Ca2V2O5 crystallizes in the orthorhombic Pbam space group. Ca(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), and four equivalent O(3) atoms. V(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form corner-sharing VO5 square pyramids. There are three inequivalent O sites. In the first O site, O(1) is bonded to four equivalent Ca(1) and two equivalent V(1) atoms to form distorted OCa4V2 octahedra that share corners with eight equivalent O(3)Ca4V2 octahedra, corners with eight equivalent O(2)Ca2V2 tetrahedra, edges with two equivalent O(1)Ca4V2 octahedra, edges with two equivalent O(2)Ca2V2 tetrahedra, and faces with four equivalent O(3)Ca4V2 octahedra. The corner-sharing octahedral tilt angles range from 61-66°. In the second O site, O(2) is bonded to two equivalent Ca(1) and two equivalent V(1) atoms to form distorted OCa2V2 tetrahedra that share corners with four equivalent O(1)Ca4V2 octahedra, corners with four equivalent O(3)Ca4V2 octahedra, corners with four equivalent O(2)Ca2V2 tetrahedra,  an edgeedge with one O(1)Ca4V2 octahedra, and edges with four equivalent O(3)Ca4V2 octahedra. The corner-sharing octahedral tilt angles range from 10-78°. In the third O site, O(3) is bonded to four equivalent Ca(1) and two equivalent V(1) atoms to form distorted OCa4V2 octahedra that share corners with four equivalent O(1)Ca4V2 octahedra, corners with six equivalent O(3)Ca4V2 octahedra, corners with four equivalent O(2)Ca2V2 tetrahedra, edges with four equivalent O(3)Ca4V2 octahedra, edges with four equivalent O(2)Ca2V2 tetrahedra, and faces with two equivalent O(1)Ca4V2 octahedra. The corner-sharing octahedral tilt angles range from 8-66°.
Ca2V2O5 crystallizes in the orthorhombic Pbam space group. Ca(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), and four equivalent O(3) atoms. Both Ca(1)-O(1) bond lengths are 2.63 Å. Both Ca(1)-O(2) bond lengths are 2.37 Å. There are a spread of Ca(1)-O(3) bond distances ranging from 2.42-2.78 Å. V(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form corner-sharing VO5 square pyramids. The V(1)-O(1) bond length is 2.00 Å. There is one shorter (1.97 Å) and one longer (2.00 Å) V(1)-O(2) bond length. Both V(1)-O(3) bond lengths are 2.00 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to four equivalent Ca(1) and two equivalent V(1) atoms to form distorted OCa4V2 octahedra that share corners with eight equivalent O(3)Ca4V2 octahedra, corners with eight equivalent O(2)Ca2V2 tetrahedra, edges with two equivalent O(1)Ca4V2 octahedra, edges with two equivalent O(2)Ca2V2 tetrahedra, and faces with four equivalent O(3)Ca4V2 octahedra. The corner-sharing octahedral tilt angles range from 61-66°. In the second O site, O(2) is bonded to two equivalent Ca(1) and two equivalent V(1) atoms to form distorted OCa2V2 tetrahedra that share corners with four equivalent O(1)Ca4V2 octahedra, corners with four equivalent O(3)Ca4V2 octahedra, corners with four equivalent O(2)Ca2V2 tetrahedra,  an edgeedge with one O(1)Ca4V2 octahedra, and edges with four equivalent O(3)Ca4V2 octahedra. The corner-sharing octahedral tilt angles range from 10-78°. In the third O site, O(3) is bonded to four equivalent Ca(1) and two equivalent V(1) atoms to form distorted OCa4V2 octahedra that share corners with four equivalent O(1)Ca4V2 octahedra, corners with six equivalent O(3)Ca4V2 octahedra, corners with four equivalent O(2)Ca2V2 tetrahedra, edges with four equivalent O(3)Ca4V2 octahedra, edges with four equivalent O(2)Ca2V2 tetrahedra, and faces with two equivalent O(1)Ca4V2 octahedra. The corner-sharing octahedral tilt angles range from 8-66°.