Co2V2O7 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(5), and one O(7) atom to form VO4 tetrahedra that share corners with three equivalent Co(1)O6 octahedra, corners with three equivalent Co(2)O6 octahedra, and  a cornercorner with one V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-62°. In the second V site, V(2) is bonded to one O(1), one O(3), one O(4), and one O(6) atom to form VO4 tetrahedra that share corners with three equivalent Co(1)O6 octahedra, corners with four equivalent Co(2)O6 octahedra, and  a cornercorner with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-59°. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(2), one O(3), one O(4), one O(6), and two equivalent O(7) atoms to form CoO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra,  an edgeedge with one Co(1)O6 octahedra, and edges with two equivalent Co(2)O6 octahedra. In the second Co site, Co(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form CoO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra, corners with four equivalent V(2)O4 tetrahedra, and edges with two equivalent Co(1)O6 octahedra. There are seven inequivalent O sites. In the first O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one Co(2) atom. In the second O site, O(6) is bonded in a distorted trigonal planar geometry to one V(2), one Co(1), and one Co(2) atom. In the third O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Co(1) atoms. In the fourth O site, O(1) is bonded in a trigonal planar geometry to one V(1), one V(2), and one Co(2) atom. In the fifth O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1), one Co(1), and one Co(2) atom. In the sixth O site, O(3) is bonded in a distorted trigonal planar geometry to one V(2), one Co(1), and one Co(2) atom. In the seventh O site, O(4) is bonded in a distorted trigonal planar geometry to one V(2), one Co(1), and one Co(2) atom.
Co2V2O7 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(5), and one O(7) atom to form VO4 tetrahedra that share corners with three equivalent Co(1)O6 octahedra, corners with three equivalent Co(2)O6 octahedra, and  a cornercorner with one V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-62°. The V(1)-O(1) bond length is 1.85 Å. The V(1)-O(2) bond length is 1.73 Å. The V(1)-O(5) bond length is 1.66 Å. The V(1)-O(7) bond length is 1.72 Å. In the second V site, V(2) is bonded to one O(1), one O(3), one O(4), and one O(6) atom to form VO4 tetrahedra that share corners with three equivalent Co(1)O6 octahedra, corners with four equivalent Co(2)O6 octahedra, and  a cornercorner with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-59°. The V(2)-O(1) bond length is 1.84 Å. The V(2)-O(3) bond length is 1.71 Å. The V(2)-O(4) bond length is 1.72 Å. The V(2)-O(6) bond length is 1.71 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(2), one O(3), one O(4), one O(6), and two equivalent O(7) atoms to form CoO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra,  an edgeedge with one Co(1)O6 octahedra, and edges with two equivalent Co(2)O6 octahedra. The Co(1)-O(2) bond length is 2.06 Å. The Co(1)-O(3) bond length is 2.05 Å. The Co(1)-O(4) bond length is 2.05 Å. The Co(1)-O(6) bond length is 2.06 Å. Both Co(1)-O(7) bond lengths are 2.03 Å. In the second Co site, Co(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form CoO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra, corners with four equivalent V(2)O4 tetrahedra, and edges with two equivalent Co(1)O6 octahedra. The Co(2)-O(1) bond length is 2.14 Å. The Co(2)-O(2) bond length is 2.05 Å. The Co(2)-O(3) bond length is 2.08 Å. The Co(2)-O(4) bond length is 2.05 Å. The Co(2)-O(5) bond length is 1.97 Å. The Co(2)-O(6) bond length is 2.04 Å. There are seven inequivalent O sites. In the first O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one Co(2) atom. In the second O site, O(6) is bonded in a distorted trigonal planar geometry to one V(2), one Co(1), and one Co(2) atom. In the third O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Co(1) atoms. In the fourth O site, O(1) is bonded in a trigonal planar geometry to one V(1), one V(2), and one Co(2) atom. In the fifth O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1), one Co(1), and one Co(2) atom. In the sixth O site, O(3) is bonded in a distorted trigonal planar geometry to one V(2), one Co(1), and one Co(2) atom. In the seventh O site, O(4) is bonded in a distorted trigonal planar geometry to one V(2), one Co(1), and one Co(2) atom.