CaV2O4 crystallizes in the orthorhombic Cmcm space group. Ca(1) is bonded in a 8-coordinate geometry to two equivalent O(2), two equivalent O(3), and four equivalent O(1) atoms. V(1) is bonded to one O(2), two equivalent O(3), and three equivalent O(1) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 0-39°. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ca(1) and three equivalent V(1) atoms to form distorted OCa2V3 trigonal bipyramids that share corners with four equivalent O(3)Ca2V4 octahedra, corners with two equivalent O(1)Ca2V3 trigonal bipyramids, edges with three equivalent O(3)Ca2V4 octahedra, and edges with five equivalent O(1)Ca2V3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 9-42°. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Ca(1) and two equivalent V(1) atoms. In the third O site, O(3) is bonded to two equivalent Ca(1) and four equivalent V(1) atoms to form distorted OCa2V4 octahedra that share corners with two equivalent O(3)Ca2V4 octahedra, corners with eight equivalent O(1)Ca2V3 trigonal bipyramids, edges with two equivalent O(3)Ca2V4 octahedra, and edges with six equivalent O(1)Ca2V3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 48°.
CaV2O4 crystallizes in the orthorhombic Cmcm space group. Ca(1) is bonded in a 8-coordinate geometry to two equivalent O(2), two equivalent O(3), and four equivalent O(1) atoms. Both Ca(1)-O(2) bond lengths are 2.37 Å. Both Ca(1)-O(3) bond lengths are 2.77 Å. All Ca(1)-O(1) bond lengths are 2.42 Å. V(1) is bonded to one O(2), two equivalent O(3), and three equivalent O(1) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 0-39°. The V(1)-O(2) bond length is 1.93 Å. Both V(1)-O(3) bond lengths are 2.15 Å. There is one shorter (2.04 Å) and two longer (2.09 Å) V(1)-O(1) bond lengths. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ca(1) and three equivalent V(1) atoms to form distorted OCa2V3 trigonal bipyramids that share corners with four equivalent O(3)Ca2V4 octahedra, corners with two equivalent O(1)Ca2V3 trigonal bipyramids, edges with three equivalent O(3)Ca2V4 octahedra, and edges with five equivalent O(1)Ca2V3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 9-42°. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Ca(1) and two equivalent V(1) atoms. In the third O site, O(3) is bonded to two equivalent Ca(1) and four equivalent V(1) atoms to form distorted OCa2V4 octahedra that share corners with two equivalent O(3)Ca2V4 octahedra, corners with eight equivalent O(1)Ca2V3 trigonal bipyramids, edges with two equivalent O(3)Ca2V4 octahedra, and edges with six equivalent O(1)Ca2V3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 48°.