CaVO2 crystallizes in the triclinic P-1 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one O(1), two equivalent O(3), and two equivalent O(4) atoms to form distorted CaO5 trigonal bipyramids that share corners with two equivalent V(2)O5 trigonal bipyramids, corners with four equivalent V(1)O5 trigonal bipyramids,  an edgeedge with one V(1)O5 trigonal bipyramid, edges with two equivalent Ca(1)O5 trigonal bipyramids, and  a faceface with one V(2)O5 trigonal bipyramid. In the second Ca site, Ca(2) is bonded in a rectangular see-saw-like geometry to one O(3), one O(4), and two equivalent O(2) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), two equivalent O(1), and two equivalent O(3) atoms to form distorted VO5 trigonal bipyramids that share corners with four equivalent Ca(1)O5 trigonal bipyramids, corners with four equivalent V(2)O5 trigonal bipyramids,  an edgeedge with one Ca(1)O5 trigonal bipyramid, and edges with two equivalent V(1)O5 trigonal bipyramids. In the second V site, V(2) is bonded to one O(1), two equivalent O(2), and two equivalent O(4) atoms to form distorted VO5 trigonal bipyramids that share corners with two equivalent Ca(1)O5 trigonal bipyramids, corners with four equivalent V(1)O5 trigonal bipyramids, edges with two equivalent V(2)O5 trigonal bipyramids, and  a faceface with one Ca(1)O5 trigonal bipyramid. 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 tetrahedra that share corners with two equivalent O(1)CaV3 tetrahedra, corners with four equivalent O(2)Ca2V3 trigonal bipyramids, corners with four equivalent O(3)Ca3V2 trigonal bipyramids,  an edgeedge with one O(3)Ca3V2 trigonal bipyramid, and edges with two equivalent O(4)Ca3V2 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Ca(2), one V(1), and two equivalent V(2) atoms to form OCa2V3 trigonal bipyramids that share corners with four equivalent O(1)CaV3 tetrahedra, corners with four equivalent O(4)Ca3V2 trigonal bipyramids,  an edgeedge with one O(4)Ca3V2 trigonal bipyramid, edges with two equivalent O(2)Ca2V3 trigonal bipyramids, and edges with two equivalent O(3)Ca3V2 trigonal bipyramids. In the third O site, O(3) is bonded to one Ca(2), two equivalent Ca(1), and two equivalent V(1) atoms to form distorted OCa3V2 trigonal bipyramids that share corners with four equivalent O(1)CaV3 tetrahedra, corners with three equivalent O(4)Ca3V2 trigonal bipyramids,  an edgeedge with one O(1)CaV3 tetrahedra,  an edgeedge with one O(4)Ca3V2 trigonal bipyramid, edges with two equivalent O(2)Ca2V3 trigonal bipyramids, and edges with two equivalent O(3)Ca3V2 trigonal bipyramids. In the fourth O site, O(4) is bonded to one Ca(2), two equivalent Ca(1), and two equivalent V(2) atoms to form distorted OCa3V2 trigonal bipyramids that share corners with three equivalent O(3)Ca3V2 trigonal bipyramids, corners with four equivalent O(2)Ca2V3 trigonal bipyramids, edges with two equivalent O(1)CaV3 tetrahedra,  an edgeedge with one O(2)Ca2V3 trigonal bipyramid,  an edgeedge with one O(3)Ca3V2 trigonal bipyramid, and edges with two equivalent O(4)Ca3V2 trigonal bipyramids.
