Mg2Ti3VS8 is Spinel-derived structured and crystallizes in the trigonal R-3m space group. Mg(1) is bonded to one S(1) and three equivalent S(2) atoms to form MgS4 tetrahedra that share corners with three equivalent V(1)S6 octahedra and corners with nine equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles are 58°. Ti(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form TiS6 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. V(1) is bonded to six equivalent S(2) atoms to form VS6 octahedra that share corners with six equivalent Mg(1)S4 tetrahedra and edges with six equivalent Ti(1)S6 octahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded to one Mg(1) and three equivalent Ti(1) atoms to form distorted SMgTi3 trigonal pyramids that share corners with three equivalent S(1)MgTi3 trigonal pyramids, corners with nine equivalent S(2)MgTi2V trigonal pyramids, and edges with three equivalent S(2)MgTi2V trigonal pyramids. In the second S site, S(2) 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 three equivalent S(1)MgTi3 trigonal pyramids, corners with nine equivalent S(2)MgTi2V trigonal pyramids,  an edgeedge with one S(1)MgTi3 trigonal pyramid, and edges with two equivalent S(2)MgTi2V trigonal pyramids.
Mg2Ti3VS8 is Spinel-derived structured and crystallizes in the trigonal R-3m space group. Mg(1) is bonded to one S(1) and three equivalent S(2) atoms to form MgS4 tetrahedra that share corners with three equivalent V(1)S6 octahedra and corners with nine equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles are 58°. The Mg(1)-S(1) bond length is 2.42 Å. All Mg(1)-S(2) bond lengths are 2.42 Å. Ti(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form TiS6 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 Ti(1)-S(1) bond lengths are 2.50 Å. All Ti(1)-S(2) bond lengths are 2.49 Å. V(1) is bonded to six equivalent S(2) atoms to form VS6 octahedra that share corners with six equivalent Mg(1)S4 tetrahedra and edges with six equivalent Ti(1)S6 octahedra. All V(1)-S(2) bond lengths are 2.49 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to one Mg(1) and three equivalent Ti(1) atoms to form distorted SMgTi3 trigonal pyramids that share corners with three equivalent S(1)MgTi3 trigonal pyramids, corners with nine equivalent S(2)MgTi2V trigonal pyramids, and edges with three equivalent S(2)MgTi2V trigonal pyramids. In the second S site, S(2) 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 three equivalent S(1)MgTi3 trigonal pyramids, corners with nine equivalent S(2)MgTi2V trigonal pyramids,  an edgeedge with one S(1)MgTi3 trigonal pyramid, and edges with two equivalent S(2)MgTi2V trigonal pyramids.