VCd2PO7 crystallizes in the monoclinic P2_1 space group. V(1) is bonded to one O(1), one O(3), one O(5), and one O(6) atom to form VO4 tetrahedra that share corners with three equivalent Cd(1)O6 octahedra, corners with three equivalent Cd(2)O6 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-61°. There are two inequivalent Cd sites. In the first Cd site, Cd(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form distorted CdO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and edges with three equivalent Cd(2)O6 octahedra. In the second Cd site, Cd(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form distorted CdO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and edges with three equivalent Cd(1)O6 octahedra. P(1) is bonded to one O(2), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent Cd(1)O6 octahedra, corners with three equivalent Cd(2)O6 octahedra, and  a cornercorner with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-60°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one Cd(1), and one Cd(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Cd(1), one Cd(2), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(1), one Cd(1), and one Cd(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Cd(1), one Cd(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to one V(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one V(1), one Cd(1), and one Cd(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Cd(1), one Cd(2), and one P(1) atom.
VCd2PO7 crystallizes in the monoclinic P2_1 space group. V(1) is bonded to one O(1), one O(3), one O(5), and one O(6) atom to form VO4 tetrahedra that share corners with three equivalent Cd(1)O6 octahedra, corners with three equivalent Cd(2)O6 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-61°. The V(1)-O(1) bond length is 1.72 Å. The V(1)-O(3) bond length is 1.73 Å. The V(1)-O(5) bond length is 1.80 Å. The V(1)-O(6) bond length is 1.72 Å. There are two inequivalent Cd sites. In the first Cd site, Cd(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form distorted CdO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and edges with three equivalent Cd(2)O6 octahedra. The Cd(1)-O(1) bond length is 2.28 Å. The Cd(1)-O(2) bond length is 2.40 Å. The Cd(1)-O(3) bond length is 2.22 Å. The Cd(1)-O(4) bond length is 2.50 Å. The Cd(1)-O(6) bond length is 2.36 Å. The Cd(1)-O(7) bond length is 2.32 Å. In the second Cd site, Cd(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form distorted CdO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and edges with three equivalent Cd(1)O6 octahedra. The Cd(2)-O(1) bond length is 2.26 Å. The Cd(2)-O(2) bond length is 2.36 Å. The Cd(2)-O(3) bond length is 2.43 Å. The Cd(2)-O(4) bond length is 2.30 Å. The Cd(2)-O(6) bond length is 2.26 Å. The Cd(2)-O(7) bond length is 2.44 Å. P(1) is bonded to one O(2), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent Cd(1)O6 octahedra, corners with three equivalent Cd(2)O6 octahedra, and  a cornercorner with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-60°. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.59 Å. The P(1)-O(7) bond length is 1.54 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one Cd(1), and one Cd(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Cd(1), one Cd(2), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(1), one Cd(1), and one Cd(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Cd(1), one Cd(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to one V(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one V(1), one Cd(1), and one Cd(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Cd(1), one Cd(2), and one P(1) atom.