CaV2O4 is Spinel-like structured and crystallizes in the trigonal P3m1 space group. There are six inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one O(9) and three equivalent O(1) atoms to form CaO4 tetrahedra that share corners with three equivalent Ca(5)O6 octahedra, corners with three equivalent V(5)O6 octahedra, and corners with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-67°. In the second Ca site, Ca(2) is bonded to one O(2) and three equivalent O(3) atoms to form CaO4 tetrahedra that share corners with three equivalent Ca(3)O6 octahedra, corners with three equivalent V(1)O6 octahedra, and corners with six equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-70°. In the third Ca site, Ca(3) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form CaO6 octahedra that share corners with three equivalent Ca(2)O4 tetrahedra, corners with three equivalent V(4)O4 tetrahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. In the fourth Ca site, Ca(4) is bonded to one O(5) and three equivalent O(7) atoms to form CaO4 tetrahedra that share corners with three equivalent V(2)O6 octahedra, corners with three equivalent V(3)O6 octahedra, and corners with six equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 59-61°. In the fifth Ca site, Ca(5) is bonded to three equivalent O(1) and three equivalent O(11) atoms to form CaO6 octahedra that share corners with three equivalent Ca(1)O4 tetrahedra, corners with three equivalent V(6)O4 tetrahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(5)O6 octahedra. In the sixth Ca site, Ca(6) is bonded to one O(12) and three equivalent O(8) atoms to form CaO4 tetrahedra that share corners with three equivalent V(3)O6 octahedra, corners with three equivalent V(5)O6 octahedra, and corners with six equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 60-63°. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(6), two equivalent O(1), and two equivalent O(4) atoms to form VO6 octahedra that share  a cornercorner with one Ca(2)O4 tetrahedra,  a cornercorner with one V(6)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(5)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. In the second V site, V(2) is bonded to one O(10), one O(5), two equivalent O(3), and two equivalent O(8) atoms to form VO6 octahedra that share  a cornercorner with one Ca(4)O4 tetrahedra,  a cornercorner with one V(4)O4 tetrahedra, corners with two equivalent Ca(2)O4 tetrahedra, corners with two equivalent Ca(6)O4 tetrahedra,  an edgeedge with one Ca(3)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. In the third V site, V(3) is bonded to three equivalent O(7) and three equivalent O(8) atoms to form VO6 octahedra that share corners with three equivalent Ca(4)O4 tetrahedra, corners with three equivalent Ca(6)O4 tetrahedra, edges with three equivalent V(2)O6 octahedra, and edges with three equivalent V(5)O6 octahedra. In the fourth V site, V(4) is bonded to one O(10) and three equivalent O(4) atoms to form VO4 tetrahedra that share corners with three equivalent Ca(3)O6 octahedra, corners with three equivalent V(2)O6 octahedra, and corners with six 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(12), one O(9), two equivalent O(11), and two equivalent O(7) atoms to form VO6 octahedra that share  a cornercorner with one Ca(1)O4 tetrahedra,  a cornercorner with one Ca(6)O4 tetrahedra, corners with two equivalent Ca(4)O4 tetrahedra, corners with two equivalent V(6)O4 tetrahedra,  an edgeedge with one Ca(5)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and edges with four equivalent V(5)O6 octahedra. In the sixth V site, V(6) is bonded to one O(6) and three equivalent O(11) atoms to form VO4 tetrahedra that share corners with three equivalent Ca(5)O6 octahedra, corners with three equivalent V(1)O6 octahedra, and corners with six equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-63°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Ca(1), one Ca(5), and two equivalent V(1) atoms to form distorted OCa2V2 tetrahedra that share corners with two equivalent O(1)Ca2V2 tetrahedra,  a cornercorner with one O(9)CaV3 trigonal pyramid, edges with two equivalent O(1)Ca2V2 tetrahedra, and  an edgeedge with one O(2)CaV3 trigonal pyramid. In the second O site, O(2) is bonded to one Ca(2) and three equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing OCaV3 trigonal pyramids. In the third O site, O(3) is bonded to one Ca(2), one Ca(3), and two equivalent V(2) atoms to form distorted OCa2V2 trigonal pyramids that share corners with four equivalent O(8)CaV3 tetrahedra,  a cornercorner with one O(2)CaV3 trigonal pyramid, corners with two equivalent O(3)Ca2V2 trigonal pyramids,  an edgeedge with one O(5)CaV3 trigonal pyramid, and edges with two equivalent O(3)Ca2V2 trigonal pyramids. