CaV2O4 is Spinel-like structured and crystallizes in the monoclinic Pm space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one O(11), one O(3), and two equivalent O(10) atoms to form CaO4 tetrahedra that share  a cornercorner with one Ca(3)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Ca(4)O6 octahedra, corners with two equivalent V(5)O6 octahedra, corners with two equivalent V(6)O6 octahedra, and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-69°. In the second Ca site, Ca(2) is bonded to one O(12), one O(4), and two equivalent O(9) atoms to form CaO4 tetrahedra that share  a cornercorner with one Ca(4)O6 octahedra,  a cornercorner with one V(6)O6 octahedra, corners with two equivalent Ca(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with four equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-69°. In the third Ca site, Ca(3) is bonded to one O(11), one O(5), two equivalent O(7), and two equivalent O(9) atoms to form CaO6 octahedra that share  a cornercorner with one Ca(1)O4 tetrahedra,  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent Ca(2)O4 tetrahedra, corners with two equivalent V(4)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. In the fourth Ca site, Ca(4) is bonded to one O(12), one O(6), two equivalent O(10), and two equivalent O(8) atoms to form CaO6 octahedra that share  a cornercorner with one Ca(2)O4 tetrahedra,  a cornercorner with one V(4)O4 tetrahedra, corners with two equivalent Ca(1)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(11), one O(2), one O(3), one O(6), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Ca(2)O4 tetrahedra,  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent Ca(1)O4 tetrahedra, corners with two equivalent V(4)O4 tetrahedra,  an edgeedge with one Ca(3)O6 octahedra,  an edgeedge with one Ca(4)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(6)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. In the second V site, V(2) is bonded to one O(1), one O(3), two equivalent O(7), and two equivalent O(9) atoms to form VO6 octahedra that share  a cornercorner with one Ca(1)O4 tetrahedra,  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent Ca(2)O4 tetrahedra, corners with two equivalent V(4)O4 tetrahedra, edges with two equivalent Ca(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. In the third V site, V(3) is bonded to one O(1), one O(5), and two equivalent O(8) atoms to form VO4 tetrahedra that share  a cornercorner with one Ca(3)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Ca(4)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(6)O6 octahedra, and corners with four equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-64°. In the fourth V site, V(4) is bonded to one O(2), one O(6), and two equivalent O(7) atoms to form VO4 tetrahedra that share  a cornercorner with one Ca(4)O6 octahedra,  a cornercorner with one V(6)O6 octahedra, corners with two equivalent Ca(3)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(5)O6 octahedra, and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-64°. In the fifth V site, V(5) is bonded to one O(1), one O(10), one O(12), one O(4), one O(5), and one O(7) atom to form VO6 octahedra that share  a cornercorner with one Ca(1)O4 tetrahedra,  a cornercorner with one V(4)O4 tetrahedra, corners with two equivalent Ca(2)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra,  an edgeedge with one Ca(3)O6 octahedra,  an edgeedge with one Ca(4)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(6)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. In the sixth V site, V(6) is bonded to one O(2), one O(4), two equivalent O(10), and two equivalent O(8) atoms to form VO6 octahedra that share  a cornercorner with one Ca(2)O4 tetrahedra,  a cornercorner with one V(4)O4 tetrahedra, corners with two equivalent Ca(1)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, edges with two equivalent Ca(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one V(2), one V(3), and two equivalent V(5) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one V(4), one V(6), and two equivalent V(1) atoms. In the third O site, O(3) is bonded to one Ca(1), one V(2), and two equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing OCaV3 trigonal pyramids. In the fourth O site, O(4) is bonded to one Ca(2), one V(6), and two equivalent V(5) atoms to form a mixture of distorted corner and edge-sharing OCaV3 trigonal pyramids. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Ca(3), one V(3), and two equivalent V(5) atoms. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Ca(4), one V(4), and two equivalent V(1) atoms. