MgTiVS4 is Spinel-derived structured and crystallizes in the orthorhombic Imma space group. Mg(1) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form MgS4 tetrahedra that share corners with six equivalent Ti(1)S6 octahedra and corners with six equivalent V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 57-59°. Ti(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form TiS6 octahedra that share corners with six equivalent Mg(1)S4 tetrahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with four equivalent V(1)S6 octahedra. V(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form VS6 octahedra that share corners with six equivalent Mg(1)S4 tetrahedra, edges with two equivalent V(1)S6 octahedra, and edges with four equivalent Ti(1)S6 octahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded to one Mg(1), two equivalent Ti(1), and one V(1) atom to form distorted SMgTi2V trigonal pyramids that share corners with six equivalent S(1)MgTi2V trigonal pyramids, corners with six equivalent S(2)MgTiV2 trigonal pyramids,  an edgeedge with one S(1)MgTi2V trigonal pyramid, and edges with two equivalent S(2)MgTiV2 trigonal pyramids. In the second S site, S(2) is bonded to one Mg(1), one Ti(1), and two equivalent V(1) atoms to form distorted SMgTiV2 trigonal pyramids that share corners with six equivalent S(1)MgTi2V trigonal pyramids, corners with six equivalent S(2)MgTiV2 trigonal pyramids,  an edgeedge with one S(2)MgTiV2 trigonal pyramid, and edges with two equivalent S(1)MgTi2V trigonal pyramids.
MgTiVS4 is Spinel-derived structured and crystallizes in the orthorhombic Imma space group. Mg(1) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form MgS4 tetrahedra that share corners with six equivalent Ti(1)S6 octahedra and corners with six equivalent V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 57-59°. Both Mg(1)-S(1) bond lengths are 2.42 Å. Both Mg(1)-S(2) bond lengths are 2.40 Å. Ti(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form TiS6 octahedra that share corners with six equivalent Mg(1)S4 tetrahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with four equivalent V(1)S6 octahedra. Both Ti(1)-S(2) bond lengths are 2.47 Å. All Ti(1)-S(1) bond lengths are 2.49 Å. V(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form VS6 octahedra that share corners with six equivalent Mg(1)S4 tetrahedra, edges with two equivalent V(1)S6 octahedra, and edges with four equivalent Ti(1)S6 octahedra. Both V(1)-S(1) bond lengths are 2.48 Å. All V(1)-S(2) bond lengths are 2.47 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to one Mg(1), two equivalent Ti(1), and one V(1) atom to form distorted SMgTi2V trigonal pyramids that share corners with six equivalent S(1)MgTi2V trigonal pyramids, corners with six equivalent S(2)MgTiV2 trigonal pyramids,  an edgeedge with one S(1)MgTi2V trigonal pyramid, and edges with two equivalent S(2)MgTiV2 trigonal pyramids. In the second S site, S(2) is bonded to one Mg(1), one Ti(1), and two equivalent V(1) atoms to form distorted SMgTiV2 trigonal pyramids that share corners with six equivalent S(1)MgTi2V trigonal pyramids, corners with six equivalent S(2)MgTiV2 trigonal pyramids,  an edgeedge with one S(2)MgTiV2 trigonal pyramid, and edges with two equivalent S(1)MgTi2V trigonal pyramids.