MgWAlS4 is Hausmannite-derived structured and crystallizes in the monoclinic Cm space group. There are two inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to one S(5), one S(6), and two equivalent S(1) atoms to form MgS4 tetrahedra that share corners with three equivalent W(1)S6 octahedra, corners with three equivalent W(2)S6 octahedra, and corners with six equivalent Al(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 44-66°. In the second Mg site, Mg(2) is bonded to one S(2), one S(3), and two equivalent S(4) atoms to form MgS4 tetrahedra that share corners with three equivalent W(1)S6 octahedra, corners with three equivalent W(2)S6 octahedra, and corners with six equivalent Al(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 54-62°. There are two inequivalent W sites. In the first W site, W(1) is bonded to one S(3), one S(5), two equivalent S(1), and two equivalent S(4) atoms to form distorted WS6 octahedra that share corners with three equivalent Mg(1)S4 tetrahedra, corners with three equivalent Mg(2)S4 tetrahedra, edges with two equivalent W(2)S6 octahedra, and edges with four equivalent Al(1)S6 octahedra. In the second W site, W(2) is bonded to one S(2), one S(6), two equivalent S(1), and two equivalent S(4) atoms to form distorted WS6 octahedra that share corners with three equivalent Mg(1)S4 tetrahedra, corners with three equivalent Mg(2)S4 tetrahedra, edges with two equivalent W(1)S6 octahedra, and edges with four equivalent Al(1)S6 octahedra. Al(1) is bonded to one S(1), one S(2), one S(3), one S(4), one S(5), and one S(6) atom to form AlS6 octahedra that share corners with three equivalent Mg(1)S4 tetrahedra, corners with three equivalent Mg(2)S4 tetrahedra, edges with two equivalent W(1)S6 octahedra, edges with two equivalent W(2)S6 octahedra, and edges with two equivalent Al(1)S6 octahedra. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to one Mg(1), one W(1), one W(2), and one Al(1) atom. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to one Mg(2), one W(2), and two equivalent Al(1) atoms. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to one Mg(2), one W(1), and two equivalent Al(1) atoms. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to one Mg(2), one W(1), one W(2), and one Al(1) atom. In the fifth S site, S(5) is bonded to one Mg(1), one W(1), and two equivalent Al(1) atoms to form a mixture of distorted edge and corner-sharing SMgAl2W tetrahedra. In the sixth S site, S(6) is bonded to one Mg(1), one W(2), and two equivalent Al(1) atoms to form a mixture of distorted edge and corner-sharing SMgAl2W tetrahedra.
MgWAlS4 is Hausmannite-derived structured and crystallizes in the monoclinic Cm space group. There are two inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to one S(5), one S(6), and two equivalent S(1) atoms to form MgS4 tetrahedra that share corners with three equivalent W(1)S6 octahedra, corners with three equivalent W(2)S6 octahedra, and corners with six equivalent Al(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 44-66°. The Mg(1)-S(5) bond length is 2.39 Å. The Mg(1)-S(6) bond length is 2.40 Å. Both Mg(1)-S(1) bond lengths are 2.46 Å. In the second Mg site, Mg(2) is bonded to one S(2), one S(3), and two equivalent S(4) atoms to form MgS4 tetrahedra that share corners with three equivalent W(1)S6 octahedra, corners with three equivalent W(2)S6 octahedra, and corners with six equivalent Al(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 54-62°. The Mg(2)-S(2) bond length is 2.45 Å. The Mg(2)-S(3) bond length is 2.45 Å. Both Mg(2)-S(4) bond lengths are 2.45 Å. There are two inequivalent W sites. In the first W site, W(1) is bonded to one S(3), one S(5), two equivalent S(1), and two equivalent S(4) atoms to form distorted WS6 octahedra that share corners with three equivalent Mg(1)S4 tetrahedra, corners with three equivalent Mg(2)S4 tetrahedra, edges with two equivalent W(2)S6 octahedra, and edges with four equivalent Al(1)S6 octahedra. The W(1)-S(3) bond length is 2.47 Å. The W(1)-S(5) bond length is 2.46 Å. Both W(1)-S(1) bond lengths are 2.39 Å. Both W(1)-S(4) bond lengths are 2.63 Å. In the second W site, W(2) is bonded to one S(2), one S(6), two equivalent S(1), and two equivalent S(4) atoms to form distorted WS6 octahedra that share corners with three equivalent Mg(1)S4 tetrahedra, corners with three equivalent Mg(2)S4 tetrahedra, edges with two equivalent W(1)S6 octahedra, and edges with four equivalent Al(1)S6 octahedra. The W(2)-S(2) bond length is 2.47 Å. The W(2)-S(6) bond length is 2.46 Å. Both W(2)-S(1) bond lengths are 2.39 Å. Both W(2)-S(4) bond lengths are 2.63 Å. Al(1) is bonded to one S(1), one S(2), one S(3), one S(4), one S(5), and one S(6) atom to form AlS6 octahedra that share corners with three equivalent Mg(1)S4 tetrahedra, corners with three equivalent Mg(2)S4 tetrahedra, edges with two equivalent W(1)S6 octahedra, edges with two equivalent W(2)S6 octahedra, and edges with two equivalent Al(1)S6 octahedra. The Al(1)-S(1) bond length is 2.49 Å. The Al(1)-S(2) bond length is 2.44 Å. The Al(1)-S(3) bond length is 2.44 Å. The Al(1)-S(4) bond length is 2.39 Å. The Al(1)-S(5) bond length is 2.47 Å. The Al(1)-S(6) bond length is 2.47 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to one Mg(1), one W(1), one W(2), and one Al(1) atom. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to one Mg(2), one W(2), and two equivalent Al(1) atoms. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to one Mg(2), one W(1), and two equivalent Al(1) atoms. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to one Mg(2), one W(1), one W(2), and one Al(1) atom. In the fifth S site, S(5) is bonded to one Mg(1), one W(1), and two equivalent Al(1) atoms to form a mixture of distorted edge and corner-sharing SMgAl2W tetrahedra. In the sixth S site, S(6) is bonded to one Mg(1), one W(2), and two equivalent Al(1) atoms to form a mixture of distorted edge and corner-sharing SMgAl2W tetrahedra.