Mn2SnS4 crystallizes in the monoclinic P2/m space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form MnS6 octahedra that share corners with six equivalent Sn(1)S6 octahedra, edges with two equivalent Mn(1)S6 octahedra, edges with two equivalent Sn(1)S6 octahedra, and edges with four equivalent Mn(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 8-13°. 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(2)S6 octahedra, edges with four equivalent Mn(1)S6 octahedra, and edges with four equivalent Sn(1)S6 octahedra. Sn(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form SnS6 octahedra that share corners with six equivalent Mn(1)S6 octahedra, edges with two equivalent Mn(1)S6 octahedra, edges with two equivalent Sn(1)S6 octahedra, and edges with four equivalent Mn(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 8-13°. There are two inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to one Mn(1), two equivalent Mn(2), and one Sn(1) atom. In the second S site, S(2) is bonded to one Mn(2), two equivalent Mn(1), and two equivalent Sn(1) atoms to form a mixture of corner and edge-sharing SMn3Sn2 square pyramids.
Mn2SnS4 crystallizes in the monoclinic P2/m space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form MnS6 octahedra that share corners with six equivalent Sn(1)S6 octahedra, edges with two equivalent Mn(1)S6 octahedra, edges with two equivalent Sn(1)S6 octahedra, and edges with four equivalent Mn(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 8-13°. Both Mn(1)-S(1) bond lengths are 2.46 Å. All Mn(1)-S(2) bond lengths are 2.54 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(2)S6 octahedra, edges with four equivalent Mn(1)S6 octahedra, and edges with four equivalent Sn(1)S6 octahedra. Both Mn(2)-S(2) bond lengths are 2.46 Å. All Mn(2)-S(1) bond lengths are 2.45 Å. Sn(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form SnS6 octahedra that share corners with six equivalent Mn(1)S6 octahedra, edges with two equivalent Mn(1)S6 octahedra, edges with two equivalent Sn(1)S6 octahedra, and edges with four equivalent Mn(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 8-13°. Both Sn(1)-S(1) bond lengths are 2.79 Å. All Sn(1)-S(2) bond lengths are 2.80 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to one Mn(1), two equivalent Mn(2), and one Sn(1) atom. In the second S site, S(2) is bonded to one Mn(2), two equivalent Mn(1), and two equivalent Sn(1) atoms to form a mixture of corner and edge-sharing SMn3Sn2 square pyramids.