CaV4O6 crystallizes in the monoclinic C2/m space group. Ca(1) is bonded in a 8-coordinate geometry to one O(6), one O(7), two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(5), two equivalent O(1), and three equivalent O(7) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the second V site, V(2) is bonded to one O(1), one O(3), two equivalent O(5), and two equivalent O(7) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 0-50°. In the third V site, V(3) is bonded to one O(2), one O(3), two equivalent O(4), and two equivalent O(6) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 0-50°. In the fourth V site, V(4) is bonded to one O(4), two equivalent O(2), and three equivalent O(6) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. There are seven inequivalent O sites. In the first O site, O(1) is bonded to two equivalent V(2) and four equivalent V(1) atoms to form OV6 octahedra that share corners with four equivalent O(7)CaV5 octahedra, corners with two equivalent O(3)Ca2V2 tetrahedra, edges with two equivalent O(1)V6 octahedra, edges with six equivalent O(7)CaV5 octahedra, and edges with four equivalent O(5)Ca2V3 square pyramids. The corner-sharing octahedral tilt angles are 3°. In the second O site, O(2) is bonded to two equivalent V(3) and four equivalent V(4) atoms to form OV6 octahedra that share corners with four equivalent O(6)CaV5 octahedra, corners with two equivalent O(3)Ca2V2 tetrahedra, edges with two equivalent O(2)V6 octahedra, edges with six equivalent O(6)CaV5 octahedra, and edges with four equivalent O(4)Ca2V3 square pyramids. The corner-sharing octahedral tilt angles are 2°. In the third O site, O(3) is bonded to two equivalent Ca(1), one V(2), and one V(3) atom to form distorted OCa2V2 tetrahedra that share  a cornercorner with one O(1)V6 octahedra,  a cornercorner with one O(2)V6 octahedra, corners with four equivalent O(4)Ca2V3 square pyramids, corners with four equivalent O(5)Ca2V3 square pyramids, corners with two equivalent O(3)Ca2V2 tetrahedra, edges with two equivalent O(6)CaV5 octahedra, edges with two equivalent O(7)CaV5 octahedra,  an edgeedge with one O(4)Ca2V3 square pyramid, and  an edgeedge with one O(5)Ca2V3 square pyramid. The corner-sharing octahedral tilt angles range from 1-2°. In the fourth O site, O(4) is bonded to two equivalent Ca(1), one V(4), and two equivalent V(3) atoms to form distorted OCa2V3 square pyramids that share corners with two equivalent O(7)CaV5 octahedra, corners with three equivalent O(6)CaV5 octahedra, corners with two equivalent O(5)Ca2V3 square pyramids, corners with four equivalent O(3)Ca2V2 tetrahedra, edges with two equivalent O(2)V6 octahedra, edges with three equivalent O(6)CaV5 octahedra,  an edgeedge with one O(5)Ca2V3 square pyramid, edges with two equivalent O(4)Ca2V3 square pyramids, and  an edgeedge with one O(3)Ca2V2 tetrahedra. The corner-sharing octahedral tilt angles range from 8-42°. In the fifth O site, O(5) is bonded to two equivalent Ca(1), one V(1), and two equivalent V(2) atoms to form distorted OCa2V3 square pyramids that share corners with two equivalent O(6)CaV5 octahedra, corners with three equivalent O(7)CaV5 octahedra, corners with two equivalent O(4)Ca2V3 square pyramids, corners with four equivalent O(3)Ca2V2 tetrahedra, edges with two equivalent O(1)V6 octahedra, edges with three equivalent O(7)CaV5 octahedra,  an edgeedge with one O(4)Ca2V3 square pyramid, edges with two equivalent O(5)Ca2V3 square pyramids, and  an