VMo3GaS8 crystallizes in the trigonal R3m space group. V(1) is bonded in a 6-coordinate geometry to three equivalent S(2) and three equivalent S(4) atoms. Mo(1) is bonded in a 6-coordinate geometry to one S(1), one S(3), two equivalent S(2), and two equivalent S(4) atoms. Ga(1) is bonded in a tetrahedral geometry to one S(1) and three equivalent S(2) atoms. There are four inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Mo(1) and one Ga(1) atom to form a mixture of distorted corner and edge-sharing SGaMo3 tetrahedra. In the second S site, S(2) is bonded to one V(1), two equivalent Mo(1), and one Ga(1) atom to form SVGaMo2 tetrahedra that share  a cornercorner with one S(1)GaMo3 tetrahedra, corners with two equivalent S(2)VGaMo2 tetrahedra,  an edgeedge with one S(1)GaMo3 tetrahedra, and edges with two equivalent S(2)VGaMo2 tetrahedra. In the third S site, S(3) is bonded in a 3-coordinate geometry to three equivalent Mo(1) atoms. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to one V(1) and two equivalent Mo(1) atoms.
VMo3GaS8 crystallizes in the trigonal R3m space group. V(1) is bonded in a 6-coordinate geometry to three equivalent S(2) and three equivalent S(4) atoms. All V(1)-S(2) bond lengths are 2.56 Å. All V(1)-S(4) bond lengths are 2.30 Å. Mo(1) is bonded in a 6-coordinate geometry to one S(1), one S(3), two equivalent S(2), and two equivalent S(4) atoms. The Mo(1)-S(1) bond length is 2.63 Å. The Mo(1)-S(3) bond length is 2.35 Å. Both Mo(1)-S(2) bond lengths are 2.61 Å. Both Mo(1)-S(4) bond lengths are 2.36 Å. Ga(1) is bonded in a tetrahedral geometry to one S(1) and three equivalent S(2) atoms. The Ga(1)-S(1) bond length is 2.32 Å. All Ga(1)-S(2) bond lengths are 2.30 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Mo(1) and one Ga(1) atom to form a mixture of distorted corner and edge-sharing SGaMo3 tetrahedra. In the second S site, S(2) is bonded to one V(1), two equivalent Mo(1), and one Ga(1) atom to form SVGaMo2 tetrahedra that share  a cornercorner with one S(1)GaMo3 tetrahedra, corners with two equivalent S(2)VGaMo2 tetrahedra,  an edgeedge with one S(1)GaMo3 tetrahedra, and edges with two equivalent S(2)VGaMo2 tetrahedra. In the third S site, S(3) is bonded in a 3-coordinate geometry to three equivalent Mo(1) atoms. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to one V(1) and two equivalent Mo(1) atoms.