VCr2O6 is Hydrophilite-derived structured and crystallizes in the orthorhombic Pbcn space group. V(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form distorted VO6 octahedra that share corners with four equivalent Cr(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-25°. Cr(1) is bonded to one O(1), two equivalent O(2), and three equivalent O(3) atoms to form CrO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent Cr(1)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-53°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to two equivalent V(1) and one Cr(1) atom. In the second O site, O(2) is bonded in a T-shaped geometry to one V(1) and two equivalent Cr(1) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to three equivalent Cr(1) atoms.
VCr2O6 is Hydrophilite-derived structured and crystallizes in the orthorhombic Pbcn space group. V(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form distorted VO6 octahedra that share corners with four equivalent Cr(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-25°. Both V(1)-O(2) bond lengths are 1.81 Å. There are two shorter (1.90 Å) and two longer (2.00 Å) V(1)-O(1) bond lengths. Cr(1) is bonded to one O(1), two equivalent O(2), and three equivalent O(3) atoms to form CrO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent Cr(1)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-53°. The Cr(1)-O(1) bond length is 2.00 Å. There is one shorter (2.00 Å) and one longer (2.03 Å) Cr(1)-O(2) bond length. There are a spread of Cr(1)-O(3) bond distances ranging from 1.91-1.97 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to two equivalent V(1) and one Cr(1) atom. In the second O site, O(2) is bonded in a T-shaped geometry to one V(1) and two equivalent Cr(1) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to three equivalent Cr(1) atoms.