edgeedge with one O(3)Ca2V2 tetrahedra. The corner-sharing octahedral tilt angles range from 7-42°. In the sixth O site, O(6) is bonded to one Ca(1), two equivalent V(3), and three equivalent V(4) atoms to form distorted OCaV5 octahedra that share  a cornercorner with one O(7)CaV5 octahedra, corners with two equivalent O(2)V6 octahedra, corners with two equivalent O(5)Ca2V3 square pyramids, corners with three equivalent O(4)Ca2V3 square pyramids, edges with three equivalent O(2)V6 octahedra, edges with four equivalent O(6)CaV5 octahedra, edges with three equivalent O(4)Ca2V3 square pyramids, and edges with two equivalent O(3)Ca2V2 tetrahedra. The corner-sharing octahedral tilt angles range from 2-54°. In the seventh O site, O(7) is bonded to one Ca(1), two equivalent V(2), and three equivalent V(1) atoms to form OCaV5 octahedra that share  a cornercorner with one O(6)CaV5 octahedra, corners with two equivalent O(1)V6 octahedra, corners with two equivalent O(4)Ca2V3 square pyramids, corners with three equivalent O(5)Ca2V3 square pyramids, edges with three equivalent O(1)V6 octahedra, edges with four equivalent O(7)CaV5 octahedra, edges with three equivalent O(5)Ca2V3 square pyramids, and edges with two equivalent O(3)Ca2V2 tetrahedra. The corner-sharing octahedral tilt angles range from 3-54°.
CaV4O6 crystallizes in the monoclinic C2/m space group. Ca(1) is bonded in a 8-coordinate geometry to one O(6), one O(7), two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms. The Ca(1)-O(6) bond length is 2.86 Å. The Ca(1)-O(7) bond length is 2.74 Å. Both Ca(1)-O(3) bond lengths are 2.32 Å. Both Ca(1)-O(4) bond lengths are 2.43 Å. Both Ca(1)-O(5) bond lengths are 2.44 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(5), two equivalent O(1), and three equivalent O(7) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. The V(1)-O(5) bond length is 2.10 Å. Both V(1)-O(1) bond lengths are 2.18 Å. There is one shorter (2.19 Å) and two longer (2.23 Å) V(1)-O(7) bond lengths. In the second V site, V(2) is bonded to one O(1), one O(3), two equivalent O(5), and two equivalent O(7) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 0-50°. The V(2)-O(1) bond length is 2.29 Å. The V(2)-O(3) bond length is 1.96 Å. Both V(2)-O(5) bond lengths are 2.05 Å. Both V(2)-O(7) bond lengths are 2.15 Å. In the third V site, V(3) is bonded to one O(2), one O(3), two equivalent O(4), and two equivalent O(6) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 0-50°. The V(3)-O(2) bond length is 2.29 Å. The V(3)-O(3) bond length is 1.97 Å. Both V(3)-O(4) bond lengths are 2.06 Å. Both V(3)-O(6) bond lengths are 2.12 Å. In the fourth V site, V(4) is bonded to one O(4), two equivalent O(2), and three equivalent O(6) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. The V(4)-O(4) bond length is 2.09 Å. Both V(4)-O(2) bond lengths are 2.19 Å. There are two shorter (2.20 Å) and one longer (2.21 Å) V(4)-O(6) bond length. There are seven inequivalent O sites. In the first O site, O(1) is bonded to two equivalent V(2) and four equivalent V(1) atoms to form OV6 octahedra that share corners with four equivalent O(7)CaV5 octahedra, corners with two equivalent O(3)Ca2V2 tetrahedra, edges with two equivalent O(1)V6 octahedra, edges with six equivalent O(7)CaV5 octahedra, and edges with four equivalent O(5)Ca2V3 square pyramids. The corner-sharing octahedral tilt angles are 3°. In the second O site, O(2) is bonded to two equivalent V(3) and four equivalent V(4) atoms