VMo2S4 crystallizes in the monoclinic C2/c space group. V(1) is bonded to one S(1), one S(4), two equivalent S(2), and two equivalent S(3) atoms to form VS6 octahedra that share corners with six equivalent Mo(1)S6 octahedra, edges with two equivalent V(1)S6 octahedra, and  a faceface with one Mo(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 48-56°. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form distorted MoS6 octahedra that share corners with six equivalent V(1)S6 octahedra, edges with two equivalent Mo(1)S6 octahedra, and  a faceface with one V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 48-56°. In the second Mo site, Mo(2) is bonded in a 6-coordinate geometry to one S(1), one S(2), two equivalent S(3), and two equivalent S(4) atoms. There are four inequivalent S sites. In the first S site, S(3) is bonded in a 5-coordinate geometry to two equivalent V(1), one Mo(1), and two equivalent Mo(2) atoms. In the second S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to one V(1), one Mo(1), and two equivalent Mo(2) atoms. In the third S site, S(1) is bonded in a 4-coordinate geometry to one V(1), one Mo(2), and two equivalent Mo(1) atoms. In the fourth S site, S(2) is bonded in a 5-coordinate geometry to two equivalent V(1), one Mo(2), and two equivalent Mo(1) atoms.
VMo2S4 crystallizes in the monoclinic C2/c space group. V(1) is bonded to one S(1), one S(4), two equivalent S(2), and two equivalent S(3) atoms to form VS6 octahedra that share corners with six equivalent Mo(1)S6 octahedra, edges with two equivalent V(1)S6 octahedra, and  a faceface with one Mo(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 48-56°. The V(1)-S(1) bond length is 2.39 Å. The V(1)-S(4) bond length is 2.46 Å. There is one shorter (2.44 Å) and one longer (2.47 Å) V(1)-S(2) bond length. There is one shorter (2.43 Å) and one longer (2.44 Å) V(1)-S(3) bond length. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form distorted MoS6 octahedra that share corners with six equivalent V(1)S6 octahedra, edges with two equivalent Mo(1)S6 octahedra, and  a faceface with one V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 48-56°. The Mo(1)-S(3) bond length is 2.50 Å. The Mo(1)-S(4) bond length is 2.44 Å. There is one shorter (2.38 Å) and one longer (2.40 Å) Mo(1)-S(1) bond length. There is one shorter (2.58 Å) and one longer (2.60 Å) Mo(1)-S(2) bond length. In the second Mo site, Mo(2) is bonded in a 6-coordinate geometry to one S(1), one S(2), two equivalent S(3), and two equivalent S(4) atoms. The Mo(2)-S(1) bond length is 2.37 Å. The Mo(2)-S(2) bond length is 2.60 Å. There is one shorter (2.53 Å) and one longer (2.65 Å) Mo(2)-S(3) bond length. There is one shorter (2.35 Å) and one longer (2.42 Å) Mo(2)-S(4) bond length. There are four inequivalent S sites. In the first S site, S(3) is bonded in a 5-coordinate geometry to two equivalent V(1), one Mo(1), and two equivalent Mo(2) atoms. In the second S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to one V(1), one Mo(1), and two equivalent Mo(2) atoms. In the third S site, S(1) is bonded in a 4-coordinate geometry to one V(1), one Mo(2), and two equivalent Mo(1) atoms. In the fourth S site, S(2) is bonded in a 5-coordinate geometry to two equivalent V(1), one Mo(2), and two equivalent Mo(1) atoms.