Ti2V2GaS8 crystallizes in the orthorhombic Imm2 space group. Ti(1) is bonded to one S(2), one S(4), two equivalent S(1), and two equivalent S(3) atoms to form TiS6 octahedra that share corners with three equivalent Ga(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 one S(1), one S(3), two equivalent S(2), and two equivalent S(4) atoms to form VS6 octahedra that share corners with three equivalent Ga(1)S4 tetrahedra, edges with two equivalent V(1)S6 octahedra, and edges with four equivalent Ti(1)S6 octahedra. Ga(1) is bonded to two equivalent S(3) and two equivalent S(4) atoms to form GaS4 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 60-64°. There are four inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to two equivalent Ti(1) and one V(1) atom. In the second S site, S(2) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent V(1) atoms. In the third S site, S(3) is bonded to two equivalent Ti(1), one V(1), and one Ga(1) atom to form STi2VGa tetrahedra that share  a cornercorner with one S(3)Ti2VGa tetrahedra, corners with two equivalent S(4)TiV2Ga tetrahedra,  an edgeedge with one S(3)Ti2VGa tetrahedra, and edges with two equivalent S(4)TiV2Ga tetrahedra. In the fourth S site, S(4) is bonded to one Ti(1), two equivalent V(1), and one Ga(1) atom to form STiV2Ga tetrahedra that share  a cornercorner with one S(4)TiV2Ga tetrahedra, corners with two equivalent S(3)Ti2VGa tetrahedra,  an edgeedge with one S(4)TiV2Ga tetrahedra, and edges with two equivalent S(3)Ti2VGa tetrahedra.
Ti2V2GaS8 crystallizes in the orthorhombic Imm2 space group. Ti(1) is bonded to one S(2), one S(4), two equivalent S(1), and two equivalent S(3) atoms to form TiS6 octahedra that share corners with three equivalent Ga(1)S4 tetrahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with four equivalent V(1)S6 octahedra. The Ti(1)-S(2) bond length is 2.34 Å. The Ti(1)-S(4) bond length is 2.61 Å. Both Ti(1)-S(1) bond lengths are 2.36 Å. Both Ti(1)-S(3) bond lengths are 2.55 Å. V(1) is bonded to one S(1), one S(3), two equivalent S(2), and two equivalent S(4) atoms to form VS6 octahedra that share corners with three equivalent Ga(1)S4 tetrahedra, edges with two equivalent V(1)S6 octahedra, and edges with four equivalent Ti(1)S6 octahedra. The V(1)-S(1) bond length is 2.37 Å. The V(1)-S(3) bond length is 2.52 Å. Both V(1)-S(2) bond lengths are 2.35 Å. Both V(1)-S(4) bond lengths are 2.53 Å. Ga(1) is bonded to two equivalent S(3) and two equivalent S(4) atoms to form GaS4 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 60-64°. Both Ga(1)-S(3) bond lengths are 2.31 Å. Both Ga(1)-S(4) bond lengths are 2.32 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to two equivalent Ti(1) and one V(1) atom. In the second S site, S(2) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent V(1) atoms. In the third S site, S(3) is bonded to two equivalent Ti(1), one V(1), and one Ga(1) atom to form STi2VGa tetrahedra that share  a cornercorner with one S(3)Ti2VGa tetrahedra, corners with two equivalent S(4)TiV2Ga tetrahedra,  an edgeedge with one S(3)Ti2VGa tetrahedra, and edges with two equivalent S(4)TiV2Ga tetrahedra. In the fourth S site, S(4) is bonded to one Ti(1), two equivalent V(1), and one Ga(1) atom to form STiV2Ga tetrahedra that share  a cornercorner with one S(4)TiV2Ga tetrahedra, corners with two equivalent S(3)Ti2VGa tetrahedra,  an edgeedge with one S(4)TiV2Ga tetrahedra, and edges with two equivalent S(3)Ti2VGa tetrahedra.