to form OV6 octahedra that share corners with four equivalent O(6)CaV5 octahedra, corners with two equivalent O(3)Ca2V2 tetrahedra, edges with two equivalent O(2)V6 octahedra, edges with six equivalent O(6)CaV5 octahedra, and edges with four equivalent O(4)Ca2V3 square pyramids. The corner-sharing octahedral tilt angles are 2°. In the third O site, O(3) is bonded to two equivalent Ca(1), one V(2), and one V(3) atom to form distorted OCa2V2 tetrahedra that share  a cornercorner with one O(1)V6 octahedra,  a cornercorner with one O(2)V6 octahedra, corners with four equivalent O(4)Ca2V3 square pyramids, corners with four equivalent O(5)Ca2V3 square pyramids, corners with two equivalent O(3)Ca2V2 tetrahedra, edges with two equivalent O(6)CaV5 octahedra, edges with two equivalent O(7)CaV5 octahedra,  an edgeedge with one O(4)Ca2V3 square pyramid, and  an edgeedge with one O(5)Ca2V3 square pyramid. The corner-sharing octahedral tilt angles range from 1-2°. In the fourth O site, O(4) is bonded to two equivalent Ca(1), one V(4), and two equivalent V(3) atoms to form distorted OCa2V3 square pyramids that share corners with two equivalent O(7)CaV5 octahedra, corners with three equivalent O(6)CaV5 octahedra, corners with two equivalent O(5)Ca2V3 square pyramids, corners with four equivalent O(3)Ca2V2 tetrahedra, edges with two equivalent O(2)V6 octahedra, edges with three equivalent O(6)CaV5 octahedra,  an edgeedge with one O(5)Ca2V3 square pyramid, edges with two equivalent O(4)Ca2V3 square pyramids, and  an edgeedge with one O(3)Ca2V2 tetrahedra. The corner-sharing octahedral tilt angles range from 8-42°. In the fifth O site, O(5) is bonded to two equivalent Ca(1), one V(1), and two equivalent V(2) atoms to form distorted OCa2V3 square pyramids that share corners with two equivalent O(6)CaV5 octahedra, corners with three equivalent O(7)CaV5 octahedra, corners with two equivalent O(4)Ca2V3 square pyramids, corners with four equivalent O(3)Ca2V2 tetrahedra, edges with two equivalent O(1)V6 octahedra, edges with three equivalent O(7)CaV5 octahedra,  an edgeedge with one O(4)Ca2V3 square pyramid, edges with two equivalent O(5)Ca2V3 square pyramids, and  an edgeedge with one O(3)Ca2V2 tetrahedra. The corner-sharing octahedral tilt angles range from 7-42°. In the sixth O site, O(6) is bonded to one Ca(1), two equivalent V(3), and three equivalent V(4) atoms to form distorted OCaV5 octahedra that share  a cornercorner with one O(7)CaV5 octahedra, corners with two equivalent O(2)V6 octahedra, corners with two equivalent O(5)Ca2V3 square pyramids, corners with three equivalent O(4)Ca2V3 square pyramids, edges with three equivalent O(2)V6 octahedra, edges with four equivalent O(6)CaV5 octahedra, edges with three equivalent O(4)Ca2V3 square pyramids, and edges with two equivalent O(3)Ca2V2 tetrahedra. The corner-sharing octahedral tilt angles range from 2-54°. In the seventh O site, O(7) is bonded to one Ca(1), two equivalent V(2), and three equivalent V(1) atoms to form OCaV5 octahedra that share  a cornercorner with one O(6)CaV5 octahedra, corners with two equivalent O(1)V6 octahedra, corners with two equivalent O(4)Ca2V3 square pyramids, corners with three equivalent O(5)Ca2V3 square pyramids, edges with three equivalent O(1)V6 octahedra, edges with four equivalent O(7)CaV5 octahedra, edges with three equivalent O(5)Ca2V3 square pyramids, and edges with two equivalent O(3)Ca2V2 tetrahedra. The corner-sharing octahedral tilt angles range from 3-54°.