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Ca(3), one V(2), one V(4), and one V(5) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Ca(4), one V(1), one V(3), and one V(6) atom. In the ninth O site, O(9) is bonded to one Ca(2), one Ca(3), one V(1), and one V(2) atom to form distorted OCa2V2 trigonal pyramids that share  a cornercorner with one O(12)Ca2V2 trigonal pyramid,  a cornercorner with one O(9)Ca2V2 trigonal pyramid,  a cornercorner with one O(4)CaV3 trigonal pyramid,  an edgeedge with one O(11)Ca2V2 trigonal pyramid,  an edgeedge with one O(9)Ca2V2 trigonal pyramid, and  an edgeedge with one O(3)CaV3 trigonal pyramid. In the tenth O site, O(10) is bonded to one Ca(1), one Ca(4), one V(5), and one V(6) atom to form distorted OCa2V2 trigonal pyramids that share  a cornercorner with one O(10)Ca2V2 trigonal pyramid,  a cornercorner with one O(11)Ca2V2 trigonal pyramid,  a cornercorner with one O(3)CaV3 trigonal pyramid,  an edgeedge with one O(10)Ca2V2 trigonal pyramid,  an edgeedge with one O(12)Ca2V2 trigonal pyramid, and  an edgeedge with one O(4)CaV3 trigonal pyramid. In the eleventh O site, O(11) is bonded to one Ca(1), one Ca(3), and two equivalent V(1) atoms to form distorted OCa2V2 trigonal pyramids that share  a cornercorner with one O(3)CaV3 trigonal pyramid, corners with two equivalent O(10)Ca2V2 trigonal pyramids,  an edgeedge with one O(3)CaV3 trigonal pyramid, and edges with two equivalent O(9)Ca2V2 trigonal pyramids. In the twelfth O site, O(12) is bonded to one Ca(2), one Ca(4), and two equivalent V(5) atoms to form distorted OCa2V2 trigonal pyramids that share  a cornercorner with one O(4)CaV3 trigonal pyramid, corners with two equivalent O(9)Ca2V2 trigonal pyramids,  an edgeedge with one O(4)CaV3 trigonal pyramid, and edges with two equivalent O(10)Ca2V2 trigonal pyramids.
CaV2O4 is Spinel-like structured and crystallizes in the monoclinic Pm space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one O(11), one O(3), and two equivalent O(10) atoms to form CaO4 tetrahedra that share  a cornercorner with one Ca(3)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Ca(4)O6 octahedra, corners with two equivalent V(5)O6 octahedra, corners with two equivalent V(6)O6 octahedra, and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-69°. The Ca(1)-O(11) bond length is 2.19 Å. The Ca(1)-O(3) bond length is 2.22 Å. Both Ca(1)-O(10) bond lengths are 2.19 Å. In the second Ca site, Ca(2) is bonded to one O(12), one O(4), and two equivalent O(9) atoms to form CaO4 tetrahedra that share  a cornercorner with one Ca(4)O6 octahedra,  a cornercorner with one V(6)O6 octahedra, corners with two equivalent Ca(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with four equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-69°. The Ca(2)-O(12) bond length is 2.19 Å. The Ca(2)-O(4) bond length is 2.23 Å. Both Ca(2)-O(9) bond lengths are 2.18 Å. In the third Ca site, Ca(3) is bonded to one O(11), one O(5), two equivalent O(7), and two equivalent O(9) atoms to form CaO6 octahedra that share  a cornercorner with one Ca(1)O4 tetrahedra,  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent Ca(2)O4 tetrahedra, corners with two equivalent V(4)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The Ca(3)-O(11) bond length is 2.25 Å. The Ca(3)-O(5) bond length is 2.31 Å. Both Ca(3)-O(7) bond lengths are 2.31 Å. Both Ca(3)-O(9) bond lengths are 2.26 Å. In the fourth Ca site, Ca(4) is bonded to one O(12), one O(6), two equivalent O(10), and two equivalent O(8) atoms to form CaO6 octahedra that share  a cornercorner with one Ca(2)O4 tetrahedra,  a cornercorner with one V(4)O4 tetrahedra, corners with two equivalent Ca(1)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The Ca(4)-O(12) bond length is 2.26 Å. The Ca(4)-O(6) bond length is 2.31 Å. Both Ca(4)-O(10) bond lengths are 2.26 Å. Both Ca(4)-O(8) bond lengths are 2.32 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(11), one O(2), one O(3), one O(6), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Ca(2)O4 tetrahedra,  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent Ca(1)O4 tetrahedra, corners with two equivalent V(4)O4 tetrahedra,  an edgeedge with one Ca(3)O6 octahedra,  an edgeedge with one Ca(4)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(6)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The V(1)-O(11) bond length is 1.98 Å. The V(1)-O(2) bond length is 2.28 Å. The V(1)-O(3) bond length is 2.08 Å. The V(1)-O(6) bond length is 2.13 Å. The V(1)-O(8) bond length is 2.12 Å. The V(1)-O(9) bond length is 1.98 Å. In the second V site, V(2) is bonded to one O(1), one O(3), two equivalent O(7), and two equivalent O(9) atoms to form VO6 octahedra that share  a cornercorner with one Ca(1)O4 tetrahedra,  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent Ca(2)O4 tetrahedra, corners with two equivalent V(4)O4 tetrahedra, edges with two equivalent Ca(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The V(2)-O(1) bond length is 2.27 Å. The V(2)-O(3) bond length is 2.09 Å. Both V(2)-O(7) bond