V2CrSe4 crystallizes in the monoclinic C2/m space group. V(1) is bonded to three equivalent Se(1) and three equivalent Se(2) atoms to form distorted VSe6 octahedra that share corners with six equivalent Cr(1)Se6 octahedra, edges with six equivalent V(1)Se6 octahedra, and  a faceface with one Cr(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 51-55°. Cr(1) is bonded to two equivalent Se(1) and four equivalent Se(2) atoms to form CrSe6 octahedra that share corners with twelve equivalent V(1)Se6 octahedra, edges with two equivalent Cr(1)Se6 octahedra, and faces with two equivalent V(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 51-55°. There are two inequivalent Se sites. In the first Se site, Se(2) is bonded in a 5-coordinate geometry to three equivalent V(1) and two equivalent Cr(1) atoms. In the second Se site, Se(1) is bonded in a 4-coordinate geometry to three equivalent V(1) and one Cr(1) atom.
V2CrSe4 crystallizes in the monoclinic C2/m space group. V(1) is bonded to three equivalent Se(1) and three equivalent Se(2) atoms to form distorted VSe6 octahedra that share corners with six equivalent Cr(1)Se6 octahedra, edges with six equivalent V(1)Se6 octahedra, and  a faceface with one Cr(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 51-55°. There is one shorter (2.44 Å) and two longer (2.46 Å) V(1)-Se(1) bond lengths. There are two shorter (2.61 Å) and one longer (2.74 Å) V(1)-Se(2) bond length. Cr(1) is bonded to two equivalent Se(1) and four equivalent Se(2) atoms to form CrSe6 octahedra that share corners with twelve equivalent V(1)Se6 octahedra, edges with two equivalent Cr(1)Se6 octahedra, and faces with two equivalent V(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 51-55°. Both Cr(1)-Se(1) bond lengths are 2.55 Å. All Cr(1)-Se(2) bond lengths are 2.57 Å. There are two inequivalent Se sites. In the first Se site, Se(2) is bonded in a 5-coordinate geometry to three equivalent V(1) and two equivalent Cr(1) atoms. In the second Se site, Se(1) is bonded in a 4-coordinate geometry to three equivalent V(1) and one Cr(1) atom.