VCrO5 crystallizes in the orthorhombic Pnma space group. V(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form distorted VO6 octahedra that share corners with two equivalent V(1)O6 octahedra and corners with four equivalent Cr(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 27°. Cr(1) is bonded to one O(1), one O(4), and two equivalent O(3) atoms to form CrO4 tetrahedra that share corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-41°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one Cr(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one Cr(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one Cr(1) atom.
VCrO5 crystallizes in the orthorhombic Pnma space group. V(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form distorted VO6 octahedra that share corners with two equivalent V(1)O6 octahedra and corners with four equivalent Cr(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 27°. The V(1)-O(1) bond length is 1.99 Å. The V(1)-O(4) bond length is 2.03 Å. There is one shorter (1.68 Å) and one longer (2.16 Å) V(1)-O(2) bond length. Both V(1)-O(3) bond lengths are 2.00 Å. Cr(1) is bonded to one O(1), one O(4), and two equivalent O(3) atoms to form CrO4 tetrahedra that share corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-41°. The Cr(1)-O(1) bond length is 1.66 Å. The Cr(1)-O(4) bond length is 1.65 Å. Both Cr(1)-O(3) bond lengths are 1.67 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one Cr(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one Cr(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one Cr(1) atom.