CaV2O4 crystallizes in the monoclinic C2/m space group. Ca(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted CaO6 pentagonal pyramids that share corners with two equivalent V(2)O6 octahedra, corners with three equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with three equivalent V(1)O6 octahedra, edges with two equivalent Ca(1)O6 pentagonal pyramids, and  a faceface with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-52°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), two equivalent O(1), and three equivalent O(3) atoms to form VO6 octahedra that share corners with four equivalent V(2)O6 octahedra, corners with three equivalent Ca(1)O6 pentagonal pyramids, edges with four equivalent V(1)O6 octahedra, and edges with three equivalent Ca(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 51-62°. In the second V site, V(2) is bonded to one O(1), two equivalent O(2), and three equivalent O(4) atoms to form distorted VO6 octahedra that share corners with four equivalent V(1)O6 octahedra, corners with two equivalent Ca(1)O6 pentagonal pyramids, edges with four equivalent V(2)O6 octahedra, edges with two equivalent Ca(1)O6 pentagonal pyramids, and  a faceface with one Ca(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 51-62°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Ca(1), one V(2), and two equivalent V(1) atoms to form OCaV3 trigonal pyramids that share  a cornercorner with one O(4)Ca2V3 square pyramid, corners with two equivalent O(3)Ca2V3 square pyramids, corners with two equivalent O(1)CaV3 trigonal pyramids, edges with two equivalent O(4)Ca2V3 square pyramids, and edges with three equivalent O(3)Ca2V3 square pyramids. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Ca(1), one V(1), and two equivalent V(2) atoms. In the third O site, O(3) is bonded to two equivalent Ca(1) and three equivalent V(1) atoms to form OCa2V3 square pyramids that share corners with two equivalent O(4)Ca2V3 square pyramids, corners with two equivalent O(1)CaV3 trigonal pyramids,  an edgeedge with one O(4)Ca2V3 square pyramid, edges with four equivalent O(3)Ca2V3 square pyramids, and edges with three equivalent O(1)CaV3 trigonal pyramids. In the fourth O site, O(4) is bonded to two equivalent Ca(1) and three equivalent V(2) atoms to form distorted OCa2V3 square pyramids that share corners with two equivalent O(3)Ca2V3 square pyramids,  a cornercorner with one O(1)CaV3 trigonal pyramid,  an edgeedge with one O(3)Ca2V3 square pyramid, edges with four equivalent O(4)Ca2V3 square pyramids, and edges with two equivalent O(1)CaV3 trigonal pyramids.
CaV2O4 crystallizes in the monoclinic C2/m space group. Ca(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted CaO6 pentagonal pyramids that share corners with two equivalent V(2)O6 octahedra, corners with three equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with three equivalent V(1)O6 octahedra, edges with two equivalent Ca(1)O6 pentagonal pyramids, and  a faceface with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-52°. The Ca(1)-O(1) bond length is 2.42 Å. The Ca(1)-O(2) bond length is 2.46 Å. Both Ca(1)-O(3) bond lengths are 2.34 Å. Both Ca(1)-O(4) bond lengths are 2.26 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), two equivalent O(1), and three equivalent O(3) atoms to form VO6 octahedra that share corners with four equivalent V(2)O6 octahedra, corners with three equivalent Ca(1)O6 pentagonal pyramids, edges with four equivalent V(1)O6 octahedra, and edges with three equivalent Ca(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 51-62°. The V(1)-O(2) bond length is 1.99 Å. Both V(1)-O(1) bond lengths are 2.04 Å. There are two shorter (2.18 Å) and one longer (2.19 Å) V(1)-O(3) bond length. In the second V site, V(2) is bonded to one O(1), two equivalent O(2), and three equivalent O(4) atoms to form distorted VO6 octahedra that share corners with four equivalent V(1)O6 octahedra, corners with two equivalent Ca(1)O6 pentagonal pyramids, edges with four equivalent V(2)O6 octahedra, edges with two equivalent Ca(1)O6 pentagonal pyramids, and  a faceface with one Ca(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 51-62°. The V(2)-O(1) bond length is 2.03 Å. Both V(2)-O(2) bond lengths are 2.08 Å. There is one shorter (2.01 Å) and two longer (2.16 Å) V(2)-O(4) bond lengths. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Ca(1), one V(2), and two equivalent V(1) atoms to form OCaV3 trigonal pyramids that share  a cornercorner with one O(4)Ca2V3 square pyramid, corners with two equivalent O(3)Ca2V3 square pyramids, corners with two equivalent O(1)CaV3 trigonal pyramids, edges with two equivalent O(4)Ca2V3 square pyramids, and edges with three equivalent O(3)Ca2V3 square pyramids. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Ca(1), one V(1), and two equivalent V(2) atoms. In the third O site, O(3) is bonded to two equivalent Ca(1) and three equivalent V(1) atoms to form OCa2V3 square pyramids that share corners with two equivalent O(4)Ca2V3 square pyramids, corners with two equivalent O(1)CaV3 trigonal pyramids,  an edgeedge with one O(4)Ca2V3 square pyramid, edges with four equivalent O(3)Ca2V3 square pyramids, and edges with three equivalent O(1)CaV3 trigonal pyramids. In the fourth O site, O(4) is bonded to two equivalent Ca(1) and three equivalent V(2) atoms to form distorted OCa2V3 square pyramids that share corners with two equivalent O(3)Ca2V3 square pyramids,  a cornercorner with one O(1)CaV3 trigonal pyramid,  an edgeedge with one O(3)Ca2V3 square pyramid, edges with four equivalent O(4)Ca2V3 square pyramids, and edges with two equivalent O(1)CaV3 trigonal pyramids.