Mg2SnS4 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form MgS6 octahedra that share corners with four equivalent Mg(2)S6 octahedra, corners with two equivalent Sn(1)S4 tetrahedra, edges with two equivalent Mg(1)S6 octahedra, edges with two equivalent Mg(2)S6 octahedra, and edges with two equivalent Sn(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-54°. In the second Mg site, Mg(2) is bonded to one S(1), one S(2), and four equivalent S(3) atoms to form MgS6 octahedra that share corners with four equivalent Mg(1)S6 octahedra, corners with four equivalent Mg(2)S6 octahedra, corners with four equivalent Sn(1)S4 tetrahedra, edges with two equivalent Mg(1)S6 octahedra, and  an edgeedge with one Sn(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-54°. Sn(1) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form SnS4 tetrahedra that share corners with two equivalent Mg(1)S6 octahedra, corners with four equivalent Mg(2)S6 octahedra,  an edgeedge with one Mg(2)S6 octahedra, and edges with two equivalent Mg(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 61-66°. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Mg(2), two equivalent Mg(1), and one Sn(1) atom to form corner-sharing SMg3Sn tetrahedra. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Mg(2), two equivalent Mg(1), and one Sn(1) atom. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Mg(1), two equivalent Mg(2), and one Sn(1) atom.
Mg2SnS4 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form MgS6 octahedra that share corners with four equivalent Mg(2)S6 octahedra, corners with two equivalent Sn(1)S4 tetrahedra, edges with two equivalent Mg(1)S6 octahedra, edges with two equivalent Mg(2)S6 octahedra, and edges with two equivalent Sn(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-54°. Both Mg(1)-S(1) bond lengths are 2.55 Å. Both Mg(1)-S(2) bond lengths are 2.63 Å. Both Mg(1)-S(3) bond lengths are 2.66 Å. In the second Mg site, Mg(2) is bonded to one S(1), one S(2), and four equivalent S(3) atoms to form MgS6 octahedra that share corners with four equivalent Mg(1)S6 octahedra, corners with four equivalent Mg(2)S6 octahedra, corners with four equivalent Sn(1)S4 tetrahedra, edges with two equivalent Mg(1)S6 octahedra, and  an edgeedge with one Sn(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-54°. The Mg(2)-S(1) bond length is 2.61 Å. The Mg(2)-S(2) bond length is 2.57 Å. There are two shorter (2.61 Å) and two longer (2.74 Å) Mg(2)-S(3) bond lengths. Sn(1) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form SnS4 tetrahedra that share corners with two equivalent Mg(1)S6 octahedra, corners with four equivalent Mg(2)S6 octahedra,  an edgeedge with one Mg(2)S6 octahedra, and edges with two equivalent Mg(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 61-66°. The Sn(1)-S(1) bond length is 2.36 Å. The Sn(1)-S(2) bond length is 2.41 Å. Both Sn(1)-S(3) bond lengths are 2.40 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Mg(2), two equivalent Mg(1), and one Sn(1) atom to form corner-sharing SMg3Sn tetrahedra. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Mg(2), two equivalent Mg(1), and one Sn(1) atom. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Mg(1), two equivalent Mg(2), and one Sn(1) atom.