Mn2AlS4 crystallizes in the orthorhombic Imma 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 edges with two equivalent Mn(1)S6 octahedra, edges with four equivalent Mn(2)S6 octahedra, and edges with four equivalent Al(1)S6 octahedra. In the second Mn site, Mn(2) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form MnS6 octahedra that share corners with six equivalent Al(1)S6 octahedra, edges with two equivalent Mn(2)S6 octahedra, edges with two equivalent Al(1)S6 octahedra, and edges with four equivalent Mn(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. Al(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form AlS6 octahedra that share corners with six equivalent Mn(2)S6 octahedra, edges with two equivalent Mn(2)S6 octahedra, edges with two equivalent Al(1)S6 octahedra, and edges with four equivalent Mn(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. 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(2), two equivalent Mn(1), and one Al(1) atom. In the second S site, S(2) is bonded to one Mn(1), two equivalent Mn(2), and two equivalent Al(1) atoms to form a mixture of corner and edge-sharing SMn3Al2 square pyramids.
Mn2AlS4 crystallizes in the orthorhombic Imma 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 edges with two equivalent Mn(1)S6 octahedra, edges with four equivalent Mn(2)S6 octahedra, and edges with four equivalent Al(1)S6 octahedra. Both Mn(1)-S(2) bond lengths are 2.36 Å. All Mn(1)-S(1) bond lengths are 2.37 Å. In the second Mn site, Mn(2) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form MnS6 octahedra that share corners with six equivalent Al(1)S6 octahedra, edges with two equivalent Mn(2)S6 octahedra, edges with two equivalent Al(1)S6 octahedra, and edges with four equivalent Mn(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. Both Mn(2)-S(1) bond lengths are 2.53 Å. All Mn(2)-S(2) bond lengths are 2.55 Å. Al(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form AlS6 octahedra that share corners with six equivalent Mn(2)S6 octahedra, edges with two equivalent Mn(2)S6 octahedra, edges with two equivalent Al(1)S6 octahedra, and edges with four equivalent Mn(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. Both Al(1)-S(1) bond lengths are 2.40 Å. All Al(1)-S(2) bond lengths are 2.46 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(2), two equivalent Mn(1), and one Al(1) atom. In the second S site, S(2) is bonded to one Mn(1), two equivalent Mn(2), and two equivalent Al(1) atoms to form a mixture of corner and edge-sharing SMn3Al2 square pyramids.