CaV5O7 crystallizes in the monoclinic Pm space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(7), and four equivalent O(5) atoms. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to two equivalent O(2), two equivalent O(8), and four equivalent O(6) atoms. There are five inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(6), two equivalent O(4), and two equivalent O(8) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 1-4°. In the second V site, V(2) is bonded to one O(2), one O(4), two equivalent O(6), and two equivalent O(8) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 1-50°. In the third V site, V(3) is bonded to one O(7), one O(8), two equivalent O(3), and two equivalent O(4) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 4-7°. In the fourth V site, V(4) is bonded to one O(4), one O(5), two equivalent O(3), 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 1-7°. In the fifth V site, V(5) 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 1-51°. There are eight inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ca(1) and two equivalent V(5) atoms to form distorted OCa2V2 tetrahedra that share corners with two equivalent O(3)V6 octahedra, corners with eight equivalent O(5)Ca2V3 square pyramids, corners with two equivalent O(1)Ca2V2 tetrahedra, edges with four equivalent O(7)CaV5 octahedra, and edges with two equivalent O(5)Ca2V3 square pyramids. The corner-sharing octahedral tilt angles are 1°. In the second O site, O(2) is bonded to two equivalent Ca(2) and two equivalent V(2) atoms to form distorted OCa2V2 tetrahedra that share corners with two equivalent O(4)V6 octahedra, corners with eight equivalent O(6)Ca2V3 square pyramids, corners with two equivalent O(2)Ca2V2 tetrahedra, edges with four equivalent O(8)CaV5 octahedra, and edges with two equivalent O(6)Ca2V3 square pyramids. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to one V(1), one V(5), two equivalent V(3), and two equivalent V(4) atoms to form OV6 octahedra that share corners with two equivalent O(7)CaV5 octahedra, corners with two equivalent O(4)V6 octahedra,  a cornercorner with one O(6)Ca2V3 square pyramid,  a cornercorner with one O(1)Ca2V2 tetrahedra, edges with two equivalent O(8)CaV5 octahedra, edges with two equivalent O(3)V6 octahedra, edges with three equivalent O(7)CaV5 octahedra, edges with three equivalent O(4)V6 octahedra, and edges with two equivalent O(5)Ca2V3 square pyramids. The corner-sharing octahedral tilt angles range from 2-4°. In the fourth O site, O(4) is bonded to one V(2), one V(4), two equivalent V(1), and two equivalent V(3) atoms to form OV6 octahedra that share corners with two equivalent O(8)CaV5 octahedra, corners with two equivalent O(3)V6 octahedra,  a cornercorner with one O(5)Ca2V3 square pyramid,  a cornercorner with one O(2)Ca2V2 tetrahedra, edges with two equivalent O(7)CaV5 octahedra, edges with two equivalent O(4)V6 octahedra, edges with three equivalent O(8)CaV5 octahedra, edges with three equivalent O(3)V6 octahedra, and edges with two equivalent O(6)Ca2V3 square pyramids. The corner-sharing octahedral tilt angles range from 4-5°. In the fifth O site, O(5) is bonded to two equivalent Ca(1), one V(4), and two equivalent V(5) atoms to form distorted OCa2V3 square pyramids that share  a cornercorner with one O(4)V6 octahedra, corners with four equivalent O(7)CaV5 octahedra, corners with two equivalent O(5)Ca2V3 square pyramids, corners with four equivalent O(1)Ca2V2 tetrahedra, edges with two equivalent O(3)V6 octahedra, edges with three equivalent O(7)CaV5 octahedra, edges with three equivalent O(5)Ca2V3 square pyramids, and  an edgeedge with one O(1)Ca2V2 tetrahedra. The corner-sharing octahedral tilt angles range from 5-42°. In the sixth O site, O(6) is bonded to two equivalent Ca(2), one V(1), and two equivalent V(2) atoms to form distorted OCa2V3 square pyramids that share  a cornercorner with one O(3)V6 octahedra, corners with four equivalent O(8)CaV5 octahedra, corners with two equivalent O(6)Ca2V3 square pyramids, corners with four equivalent O(2)Ca2V2 tetrahedra, edges with two equivalent O(4)V6 octahedra, edges with three