CaV2O4 crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form distorted CaO6 pentagonal pyramids that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-16°. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(3) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form VO6 octahedra that share corners with three equivalent Ca(1)O6 pentagonal pyramids, edges with two equivalent V(1)O6 octahedra, edges with four equivalent V(2)O6 octahedra, and  an edgeedge with one Ca(1)O6 pentagonal pyramid. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share edges with two equivalent V(2)O6 octahedra, edges with four equivalent V(1)O6 octahedra, and edges with two equivalent Ca(1)O6 pentagonal pyramids. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Ca(1), one V(1), and two equivalent V(2) atoms. In the second O site, O(2) is bonded to one Ca(2), one V(1), and two equivalent V(2) atoms to form OCaV3 trigonal pyramids that share corners with four equivalent O(3)Ca2V3 trigonal bipyramids, corners with three equivalent O(2)CaV3 trigonal pyramids, and edges with four equivalent O(3)Ca2V3 trigonal bipyramids. In the third O site, O(3) is bonded to one Ca(1), one Ca(2), one V(2), and two equivalent V(1) atoms to form OCa2V3 trigonal bipyramids that share corners with five equivalent O(3)Ca2V3 trigonal bipyramids, corners with two equivalent O(2)CaV3 trigonal pyramids, edges with four equivalent O(3)Ca2V3 trigonal bipyramids, and edges with two equivalent O(2)CaV3 trigonal pyramids.
CaV2O4 crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form distorted CaO6 pentagonal pyramids that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-16°. Both Ca(1)-O(1) bond lengths are 2.29 Å. All Ca(1)-O(3) bond lengths are 2.41 Å. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(3) atoms. Both Ca(2)-O(2) bond lengths are 2.31 Å. All Ca(2)-O(3) bond lengths are 2.42 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form VO6 octahedra that share corners with three equivalent Ca(1)O6 pentagonal pyramids, edges with two equivalent V(1)O6 octahedra, edges with four equivalent V(2)O6 octahedra, and  an edgeedge with one Ca(1)O6 pentagonal pyramid. The V(1)-O(1) bond length is 1.95 Å. The V(1)-O(2) bond length is 2.01 Å. There are two shorter (2.04 Å) and two longer (2.08 Å) V(1)-O(3) bond lengths. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share edges with two equivalent V(2)O6 octahedra, edges with four equivalent V(1)O6 octahedra, and edges with two equivalent Ca(1)O6 pentagonal pyramids. Both V(2)-O(1) bond lengths are 2.02 Å. Both V(2)-O(2) bond lengths are 2.01 Å. Both V(2)-O(3) bond lengths are 2.04 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Ca(1), one V(1), and two equivalent V(2) atoms. In the second O site, O(2) is bonded to one Ca(2), one V(1), and two equivalent V(2) atoms to form OCaV3 trigonal pyramids that share corners with four equivalent O(3)Ca2V3 trigonal bipyramids, corners with three equivalent O(2)CaV3 trigonal pyramids, and edges with four equivalent O(3)Ca2V3 trigonal bipyramids. In the third O site, O(3) is bonded to one Ca(1), one Ca(2), one V(2), and two equivalent V(1) atoms to form OCa2V3 trigonal bipyramids that share corners with five equivalent O(3)Ca2V3 trigonal bipyramids, corners with two equivalent O(2)CaV3 trigonal pyramids, edges with four equivalent O(3)Ca2V3 trigonal bipyramids, and edges with two equivalent O(2)CaV3 trigonal pyramids.