CoVO4 crystallizes in the orthorhombic Pnma space group. V(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form VO4 tetrahedra that share corners with four equivalent Co(1)O6 octahedra and  an edgeedge with one Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-61°. Co(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form CoO6 octahedra that share corners with four equivalent Co(1)O6 octahedra, corners with four equivalent V(1)O4 tetrahedra, and  an edgeedge with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 45°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Co(1) atoms. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one Co(1) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one V(1) and one Co(1) atom.
CoVO4 crystallizes in the orthorhombic Pnma space group. V(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form VO4 tetrahedra that share corners with four equivalent Co(1)O6 octahedra and  an edgeedge with one Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-61°. The V(1)-O(2) bond length is 1.72 Å. The V(1)-O(3) bond length is 1.70 Å. Both V(1)-O(1) bond lengths are 1.80 Å. Co(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form CoO6 octahedra that share corners with four equivalent Co(1)O6 octahedra, corners with four equivalent V(1)O4 tetrahedra, and  an edgeedge with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 45°. The Co(1)-O(2) bond length is 1.91 Å. The Co(1)-O(3) bond length is 1.87 Å. There are two shorter (1.92 Å) and two longer (2.01 Å) Co(1)-O(1) bond lengths. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Co(1) atoms. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one Co(1) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one V(1) and one Co(1) atom.