4 octahedra, corners with four equivalent Bi(1)S5 square pyramids, edges with two equivalent Mn(1)S6 octahedra, and edges with six equivalent Bi(1)S5 square pyramids. The corner-sharing octahedral tilt angles are 42°. Both Mn(1)-S(2) bond lengths are 2.53 Å. All Mn(1)-S(1) bond lengths are 2.67 Å. In the second Mn site, Mn(2) is bonded to two equivalent S(2) and four equivalent Br(1) atoms to form MnS2Br4 octahedra that share corners with two equivalent Mn(1)S6 octahedra, corners with four equivalent Bi(1)S5 square pyramids, and edges with two equivalent Mn(2)S2Br4 octahedra. The corner-sharing octahedral tilt angles are 42°. Both Mn(2)-S(2) bond lengths are 2.57 Å. All Mn(2)-Br(1) bond lengths are 2.70 Å. Bi(1) is bonded to two equivalent S(2) and three equivalent S(1) atoms to form distorted BiS5 square pyramids that share corners with two equivalent Mn(2)S2Br4 octahedra, corners with two equivalent Mn(1)S6 octahedra, edges with three equivalent Mn(1)S6 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(2) bond lengths are 2.72 Å. There is one shorter (2.61 Å) and two longer (3.04 Å) Bi(1)-S(1) bond lengths. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Mn(1) and three equivalent Bi(1) atoms to form a mixture of distorted edge and corner-sharing SMn2Bi3 square pyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Mn(1), one Mn(2), and two equivalent Bi(1) atoms. Br(1) is bonded in an L-shaped geometry to two equivalent Mn(2) atoms.