lengths are 2.13 Å. Both V(2)-O(9) bond lengths are 1.98 Å. In the third V site, V(3) is bonded to one O(1), one O(5), and two equivalent O(8) atoms to form VO4 tetrahedra that share  a cornercorner with one Ca(3)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Ca(4)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(6)O6 octahedra, and corners with four equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-64°. The V(3)-O(1) bond length is 2.01 Å. The V(3)-O(5) bond length is 1.99 Å. Both V(3)-O(8) bond lengths are 1.99 Å. In the fourth V site, V(4) is bonded to one O(2), one O(6), and two equivalent O(7) atoms to form VO4 tetrahedra that share  a cornercorner with one Ca(4)O6 octahedra,  a cornercorner with one V(6)O6 octahedra, corners with two equivalent Ca(3)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(5)O6 octahedra, and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-64°. The V(4)-O(2) bond length is 2.01 Å. The V(4)-O(6) bond length is 1.99 Å. Both V(4)-O(7) bond lengths are 1.99 Å. In the fifth V site, V(5) is bonded to one O(1), one O(10), one O(12), one O(4), one O(5), and one O(7) atom to form VO6 octahedra that share  a cornercorner with one Ca(1)O4 tetrahedra,  a cornercorner with one V(4)O4 tetrahedra, corners with two equivalent Ca(2)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra,  an edgeedge with one Ca(3)O6 octahedra,  an edgeedge with one Ca(4)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(6)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The V(5)-O(1) bond length is 2.29 Å. The V(5)-O(10) bond length is 1.98 Å. The V(5)-O(12) bond length is 1.98 Å. The V(5)-O(4) bond length is 2.08 Å. The V(5)-O(5) bond length is 2.12 Å. The V(5)-O(7) bond length is 2.12 Å. In the sixth V site, V(6) is bonded to one O(2), one O(4), two equivalent O(10), and two equivalent O(8) atoms to form VO6 octahedra that share  a cornercorner with one Ca(2)O4 tetrahedra,  a cornercorner with one V(4)O4 tetrahedra, corners with two equivalent Ca(1)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, edges with two equivalent Ca(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The V(6)-O(2) bond length is 2.27 Å. The V(6)-O(4) bond length is 2.09 Å. Both V(6)-O(10) bond lengths are 1.98 Å. Both V(6)-O(8) bond lengths are 2.13 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one V(2), one V(3), and two equivalent V(5) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one V(4), one V(6), and two equivalent V(1) atoms. In the third O site, O(3) is bonded to one Ca(1), one V(2), and two equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing OCaV3 trigonal pyramids. In the fourth O site, O(4) is bonded to one Ca(2), one V(6), and two equivalent V(5) atoms to form a mixture of distorted corner and edge-sharing OCaV3 trigonal pyramids. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Ca(3), one V(3), and two equivalent V(5) atoms. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Ca(4), one V(4), and two equivalent V(1) atoms. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Ca(3), one V(2), one V(4), and one V(5) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Ca(4), one V(1), one V(3), and one V(6) atom. In the ninth O site, O(9) is bonded to one Ca(2), one Ca(3), one V(1), and one V(2) atom to form distorted OCa2V2 trigonal pyramids that share  a cornercorner with one O(12)Ca2V2 trigonal pyramid,  a cornercorner with one O(9)Ca2V2 trigonal pyramid,  a cornercorner with one O(4)CaV3 trigonal pyramid,  an edgeedge with one O(11)Ca2V2 trigonal pyramid,  an edgeedge with one O(9)Ca2V2 trigonal pyramid, and  an edgeedge with one O(3)CaV3 trigonal pyramid. In the tenth O site, O(10) is bonded to one Ca(1), one Ca(4), one V(5), and one V(6) atom to form distorted OCa2V2 trigonal pyramids that share  a cornercorner with one O(10)Ca2V2 trigonal pyramid,  a cornercorner with one O(11)Ca2V2 trigonal pyramid,  a cornercorner with one O(3)CaV3 trigonal pyramid,  an edgeedge with one O(10)Ca2V2 trigonal pyramid,  an edgeedge with one O(12)Ca2V2 trigonal pyramid, and  an edgeedge with one O(4)CaV3 trigonal pyramid. In the eleventh O site, O(11) is bonded to one Ca(1), one Ca(3), and two equivalent V(1) atoms to form distorted OCa2V2 trigonal pyramids that share  a cornercorner with one O(3)CaV3 trigonal pyramid, corners with two equivalent O(10)Ca2V2 trigonal pyramids,  an edgeedge with one O(3)CaV3 trigonal pyramid, and edges with two equivalent O(9)Ca2V2 trigonal pyramids. In the twelfth O site, O(12) is bonded to one Ca(2), one Ca(4), and two equivalent V(5) atoms to form distorted OCa2V2 trigonal pyramids that share  a cornercorner with one O(4)CaV3 trigonal pyramid, corners with two equivalent O(9)Ca2V2 trigonal pyramids,  an edgeedge with one O(4)CaV3 trigonal pyramid, and edges with two equivalent O(10)Ca2V2 trigonal pyramids.