V(CrTe2)2 crystallizes in the monoclinic C2/m space group. V(1) is bonded to two equivalent Te(1) and four equivalent Te(2) atoms to form VTe6 octahedra that share corners with twelve equivalent Cr(1)Te6 octahedra, edges with two equivalent V(1)Te6 octahedra, and faces with two equivalent Cr(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 50-52°. Cr(1) is bonded to three equivalent Te(1) and three equivalent Te(2) atoms to form CrTe6 octahedra that share corners with six equivalent V(1)Te6 octahedra, edges with six equivalent Cr(1)Te6 octahedra, and  a faceface with one V(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 50-52°. There are two inequivalent Te sites. In the first Te site, Te(2) is bonded to two equivalent V(1) and three equivalent Cr(1) atoms to form a mixture of distorted edge and corner-sharing TeV2Cr3 square pyramids. In the second Te site, Te(1) is bonded in a rectangular see-saw-like geometry to one V(1) and three equivalent Cr(1) atoms.
V(CrTe2)2 crystallizes in the monoclinic C2/m space group. V(1) is bonded to two equivalent Te(1) and four equivalent Te(2) atoms to form VTe6 octahedra that share corners with twelve equivalent Cr(1)Te6 octahedra, edges with two equivalent V(1)Te6 octahedra, and faces with two equivalent Cr(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 50-52°. Both V(1)-Te(1) bond lengths are 2.77 Å. All V(1)-Te(2) bond lengths are 2.79 Å. Cr(1) is bonded to three equivalent Te(1) and three equivalent Te(2) atoms to form CrTe6 octahedra that share corners with six equivalent V(1)Te6 octahedra, edges with six equivalent Cr(1)Te6 octahedra, and  a faceface with one V(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 50-52°. There are two shorter (2.72 Å) and one longer (2.75 Å) Cr(1)-Te(1) bond length. There is one shorter (2.80 Å) and two longer (2.85 Å) Cr(1)-Te(2) bond lengths. There are two inequivalent Te sites. In the first Te site, Te(2) is bonded to two equivalent V(1) and three equivalent Cr(1) atoms to form a mixture of distorted edge and corner-sharing TeV2Cr3 square pyramids. In the second Te site, Te(1) is bonded in a rectangular see-saw-like geometry to one V(1) and three equivalent Cr(1) atoms.