Mn4ZnS8 crystallizes in the trigonal R-3m space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to six equivalent S(1) atoms to form MnS6 octahedra that share corners with six equivalent Zn(1)S6 octahedra and edges with six equivalent Mn(2)S6 octahedra. The corner-sharing octahedral tilt angles are 7°. In the second Mn site, Mn(2) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form MnS6 octahedra that share edges with two equivalent Mn(1)S6 octahedra, edges with two equivalent Zn(1)S6 octahedra, and edges with four equivalent Mn(2)S6 octahedra. Zn(1) is bonded to six equivalent S(1) atoms to form ZnS6 octahedra that share corners with six equivalent Mn(1)S6 octahedra and edges with six equivalent Mn(2)S6 octahedra. The corner-sharing octahedral tilt angles are 7°. There are two inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Mn(1), two equivalent Mn(2), and one Zn(1) atom. In the second S site, S(2) is bonded in a distorted T-shaped geometry to three equivalent Mn(2) atoms.
Mn4ZnS8 crystallizes in the trigonal R-3m space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to six equivalent S(1) atoms to form MnS6 octahedra that share corners with six equivalent Zn(1)S6 octahedra and edges with six equivalent Mn(2)S6 octahedra. The corner-sharing octahedral tilt angles are 7°. All Mn(1)-S(1) bond lengths are 2.45 Å. In the second Mn site, Mn(2) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form MnS6 octahedra that share edges with two equivalent Mn(1)S6 octahedra, edges with two equivalent Zn(1)S6 octahedra, and edges with four equivalent Mn(2)S6 octahedra. Both Mn(2)-S(2) bond lengths are 2.36 Å. All Mn(2)-S(1) bond lengths are 2.36 Å. Zn(1) is bonded to six equivalent S(1) atoms to form ZnS6 octahedra that share corners with six equivalent Mn(1)S6 octahedra and edges with six equivalent Mn(2)S6 octahedra. The corner-sharing octahedral tilt angles are 7°. All Zn(1)-S(1) bond lengths are 2.49 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Mn(1), two equivalent Mn(2), and one Zn(1) atom. In the second S site, S(2) is bonded in a distorted T-shaped geometry to three equivalent Mn(2) atoms.