CaV2(PO4)2 crystallizes in the monoclinic C2/c space group. Ca(1) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(4), one O(5), one O(6), and two equivalent O(8) atoms. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(4), one O(6), one O(7), and two equivalent O(3) atoms to form distorted VO6 octahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 9-94°. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form distorted VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 94°. In the third V site, V(3) is bonded to two equivalent O(5), two equivalent O(6), and two equivalent O(7) atoms to form distorted VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(4), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-61°. In the second P site, P(2) is bonded to one O(2), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-78°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Ca(1), one V(2), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), and one P(2) atom. In the third O site, O(3) is bonded in a 1-coordinate geometry to one V(2), two equivalent V(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), one V(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Ca(1), one V(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Ca(1), one V(1), one V(3), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to two equivalent Ca(1) and one P(1) atom.
CaV2(PO4)2 crystallizes in the monoclinic C2/c space group. Ca(1) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(4), one O(5), one O(6), and two equivalent O(8) atoms. The Ca(1)-O(1) bond length is 2.37 Å. The Ca(1)-O(2) bond length is 2.44 Å. The Ca(1)-O(4) bond length is 2.69 Å. The Ca(1)-O(5) bond length is 2.67 Å. The Ca(1)-O(6) bond length is 2.52 Å. There is one shorter (2.31 Å) and one longer (2.45 Å) Ca(1)-O(8) bond length. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(4), one O(6), one O(7), and two equivalent O(3) atoms to form distorted VO6 octahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 9-94°. The V(1)-O(2) bond length is 2.10 Å. The V(1)-O(4) bond length is 2.14 Å. The V(1)-O(6) bond length is 2.21 Å. The V(1)-O(7) bond length is 2.13 Å. There is one shorter (2.34 Å) and one longer (2.69 Å) V(1)-O(3) bond length. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form distorted VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 94°. Both V(2)-O(1) bond lengths are 2.15 Å. Both V(2)-O(3) bond lengths are 2.51 Å. Both V(2)-O(4) bond lengths are 2.12 Å. In the third V site, V(3) is bonded to two equivalent O(5), two equivalent O(6), and two equivalent O(7) atoms to form distorted VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. Both V(3)-O(5) bond lengths are 2.13 Å. Both V(3)-O(6) bond lengths are 2.43 Å. Both V(3)-O(7) bond lengths are 2.13 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(4), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-61°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.57 Å. The P(1)-O(7) bond length is 1.55 Å. The P(1)-O(8) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(2), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-78°. The P(2)-O(2) bond length is 1.55 Å. The P(2)-O(3) bond length is 1.58 Å. The P(2)-O(5) bond length is 1.53 Å. The P(2)-O(6) bond length is 1.57 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Ca(1), one V(2), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), and one P(2) atom. In the third O site, O(3) is bonded in a 1-coordinate geometry to one V(2), two equivalent V(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), one V(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Ca(1), one V(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Ca(1), one V(1), one V(3), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to two equivalent Ca(1) and one P(1) atom.