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Ca(3), one V(4), and two equivalent V(1) atoms. In the fifth O site, O(5) is bonded to one Ca(4) and three equivalent V(2) atoms to form distorted OCaV3 trigonal pyramids that share corners with three equivalent O(7)CaV3 tetrahedra, corners with six equivalent O(8)CaV3 tetrahedra, and edges with three equivalent O(3)Ca2V2 trigonal pyramids. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one V(6) and three equivalent V(1) atoms. In the seventh O site, O(7) is bonded to one Ca(4), one V(3), and two equivalent V(5) atoms to form a mixture of edge and corner-sharing OCaV3 tetrahedra. In the eighth O site, O(8) is bonded to one Ca(6), one V(3), and two equivalent V(2) atoms to form OCaV3 tetrahedra that share  a cornercorner with one O(12)CaV3 tetrahedra, corners with two equivalent O(8)CaV3 tetrahedra, corners with three equivalent O(7)CaV3 tetrahedra, corners with two equivalent O(5)CaV3 trigonal pyramids, corners with four equivalent O(3)Ca2V2 trigonal pyramids, and edges with two equivalent O(8)CaV3 tetrahedra. In the ninth O site, O(9) is bonded to one Ca(1) and three equivalent V(5) atoms to form distorted OCaV3 trigonal pyramids that share corners with three equivalent O(1)Ca2V2 tetrahedra, corners with three equivalent O(12)CaV3 tetrahedra, and edges with three equivalent O(7)CaV3 tetrahedra. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one V(4) and three equivalent V(2) atoms. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Ca(5), one V(6), and two equivalent V(5) atoms. In the twelfth O site, O(12) is bonded to one Ca(6) and three equivalent V(5) atoms to form corner-sharing OCaV3 tetrahedra.
CaV2O4 is Spinel-like structured and crystallizes in the trigonal P3m1 space group. There are six inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one O(9) and three equivalent O(1) atoms to form CaO4 tetrahedra that share corners with three equivalent Ca(5)O6 octahedra, corners with three equivalent V(5)O6 octahedra, and corners with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-67°. The Ca(1)-O(9) bond length is 2.31 Å. All Ca(1)-O(1) bond lengths are 2.18 Å. In the second Ca site, Ca(2) is bonded to one O(2) and three equivalent O(3) atoms to form CaO4 tetrahedra that share corners with three equivalent Ca(3)O6 octahedra, corners with three equivalent V(1)O6 octahedra, and corners with six equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-70°. The Ca(2)-O(2) bond length is 2.21 Å. All Ca(2)-O(3) bond lengths are 2.19 Å. In the third Ca site, Ca(3) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form CaO6 octahedra that share corners with three equivalent Ca(2)O4 tetrahedra, corners with three equivalent V(4)O4 tetrahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. All Ca(3)-O(3) bond lengths are 2.29 Å. All Ca(3)-O(4) bond lengths are 2.34 Å. In the fourth Ca site, Ca(4) is bonded to one O(5) and three equivalent O(7) atoms to form CaO4 tetrahedra that share corners with three equivalent V(2)O6 octahedra, corners with three equivalent V(3)O6 octahedra, and corners with six equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 59-61°. The Ca(4)-O(5) bond length is 2.17 Å. All Ca(4)-O(7) bond lengths are 2.19 Å. In the fifth Ca site, Ca(5) is bonded to three equivalent O(1) and three equivalent O(11) atoms to form CaO6 octahedra that share corners with three equivalent Ca(1)O4 tetrahedra, corners with three equivalent V(6)O4 tetrahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(5)O6 octahedra. All Ca(5)-O(1) bond lengths are 2.27 Å. All Ca(5)-O(11) bond lengths are 2.33 Å. In the sixth Ca site, Ca(6) is bonded to one O(12) and three equivalent O(8) atoms to form CaO4 tetrahedra that share corners with three equivalent V(3)O6 octahedra, corners with three equivalent V(5)O6 octahedra, and corners with six equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 60-63°. The Ca(6)-O(12) bond length is 2.30 Å. All Ca(6)-O(8) bond lengths are 2.21 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(6), two equivalent O(1), and two equivalent O(4) atoms to form VO6 octahedra that share  a cornercorner with one Ca(2)O4 tetrahedra,  a cornercorner with one V(6)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(5)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The V(1)-O(2) bond length is 2.08 Å. The V(1)-O(6) bond length is 2.27 Å. Both V(1)-O(1) bond lengths are 1.99 Å. Both V(1)-O(4) bond lengths are 2.12 Å. In the second V site, V(2) is bonded to one O(10), one O(5), two equivalent O(3), and two equivalent O(8) atoms to form VO6 octahedra that share  a cornercorner with one