CaV5O7 crystallizes in the orthorhombic Cmcm space group. Ca(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(4), and four equivalent O(3) atoms. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(3), two equivalent O(4), and three equivalent O(2) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 1-4°. In the second V site, V(2) is bonded to two equivalent O(4) and four equivalent O(2) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 4°. In the third V site, V(3) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 1-49°. There are four inequivalent O sites. In the first O site, O(4) is bonded to one Ca(1), one V(2), two equivalent V(1), and two equivalent V(3) atoms to form distorted OCaV5 octahedra that share corners with two equivalent O(4)CaV5 octahedra, corners with two equivalent O(2)V6 octahedra, corners with four equivalent O(3)Ca2V3 square pyramids, edges with two equivalent O(4)CaV5 octahedra, edges with five equivalent O(2)V6 octahedra, edges with three equivalent O(3)Ca2V3 square pyramids, and edges with two equivalent O(1)Ca2V2 tetrahedra. The corner-sharing octahedral tilt angles range from 0-53°. In the second O site, O(1) is bonded to two equivalent Ca(1) and two equivalent V(3) atoms to form distorted OCa2V2 tetrahedra that share corners with two equivalent O(2)V6 octahedra, corners with eight equivalent O(3)Ca2V3 square pyramids, corners with two equivalent O(1)Ca2V2 tetrahedra, edges with four equivalent O(4)CaV5 octahedra, and edges with two equivalent O(3)Ca2V3 square pyramids. The corner-sharing octahedra are not tilted. In the third O site, O(2) is bonded to one V(3), two equivalent V(2), and three equivalent V(1) atoms to form OV6 octahedra that share corners with two equivalent O(4)CaV5 octahedra, corners with two equivalent O(2)V6 octahedra,  a cornercorner with one O(3)Ca2V3 square pyramid,  a cornercorner with one O(1)Ca2V2 tetrahedra, edges with five equivalent O(4)CaV5 octahedra, edges with five equivalent O(2)V6 octahedra, and edges with two equivalent O(3)Ca2V3 square pyramids. The corner-sharing octahedral tilt angles range from 0-2°. In the fourth O site, O(3) is bonded to two equivalent Ca(1), one V(1), and two equivalent V(3) atoms to form distorted OCa2V3 square pyramids that share  a cornercorner with one O(2)V6 octahedra, corners with four equivalent O(4)CaV5 octahedra, corners with two equivalent O(3)Ca2V3 square pyramids, corners with four equivalent O(1)Ca2V2 tetrahedra, edges with two equivalent O(2)V6 octahedra, edges with three equivalent O(4)CaV5 octahedra, edges with three equivalent O(3)Ca2V3 square pyramids, and  an edgeedge with one O(1)Ca2V2 tetrahedra. The corner-sharing octahedral tilt angles range from 8-42°.
CaV5O7 crystallizes in the orthorhombic Cmcm space group. Ca(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(4), and four equivalent O(3) atoms. Both Ca(1)-O(1) bond lengths are 2.32 Å. Both Ca(1)-O(4) bond lengths are 2.82 Å. All Ca(1)-O(3) bond lengths are 2.43 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(3), two equivalent O(4), and three equivalent O(2) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 1-4°. The V(1)-O(3) bond length is 2.09 Å. Both V(1)-O(4) bond lengths are 2.20 Å. There are two shorter (2.22 Å) and one longer (2.25 Å) V(1)-O(2) bond length. In the second V site, V(2) is bonded to two equivalent O(4) and four equivalent O(2) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 4°. Both V(2)-O(4) bond lengths are 2.19 Å. All V(2)-O(2) bond lengths are 2.18 Å. In the third V site, V(3) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 1-49°. The V(3)-O(1) bond length is 1.97 Å. The V(3)-O(2) bond length is 2.21 Å. Both V(3)-O(3) bond lengths are 2.06 Å. Both V(3)-O(4) bond lengths are 2.13 Å. There are four inequivalent O sites. In the first O site, O(4) is bonded to one Ca(1), one V(2), two equivalent V(1), and two equivalent V(3) atoms to form distorted OCaV5 octahedra that share corners with two equivalent O(4)CaV5 octahedra, corners with two equivalent O(2)V6 octahedra, corners with four equivalent O(3)Ca2V3 square pyramids, edges with two equivalent O(4)CaV5 octahedra, edges with five equivalent O(2)V6 octahedra, edges with three equivalent O(3)Ca2V3 square pyramids, and edges with two equivalent O(1)Ca2V2 tetrahedra. The corner-sharing octahedral tilt angles range from 0-53°. In the second O site, O(1) is bonded to two equivalent Ca(1) and two equivalent V(3) atoms to form distorted OCa2V2 tetrahedra that share corners with two equivalent O(2)V6 octahedra, corners with eight equivalent O(3)Ca2V3 square pyramids, corners with two equivalent O(1)Ca2V2 tetrahedra, edges with four equivalent O(4)CaV5 octahedra, and edges with two equivalent O(3)Ca2V3 square pyramids. The corner-sharing octahedra are not tilted. In the third O site, O(2) is bonded to one V(3), two equivalent V(2), and three equivalent V(1) atoms to form OV6 octahedra that share corners with two equivalent O(4)CaV5 octahedra, corners with two equivalent O(2)V6 octahedra,  a cornercorner with one O(3)Ca2V3 square pyramid,  a cornercorner with one O(1)Ca2V2 tetrahedra, edges with five equivalent O(4)CaV5 octahedra, edges with five equivalent O(2)V6 octahedra, and edges with two equivalent O(3)Ca2V3 square pyramids. The corner-sharing octahedral tilt angles range from 0-2°. In the fourth O site, O(3) is bonded to two equivalent Ca(1), one V(1), and two equivalent V(3) atoms to form distorted OCa2V3 square pyramids that share  a cornercorner with one O(2)V6 octahedra, corners with four equivalent O(4)CaV5 octahedra, corners with two equivalent O(3)Ca2V3 square pyramids, corners with four equivalent O(1)Ca2V2 tetrahedra, edges with two equivalent O(2)V6 octahedra, edges with three equivalent O(4)CaV5 octahedra, edges with three equivalent O(3)Ca2V3 square pyramids, and  an edgeedge with one O(1)Ca2V2 tetrahedra. The corner-sharing octahedral tilt angles range from 8-42°.