CaVO2 crystallizes in the triclinic P-1 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one O(1), two equivalent O(3), and two equivalent O(4) atoms to form distorted CaO5 trigonal bipyramids that share corners with two equivalent V(2)O5 trigonal bipyramids, corners with four equivalent V(1)O5 trigonal bipyramids,  an edgeedge with one V(1)O5 trigonal bipyramid, edges with two equivalent Ca(1)O5 trigonal bipyramids, and  a faceface with one V(2)O5 trigonal bipyramid. The Ca(1)-O(1) bond length is 2.29 Å. Both Ca(1)-O(3) bond lengths are 2.33 Å. Both Ca(1)-O(4) bond lengths are 2.36 Å. In the second Ca site, Ca(2) is bonded in a rectangular see-saw-like geometry to one O(3), one O(4), and two equivalent O(2) atoms. The Ca(2)-O(3) bond length is 2.20 Å. The Ca(2)-O(4) bond length is 2.23 Å. There is one shorter (2.31 Å) and one longer (2.32 Å) Ca(2)-O(2) bond length. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), two equivalent O(1), and two equivalent O(3) atoms to form distorted VO5 trigonal bipyramids that share corners with four equivalent Ca(1)O5 trigonal bipyramids, corners with four equivalent V(2)O5 trigonal bipyramids,  an edgeedge with one Ca(1)O5 trigonal bipyramid, and edges with two equivalent V(1)O5 trigonal bipyramids. The V(1)-O(2) bond length is 2.20 Å. Both V(1)-O(1) bond lengths are 2.08 Å. Both V(1)-O(3) bond lengths are 2.28 Å. In the second V site, V(2) is bonded to one O(1), two equivalent O(2), and two equivalent O(4) atoms to form distorted VO5 trigonal bipyramids that share corners with two equivalent Ca(1)O5 trigonal bipyramids, corners with four equivalent V(1)O5 trigonal bipyramids, edges with two equivalent V(2)O5 trigonal bipyramids, and  a faceface with one Ca(1)O5 trigonal bipyramid. The V(2)-O(1) bond length is 2.07 Å. There is one shorter (2.21 Å) and one longer (2.22 Å) V(2)-O(2) bond length. Both V(2)-O(4) bond lengths are 2.23 Å. 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 tetrahedra that share corners with two equivalent O(1)CaV3 tetrahedra, corners with four equivalent O(2)Ca2V3 trigonal bipyramids, corners with four equivalent O(3)Ca3V2 trigonal bipyramids,  an edgeedge with one O(3)Ca3V2 trigonal bipyramid, and edges with two equivalent O(4)Ca3V2 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Ca(2), one V(1), and two equivalent V(2) atoms to form OCa2V3 trigonal bipyramids that share corners with four equivalent O(1)CaV3 tetrahedra, corners with four equivalent O(4)Ca3V2 trigonal bipyramids,  an edgeedge with one O(4)Ca3V2 trigonal bipyramid, edges with two equivalent O(2)Ca2V3 trigonal bipyramids, and edges with two equivalent O(3)Ca3V2 trigonal bipyramids. In the third O site, O(3) is bonded to one Ca(2), two equivalent Ca(1), and two equivalent V(1) atoms to form distorted OCa3V2 trigonal bipyramids that share corners with four equivalent O(1)CaV3 tetrahedra, corners with three equivalent O(4)Ca3V2 trigonal bipyramids,  an edgeedge with one O(1)CaV3 tetrahedra,  an edgeedge with one O(4)Ca3V2 trigonal bipyramid, edges with two equivalent O(2)Ca2V3 trigonal bipyramids, and edges with two equivalent O(3)Ca3V2 trigonal bipyramids. In the fourth O site, O(4) is bonded to one Ca(2), two equivalent Ca(1), and two equivalent V(2) atoms to form distorted OCa3V2 trigonal bipyramids that share corners with three equivalent O(3)Ca3V2 trigonal bipyramids, corners with four equivalent O(2)Ca2V3 trigonal bipyramids, edges with two equivalent O(1)CaV3 tetrahedra,  an edgeedge with one O(2)Ca2V3 trigonal bipyramid,  an edgeedge with one O(3)Ca3V2 trigonal bipyramid, and edges with two equivalent O(4)Ca3V2 trigonal bipyramids.