V2CrTe4 crystallizes in the monoclinic Cm space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one Te(2), one Te(4), two equivalent Te(1), and two equivalent Te(3) atoms to form VTe6 octahedra that share corners with six equivalent V(2)Te6 octahedra, edges with two equivalent V(1)Te6 octahedra, edges with four equivalent Cr(1)Te6 octahedra, and  a faceface with one V(2)Te6 octahedra. The corner-sharing octahedral tilt angles range from 50-52°. In the second V site, V(2) is bonded to one Te(1), one Te(2), two equivalent Te(3), and two equivalent Te(4) atoms to form VTe6 octahedra that share corners with six equivalent V(1)Te6 octahedra, corners with six equivalent Cr(1)Te6 octahedra, edges with two equivalent V(2)Te6 octahedra,  a faceface with one V(1)Te6 octahedra, and  a faceface with one Cr(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 50-52°. Cr(1) is bonded to one Te(1), one Te(3), two equivalent Te(2), and two equivalent Te(4) atoms to form CrTe6 octahedra that share corners with six equivalent V(2)Te6 octahedra, edges with two equivalent Cr(1)Te6 octahedra, edges with four equivalent V(1)Te6 octahedra, and  a faceface with one V(2)Te6 octahedra. The corner-sharing octahedral tilt angles range from 50-52°. There are four inequivalent Te sites. In the first Te site, Te(1) is bonded in a rectangular see-saw-like geometry to one V(2), two equivalent V(1), and one Cr(1) atom. In the second Te site, Te(2) is bonded in a rectangular see-saw-like geometry to one V(1), one V(2), and two equivalent Cr(1) atoms. In the third Te site, Te(3) is bonded to two equivalent V(1), two equivalent V(2), and one Cr(1) atom to form distorted TeV4Cr square pyramids that share corners with two equivalent Te(4)V3Cr2 trigonal bipyramids, edges with two equivalent Te(3)V4Cr square pyramids, and edges with three equivalent Te(4)V3Cr2 trigonal bipyramids. In the fourth Te site, Te(4) is bonded to one V(1), two equivalent V(2), and two equivalent Cr(1) atoms to form distorted TeV3Cr2 trigonal bipyramids that share corners with two equivalent Te(3)V4Cr square pyramids, edges with three equivalent Te(3)V4Cr square pyramids, and edges with two equivalent Te(4)V3Cr2 trigonal bipyramids.
V2CrTe4 crystallizes in the monoclinic Cm space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one Te(2), one Te(4), two equivalent Te(1), and two equivalent Te(3) atoms to form VTe6 octahedra that share corners with six equivalent V(2)Te6 octahedra, edges with two equivalent V(1)Te6 octahedra, edges with four equivalent Cr(1)Te6 octahedra, and  a faceface with one V(2)Te6 octahedra. The corner-sharing octahedral tilt angles range from 50-52°. The V(1)-Te(2) bond length is 2.77 Å. The V(1)-Te(4) bond length is 2.83 Å. Both V(1)-Te(1) bond lengths are 2.74 Å. Both V(1)-Te(3) bond lengths are 2.84 Å. In the second V site, V(2) is bonded to one Te(1), one Te(2), two equivalent Te(3), and two equivalent Te(4) atoms to form VTe6 octahedra that share corners with six equivalent V(1)Te6 octahedra, corners with six equivalent Cr(1)Te6 octahedra, edges with two equivalent V(2)Te6 octahedra,  a faceface with one V(1)Te6 octahedra, and  a faceface with one Cr(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 50-52°. The V(2)-Te(1) bond length is 2.77 Å. The V(2)-Te(2) bond length is 2.77 Å. Both V(2)-Te(3) bond lengths are 2.79 Å. Both V(2)-Te(4) bond lengths are 2.82 Å. Cr(1) is bonded to one Te(1), one Te(3), two equivalent Te(2), and two equivalent Te(4) atoms to form CrTe6 octahedra that share corners with six equivalent V(2)Te6 octahedra, edges with two equivalent Cr(1)Te6 octahedra, edges with four equivalent V(1)Te6 octahedra, and  a faceface with one V(2)Te6 octahedra. The corner-sharing octahedral tilt angles range from 50-52°. The Cr(1)-Te(1) bond length is 2.75 Å. The Cr(1)-Te(3) bond length is 2.80 Å. Both Cr(1)-Te(2) bond lengths are 2.72 Å. Both Cr(1)-Te(4) bond lengths are 2.87 Å. There are four inequivalent Te sites. In the first Te site, Te(1) is bonded in a rectangular see-saw-like geometry to one V(2), two equivalent V(1), and one Cr(1) atom. In the second Te site, Te(2) is bonded in a rectangular see-saw-like geometry to one V(1), one V(2), and two equivalent Cr(1) atoms. In the third Te site, Te(3) is bonded to two equivalent V(1), two equivalent V(2), and one Cr(1) atom to form distorted TeV4Cr square pyramids that share corners with two equivalent Te(4)V3Cr2 trigonal bipyramids, edges with two equivalent Te(3)V4Cr square pyramids, and edges with three equivalent Te(4)V3Cr2 trigonal bipyramids. In the fourth Te site, Te(4) is bonded to one V(1), two equivalent V(2), and two equivalent Cr(1) atoms to form distorted TeV3Cr2 trigonal bipyramids that share corners with two equivalent Te(3)V4Cr square pyramids, edges with three equivalent Te(3)V4Cr square pyramids, and edges with two equivalent Te(4)V3Cr2 trigonal bipyramids.