equivalent O(8)CaV5 octahedra, edges with three equivalent O(6)Ca2V3 square pyramids, and  an edgeedge with one O(2)Ca2V2 tetrahedra. The corner-sharing octahedral tilt angles range from 4-42°. In the seventh O site, O(7) is bonded to one Ca(1), one V(3), two equivalent V(4), and two equivalent V(5) atoms to form distorted OCaV5 octahedra that share  a cornercorner with one O(7)CaV5 octahedra,  a cornercorner with one O(8)CaV5 octahedra, corners with two equivalent O(3)V6 octahedra, corners with four equivalent O(5)Ca2V3 square pyramids, edges with two equivalent O(7)CaV5 octahedra, edges with two equivalent O(4)V6 octahedra, edges with three equivalent O(3)V6 octahedra, edges with three equivalent O(5)Ca2V3 square pyramids, and edges with two equivalent O(1)Ca2V2 tetrahedra. The corner-sharing octahedral tilt angles range from 0-54°. In the eighth O site, O(8) is bonded to one Ca(2), one V(3), two equivalent V(1), and two equivalent V(2) atoms to form distorted OCaV5 octahedra that share  a cornercorner with one O(7)CaV5 octahedra,  a cornercorner with one O(8)CaV5 octahedra, corners with two equivalent O(4)V6 octahedra, corners with four equivalent O(6)Ca2V3 square pyramids, edges with two equivalent O(8)CaV5 octahedra, edges with two equivalent O(3)V6 octahedra, edges with three equivalent O(4)V6 octahedra, edges with three equivalent O(6)Ca2V3 square pyramids, and edges with two equivalent O(2)Ca2V2 tetrahedra. The corner-sharing octahedral tilt angles range from 0-53°.
CaV5O7 crystallizes in the monoclinic Pm space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(7), and four equivalent O(5) atoms. There is one shorter (2.32 Å) and one longer (2.33 Å) Ca(1)-O(1) bond length. Both Ca(1)-O(7) bond lengths are 2.85 Å. All Ca(1)-O(5) bond lengths are 2.44 Å. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to two equivalent O(2), two equivalent O(8), and four equivalent O(6) atoms. Both Ca(2)-O(2) bond lengths are 2.33 Å. Both Ca(2)-O(8) bond lengths are 2.76 Å. All Ca(2)-O(6) bond lengths are 2.45 Å. There are five inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(6), two equivalent O(4), and two equivalent O(8) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 1-4°. The V(1)-O(3) bond length is 2.24 Å. The V(1)-O(6) bond length is 2.11 Å. There is one shorter (2.19 Å) and one longer (2.20 Å) V(1)-O(4) bond length. There is one shorter (2.24 Å) and one longer (2.25 Å) V(1)-O(8) bond length. In the second V site, V(2) is bonded to one O(2), one O(4), two equivalent O(6), and two equivalent O(8) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 1-50°. The V(2)-O(2) bond length is 1.96 Å. The V(2)-O(4) bond length is 2.21 Å. Both V(2)-O(6) bond lengths are 2.06 Å. There is one shorter (2.15 Å) and one longer (2.16 Å) V(2)-O(8) bond length. In the third V site, V(3) is bonded to one O(7), one O(8), two equivalent O(3), and two equivalent O(4) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 4-7°. The V(3)-O(7) bond length is 2.20 Å. The V(3)-O(8) bond length is 2.16 Å. There is one shorter (2.18 Å) and one longer (2.19 Å) V(3)-O(3) bond length. Both V(3)-O(4) bond lengths are 2.18 Å. In the fourth V site, V(4) is bonded to one O(4), one O(5), two equivalent O(3), 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 1-7°. The V(4)-O(4) bond length is 2.25 Å. The V(4)-O(5) bond length is 2.09 Å. Both V(4)-O(3) bond lengths are 2.21 Å. Both V(4)-O(7) bond lengths are 2.23 Å. In the fifth V site, V(5) 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 1-51°. The V(5)-O(1) bond length is 1.97 Å. The V(5)-O(3) bond length is 2.18 Å. Both V(5)-O(5) bond lengths are 2.06 Å. Both V(5)-O(7) bond lengths are 2.16 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ca(1) and two equivalent V(5) atoms to form distorted OCa2V2 tetrahedra that share corners with two equivalent O(3)V6 octahedra, corners with eight equivalent O(5)Ca2V3 square pyramids, corners with two equivalent O(1)Ca2V2 tetrahedra, edges with four equivalent O(7)CaV5 octahedra, and edges with two equivalent O(5)Ca2V3 square pyramids. The corner-sharing octahedral tilt angles are 1°. In the second O site, O(2) is bonded to two equivalent Ca(2) and two equivalent V(2) atoms to form distorted OCa2V2 tetrahedra that share corners with two equivalent O(4)V6 octahedra, corners with eight equivalent O(6)Ca2V3 square pyramids, corners with two equivalent O(2)Ca2V2 tetrahedra, edges with four equivalent O(8)CaV5 octahedra, and edges with two equivalent O(6)Ca2V3 square pyramids. