MnBi4S7 crystallizes in the monoclinic C2/m space group. Mn(1) is bonded to two equivalent S(1) and four equivalent S(3) atoms to form MnS6 octahedra that share corners with two equivalent Bi(1)S6 octahedra, corners with four equivalent Bi(2)S5 square pyramids, edges with two equivalent Mn(1)S6 octahedra, and edges with six equivalent Bi(2)S5 square pyramids. The corner-sharing octahedral tilt angles are 50°. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(1), two equivalent S(4), and three equivalent S(2) atoms to form BiS6 octahedra that share  a cornercorner with one Mn(1)S6 octahedra, corners with two equivalent Bi(1)S6 octahedra, corners with two equivalent Bi(2)S5 square pyramids, and edges with five equivalent Bi(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 0-50°. In the second Bi site, Bi(2) is bonded to two equivalent S(1) and three equivalent S(3) atoms to form distorted BiS5 square pyramids that share corners with two equivalent Mn(1)S6 octahedra, corners with two equivalent Bi(1)S6 octahedra, edges with three equivalent Mn(1)S6 octahedra, and edges with four equivalent Bi(2)S5 square pyramids. The corner-sharing octahedral tilt angles range from 14-65°. There are four inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to one Mn(1), one Bi(1), and two equivalent Bi(2) atoms. In the second S site, S(2) is bonded in a distorted T-shaped geometry to three equivalent Bi(1) atoms. In the third S site, S(3) is bonded to two equivalent Mn(1) and three equivalent Bi(2) atoms to form a mixture of edge and corner-sharing SMn2Bi3 square pyramids. In the fourth S site, S(4) is bonded in a square co-planar geometry to four equivalent Bi(1) atoms.
MnBi4S7 crystallizes in the monoclinic C2/m space group. Mn(1) is bonded to two equivalent S(1) and four equivalent S(3) atoms to form MnS6 octahedra that share corners with two equivalent Bi(1)S6 octahedra, corners with four equivalent Bi(2)S5 square pyramids, edges with two equivalent Mn(1)S6 octahedra, and edges with six equivalent Bi(2)S5 square pyramids. The corner-sharing octahedral tilt angles are 50°. Both Mn(1)-S(1) bond lengths are 2.47 Å. All Mn(1)-S(3) bond lengths are 2.72 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(1), two equivalent S(4), and three equivalent S(2) atoms to form BiS6 octahedra that share  a cornercorner with one Mn(1)S6 octahedra, corners with two equivalent Bi(1)S6 octahedra, corners with two equivalent Bi(2)S5 square pyramids, and edges with five equivalent Bi(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 0-50°. The Bi(1)-S(1) bond length is 2.94 Å. Both Bi(1)-S(4) bond lengths are 2.80 Å. There is one shorter (2.73 Å) and two longer (2.78 Å) Bi(1)-S(2) bond lengths. In the second Bi site, Bi(2) is bonded to two equivalent S(1) and three equivalent S(3) atoms to form distorted BiS5 square pyramids that share corners with two equivalent Mn(1)S6 octahedra, corners with two equivalent Bi(1)S6 octahedra, edges with three equivalent Mn(1)S6 octahedra, and edges with four equivalent Bi(2)S5 square pyramids. The corner-sharing octahedral tilt angles range from 14-65°. Both Bi(2)-S(1) bond lengths are 2.72 Å. There is one shorter (2.63 Å) and two longer (3.01 Å) Bi(2)-S(3) bond lengths. There are four inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to one Mn(1), one Bi(1), and two equivalent Bi(2) atoms. In the second S site, S(2) is bonded in a distorted T-shaped geometry to three equivalent Bi(1) atoms. In the third S site, S(3) is bonded to two equivalent Mn(1) and three equivalent Bi(2) atoms to form a mixture of edge and corner-sharing SMn2Bi3 square pyramids. In the fourth S site, S(4) is bonded in a square co-planar geometry to four equivalent Bi(1) atoms.