V8GaGeS16 crystallizes in the tetragonal P-4m2 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one S(3), two equivalent S(4), and three equivalent S(1) atoms to form distorted VS6 octahedra that share  a cornercorner with one Ga(1)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, edges with two equivalent V(2)S6 octahedra, and edges with four equivalent V(1)S6 octahedra. In the second V site, V(2) is bonded to one S(4), two equivalent S(3), and three equivalent S(2) atoms to form distorted VS6 octahedra that share  a cornercorner with one Ge(1)S4 tetrahedra, corners with two equivalent Ga(1)S4 tetrahedra, edges with two equivalent V(1)S6 octahedra, and edges with four equivalent V(2)S6 octahedra. Ga(1) is bonded to four equivalent S(3) atoms to form GaS4 tetrahedra that share corners with four equivalent V(1)S6 octahedra and corners with eight equivalent V(2)S6 octahedra. The corner-sharing octahedral tilt angles are 65°. Ge(1) is bonded to four equivalent S(4) atoms to form GeS4 tetrahedra that share corners with four equivalent V(2)S6 octahedra and corners with eight equivalent V(1)S6 octahedra. The corner-sharing octahedral tilt angles are 64°. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to three equivalent V(1) atoms. In the second S site, S(2) is bonded in a 3-coordinate geometry to three equivalent V(2) atoms. In the third S site, S(3) is bonded to one V(1), two equivalent V(2), and one Ga(1) atom to form SV3Ga tetrahedra that share corners with three equivalent S(3)V3Ga tetrahedra,  an edgeedge with one S(3)V3Ga tetrahedra, and edges with two equivalent S(4)V3Ge tetrahedra. In the fourth S site, S(4) is bonded to one V(2), two equivalent V(1), and one Ge(1) atom to form SV3Ge tetrahedra that share corners with three equivalent S(4)V3Ge tetrahedra,  an edgeedge with one S(4)V3Ge tetrahedra, and edges with two equivalent S(3)V3Ga tetrahedra.
V8GaGeS16 crystallizes in the tetragonal P-4m2 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one S(3), two equivalent S(4), and three equivalent S(1) atoms to form distorted VS6 octahedra that share  a cornercorner with one Ga(1)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, edges with two equivalent V(2)S6 octahedra, and edges with four equivalent V(1)S6 octahedra. The V(1)-S(3) bond length is 2.54 Å. Both V(1)-S(4) bond lengths are 2.57 Å. All V(1)-S(1) bond lengths are 2.30 Å. In the second V site, V(2) is bonded to one S(4), two equivalent S(3), and three equivalent S(2) atoms to form distorted VS6 octahedra that share  a cornercorner with one Ge(1)S4 tetrahedra, corners with two equivalent Ga(1)S4 tetrahedra, edges with two equivalent V(1)S6 octahedra, and edges with four equivalent V(2)S6 octahedra. The V(2)-S(4) bond length is 2.56 Å. Both V(2)-S(3) bond lengths are 2.55 Å. All V(2)-S(2) bond lengths are 2.30 Å. Ga(1) is bonded to four equivalent S(3) atoms to form GaS4 tetrahedra that share corners with four equivalent V(1)S6 octahedra and corners with eight equivalent V(2)S6 octahedra. The corner-sharing octahedral tilt angles are 65°. All Ga(1)-S(3) bond lengths are 2.31 Å. Ge(1) is bonded to four equivalent S(4) atoms to form GeS4 tetrahedra that share corners with four equivalent V(2)S6 octahedra and corners with eight equivalent V(1)S6 octahedra. The corner-sharing octahedral tilt angles are 64°. All Ge(1)-S(4) bond lengths are 2.29 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to three equivalent V(1) atoms. In the second S site, S(2) is bonded in a 3-coordinate geometry to three equivalent V(2) atoms. In the third S site, S(3) is bonded to one V(1), two equivalent V(2), and one Ga(1) atom to form SV3Ga tetrahedra that share corners with three equivalent S(3)V3Ga tetrahedra,  an edgeedge with one S(3)V3Ga tetrahedra, and edges with two equivalent S(4)V3Ge tetrahedra. In the fourth S site, S(4) is bonded to one V(2), two equivalent V(1), and one Ge(1) atom to form SV3Ge tetrahedra that share corners with three equivalent S(4)V3Ge tetrahedra,  an edgeedge with one S(4)V3Ge tetrahedra, and edges with two equivalent S(3)V3Ga tetrahedra.