V(CrS2)2 crystallizes in the monoclinic C2/m space group. V(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form VS6 octahedra that share corners with twelve equivalent Cr(1)S6 octahedra, edges with two equivalent V(1)S6 octahedra, and faces with two equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. Cr(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form CrS6 octahedra that share corners with six equivalent V(1)S6 octahedra, edges with six equivalent Cr(1)S6 octahedra, and  a faceface with one V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. There are two inequivalent S sites. In the first S site, S(2) is bonded to two equivalent V(1) and three equivalent Cr(1) atoms to form a mixture of distorted corner and edge-sharing SV2Cr3 trigonal bipyramids. In the second S site, S(1) is bonded in a rectangular see-saw-like geometry to one V(1) and three equivalent Cr(1) atoms.
V(CrS2)2 crystallizes in the monoclinic C2/m space group. V(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form VS6 octahedra that share corners with twelve equivalent Cr(1)S6 octahedra, edges with two equivalent V(1)S6 octahedra, and faces with two equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. Both V(1)-S(1) bond lengths are 2.42 Å. All V(1)-S(2) bond lengths are 2.46 Å. Cr(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form CrS6 octahedra that share corners with six equivalent V(1)S6 octahedra, edges with six equivalent Cr(1)S6 octahedra, and  a faceface with one V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. There are two shorter (2.36 Å) and one longer (2.38 Å) Cr(1)-S(1) bond length. There is one shorter (2.46 Å) and two longer (2.47 Å) Cr(1)-S(2) bond lengths. There are two inequivalent S sites. In the first S site, S(2) is bonded to two equivalent V(1) and three equivalent Cr(1) atoms to form a mixture of distorted corner and edge-sharing SV2Cr3 trigonal bipyramids. In the second S site, S(1) is bonded in a rectangular see-saw-like geometry to one V(1) and three equivalent Cr(1) atoms.