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to one V(1), one V(5), two equivalent V(3), and two equivalent V(4) atoms to form OV6 octahedra that share corners with two equivalent O(7)CaV5 octahedra, corners with two equivalent O(4)V6 octahedra,  a cornercorner with one O(6)Ca2V3 square pyramid,  a cornercorner with one O(1)Ca2V2 tetrahedra, edges with two equivalent O(8)CaV5 octahedra, edges with two equivalent O(3)V6 octahedra, edges with three equivalent O(7)CaV5 octahedra, edges with three equivalent O(4)V6 octahedra, and edges with two equivalent O(5)Ca2V3 square pyramids. The corner-sharing octahedral tilt angles range from 2-4°. In the fourth O site, O(4) is bonded to one V(2), one V(4), two equivalent V(1), and two equivalent V(3) atoms to form OV6 octahedra that share corners with two equivalent O(8)CaV5 octahedra, corners with two equivalent O(3)V6 octahedra,  a cornercorner with one O(5)Ca2V3 square pyramid,  a cornercorner with one O(2)Ca2V2 tetrahedra, edges with two equivalent O(7)CaV5 octahedra, edges with two equivalent O(4)V6 octahedra, edges with three equivalent O(8)CaV5 octahedra, edges with three equivalent O(3)V6 octahedra, and edges with two equivalent O(6)Ca2V3 square pyramids. The corner-sharing octahedral tilt angles range from 4-5°. In the fifth O site, O(5) is bonded to two equivalent Ca(1), one V(4), and two equivalent V(5) atoms to form distorted OCa2V3 square pyramids that share  a cornercorner with one O(4)V6 octahedra, corners with four equivalent O(7)CaV5 octahedra, corners with two equivalent O(5)Ca2V3 square pyramids, corners with four equivalent O(1)Ca2V2 tetrahedra, edges with two equivalent O(3)V6 octahedra, edges with three equivalent O(7)CaV5 octahedra, edges with three equivalent O(5)Ca2V3 square pyramids, and  an edgeedge with one O(1)Ca2V2 tetrahedra. The corner-sharing octahedral tilt angles range from 5-42°. In the sixth O site, O(6) is bonded to two equivalent Ca(2), one V(1), and two equivalent V(2) atoms to form distorted OCa2V3 square pyramids that share  a cornercorner with one O(3)V6 octahedra, corners with four equivalent O(8)CaV5 octahedra, corners with two equivalent O(6)Ca2V3 square pyramids, corners with four equivalent O(2)Ca2V2 tetrahedra, edges with two equivalent O(4)V6 octahedra, edges with three equivalent O(8)CaV5 octahedra, edges with three equivalent O(6)Ca2V3 square pyramids, and  an edgeedge with one O(2)Ca2V2 tetrahedra. The corner-sharing octahedral tilt angles range from 4-42°. In the seventh O site, O(7) is bonded to one Ca(1), one V(3), two equivalent V(4), and two equivalent V(5) atoms to form distorted OCaV5 octahedra that share  a cornercorner with one O(7)CaV5 octahedra,  a cornercorner with one O(8)CaV5 octahedra, corners with two equivalent O(3)V6 octahedra, corners with four equivalent O(5)Ca2V3 square pyramids, edges with two equivalent O(7)CaV5 octahedra, edges with two equivalent O(4)V6 octahedra, edges with three equivalent O(3)V6 octahedra, edges with three equivalent O(5)Ca2V3 square pyramids, and edges with two equivalent O(1)Ca2V2 tetrahedra. The corner-sharing octahedral tilt angles range from 0-54°. In the eighth O site, O(8) is bonded to one Ca(2), one V(3), two equivalent V(1), and two equivalent V(2) atoms to form distorted OCaV5 octahedra that share  a cornercorner with one O(7)CaV5 octahedra,  a cornercorner with one O(8)CaV5 octahedra, corners with two equivalent O(4)V6 octahedra, corners with four equivalent O(6)Ca2V3 square pyramids, edges with two equivalent O(8)CaV5 octahedra, edges with two equivalent O(3)V6 octahedra, edges with three equivalent O(4)V6 octahedra, edges with three equivalent O(6)Ca2V3 square pyramids, and edges with two equivalent O(2)Ca2V2 tetrahedra. The corner-sharing octahedral tilt angles range from 0-53°.