Mg2TiW3S8 is Spinel-derived structured and crystallizes in the monoclinic C2 space group. Mg(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form MgS4 tetrahedra that share corners with three equivalent Ti(1)S6 octahedra, corners with three equivalent W(2)S6 octahedra, and corners with six equivalent W(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-66°. Ti(1) is bonded to two equivalent S(1), two equivalent S(3), and two equivalent S(4) atoms to form TiS6 octahedra that share corners with six equivalent Mg(1)S4 tetrahedra, edges with two equivalent W(2)S6 octahedra, and edges with four equivalent W(1)S6 octahedra. There are two inequivalent W sites. In the first W site, W(1) is bonded to one S(1), one S(4), two equivalent S(2), and two equivalent S(3) atoms to form WS6 octahedra that share corners with six equivalent Mg(1)S4 tetrahedra, edges with two equivalent Ti(1)S6 octahedra, edges with two equivalent W(1)S6 octahedra, and edges with two equivalent W(2)S6 octahedra. In the second W site, W(2) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms to form WS6 octahedra that share corners with six equivalent Mg(1)S4 tetrahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with four equivalent W(1)S6 octahedra. There are four inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Mg(1), one Ti(1), one W(1), and one W(2) atom. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one W(2), and two equivalent W(1) atoms. In the third S site, S(3) is bonded to one Mg(1), one Ti(1), and two equivalent W(1) atoms to form distorted corner-sharing SMgTiW2 trigonal pyramids. In the fourth S site, S(4) is bonded in a rectangular see-saw-like geometry to one Mg(1), one Ti(1), one W(1), and one W(2) atom.
Mg2TiW3S8 is Spinel-derived structured and crystallizes in the monoclinic C2 space group. Mg(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form MgS4 tetrahedra that share corners with three equivalent Ti(1)S6 octahedra, corners with three equivalent W(2)S6 octahedra, and corners with six equivalent W(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-66°. The Mg(1)-S(1) bond length is 2.40 Å. The Mg(1)-S(2) bond length is 2.42 Å. The Mg(1)-S(3) bond length is 2.39 Å. The Mg(1)-S(4) bond length is 2.40 Å. Ti(1) is bonded to two equivalent S(1), two equivalent S(3), and two equivalent S(4) atoms to form TiS6 octahedra that share corners with six equivalent Mg(1)S4 tetrahedra, edges with two equivalent W(2)S6 octahedra, and edges with four equivalent W(1)S6 octahedra. Both Ti(1)-S(1) bond lengths are 2.49 Å. Both Ti(1)-S(3) bond lengths are 2.50 Å. Both Ti(1)-S(4) bond lengths are 2.49 Å. There are two inequivalent W sites. In the first W site, W(1) is bonded to one S(1), one S(4), two equivalent S(2), and two equivalent S(3) atoms to form WS6 octahedra that share corners with six equivalent Mg(1)S4 tetrahedra, edges with two equivalent Ti(1)S6 octahedra, edges with two equivalent W(1)S6 octahedra, and edges with two equivalent W(2)S6 octahedra. The W(1)-S(1) bond length is 2.48 Å. The W(1)-S(4) bond length is 2.48 Å. Both W(1)-S(2) bond lengths are 2.50 Å. Both W(1)-S(3) bond lengths are 2.49 Å. In the second W site, W(2) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms to form WS6 octahedra that share corners with six equivalent Mg(1)S4 tetrahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with four equivalent W(1)S6 octahedra. Both W(2)-S(1) bond lengths are 2.48 Å. Both W(2)-S(2) bond lengths are 2.50 Å. Both W(2)-S(4) bond lengths are 2.48 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Mg(1), one Ti(1), one W(1), and one W(2) atom. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one W(2), and two equivalent W(1) atoms. In the third S site, S(3) is bonded to one Mg(1), one Ti(1), and two equivalent W(1) atoms to form distorted corner-sharing SMgTiW2 trigonal pyramids. In the fourth S site, S(4) is bonded in a rectangular see-saw-like geometry to one Mg(1), one Ti(1), one W(1), and one W(2) atom.