V2CrS4 crystallizes in the monoclinic C2/m space group. V(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form distorted VS6 octahedra that share corners with six equivalent Cr(1)S6 octahedra, edges with six equivalent V(1)S6 octahedra, and  a faceface with one Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-55°. Cr(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form CrS6 octahedra that share corners with twelve equivalent V(1)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, and faces with two equivalent V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-55°. There are two inequivalent S sites. In the first S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to three equivalent V(1) and one Cr(1) atom. In the second S site, S(1) is bonded in a 5-coordinate geometry to three equivalent V(1) and two equivalent Cr(1) atoms.
V2CrS4 crystallizes in the monoclinic C2/m space group. V(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form distorted VS6 octahedra that share corners with six equivalent Cr(1)S6 octahedra, edges with six equivalent V(1)S6 octahedra, and  a faceface with one Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-55°. There are two shorter (2.51 Å) and one longer (2.57 Å) V(1)-S(1) bond length. There is one shorter (2.30 Å) and two longer (2.31 Å) V(1)-S(2) bond lengths. Cr(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form CrS6 octahedra that share corners with twelve equivalent V(1)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, and faces with two equivalent V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-55°. Both Cr(1)-S(2) bond lengths are 2.41 Å. All Cr(1)-S(1) bond lengths are 2.43 Å. There are two inequivalent S sites. In the first S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to three equivalent V(1) and one Cr(1) atom. In the second S site, S(1) is bonded in a 5-coordinate geometry to three equivalent V(1) and two equivalent Cr(1) atoms.