Ca(4)O4 tetrahedra,  a cornercorner with one V(4)O4 tetrahedra, corners with two equivalent Ca(2)O4 tetrahedra, corners with two equivalent Ca(6)O4 tetrahedra,  an edgeedge with one Ca(3)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The V(2)-O(10) bond length is 2.31 Å. The V(2)-O(5) bond length is 2.09 Å. Both V(2)-O(3) bond lengths are 1.99 Å. Both V(2)-O(8) bond lengths are 2.07 Å. In the third V site, V(3) is bonded to three equivalent O(7) and three equivalent O(8) atoms to form VO6 octahedra that share corners with three equivalent Ca(4)O4 tetrahedra, corners with three equivalent Ca(6)O4 tetrahedra, edges with three equivalent V(2)O6 octahedra, and edges with three equivalent V(5)O6 octahedra. All V(3)-O(7) bond lengths are 2.08 Å. All V(3)-O(8) bond lengths are 2.04 Å. In the fourth V site, V(4) is bonded to one O(10) and three equivalent O(4) atoms to form VO4 tetrahedra that share corners with three equivalent Ca(3)O6 octahedra, corners with three equivalent V(2)O6 octahedra, and corners with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-64°. The V(4)-O(10) bond length is 1.96 Å. All V(4)-O(4) bond lengths are 2.02 Å. In the fifth V site, V(5) is bonded to one O(12), one O(9), two equivalent O(11), and two equivalent O(7) atoms to form VO6 octahedra that share  a cornercorner with one Ca(1)O4 tetrahedra,  a cornercorner with one Ca(6)O4 tetrahedra, corners with two equivalent Ca(4)O4 tetrahedra, corners with two equivalent V(6)O4 tetrahedra,  an edgeedge with one Ca(5)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and edges with four equivalent V(5)O6 octahedra. The V(5)-O(12) bond length is 2.08 Å. The V(5)-O(9) bond length is 2.06 Å. Both V(5)-O(11) bond lengths are 2.16 Å. Both V(5)-O(7) bond lengths are 2.05 Å. In the sixth V site, V(6) is bonded to one O(6) and three equivalent O(11) atoms to form VO4 tetrahedra that share corners with three equivalent Ca(5)O6 octahedra, corners with three equivalent V(1)O6 octahedra, and corners with six equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-63°. The V(6)-O(6) bond length is 1.98 Å. All V(6)-O(11) bond lengths are 1.98 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Ca(1), one Ca(5), and two equivalent V(1) atoms to form distorted OCa2V2 tetrahedra that share corners with two equivalent O(1)Ca2V2 tetrahedra,  a cornercorner with one O(9)CaV3 trigonal pyramid, edges with two equivalent O(1)Ca2V2 tetrahedra, and  an edgeedge with one O(2)CaV3 trigonal pyramid. In the second O site, O(2) is bonded to one Ca(2) and three equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing OCaV3 trigonal pyramids. In the third O site, O(3) is bonded to one Ca(2), one Ca(3), and two equivalent V(2) atoms to form distorted OCa2V2 trigonal pyramids that share corners with four equivalent O(8)CaV3 tetrahedra,  a cornercorner with one O(2)CaV3 trigonal pyramid, corners with two equivalent O(3)Ca2V2 trigonal pyramids,  an edgeedge with one O(5)CaV3 trigonal pyramid, and edges with two equivalent O(3)Ca2V2 trigonal pyramids. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Ca(3), one V(4), and two equivalent V(1) atoms. In the fifth O site, O(5) is bonded to one Ca(4) and three equivalent V(2) atoms to form distorted OCaV3 trigonal pyramids that share corners with three equivalent O(7)CaV3 tetrahedra, corners with six equivalent O(8)CaV3 tetrahedra, and edges with three equivalent O(3)Ca2V2 trigonal pyramids. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one V(6) and three equivalent V(1) atoms. In the seventh O site, O(7) is bonded to one Ca(4), one V(3), and two equivalent V(5) atoms to form a mixture of edge and corner-sharing OCaV3 tetrahedra. In the eighth O site, O(8) is bonded to one Ca(6), one V(3), and two equivalent V(2) atoms to form OCaV3 tetrahedra that share  a cornercorner with one O(12)CaV3 tetrahedra, corners with two equivalent O(8)CaV3 tetrahedra, corners with three equivalent O(7)CaV3 tetrahedra, corners with two equivalent O(5)CaV3 trigonal pyramids, corners with four equivalent O(3)Ca2V2 trigonal pyramids, and edges with two equivalent O(8)CaV3 tetrahedra. In the ninth O site, O(9) is bonded to one Ca(1) and three equivalent V(5) atoms to form distorted OCaV3 trigonal pyramids that share corners with three equivalent O(1)Ca2V2 tetrahedra, corners with three equivalent O(12)CaV3 tetrahedra, and edges with three equivalent O(7)CaV3 tetrahedra. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one V(4) and three equivalent V(2) atoms. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Ca(5), one V(6), and two equivalent V(5) atoms. In the twelfth O site, O(12) is bonded to one Ca(6) and three equivalent V(5) atoms to form corner-sharing OCaV3 tetrahedra.