VO(PO3)2 crystallizes in the triclinic P-1 space group. V(1) is bonded to one O(1), one O(3), one O(5), one O(7), and two equivalent O(6) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one 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(5), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-46°. In the second P site, P(2) is bonded to one O(2), one O(3), one O(4), and one O(6) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-57°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees 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 two equivalent V(1) and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one V(1) and one P(1) atom.
VO(PO3)2 crystallizes in the triclinic P-1 space group. V(1) is bonded to one O(1), one O(3), one O(5), one O(7), and two equivalent O(6) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The V(1)-O(1) bond length is 1.92 Å. The V(1)-O(3) bond length is 1.90 Å. The V(1)-O(5) bond length is 1.89 Å. The V(1)-O(7) bond length is 1.97 Å. There is one shorter (2.05 Å) and one longer (2.10 Å) V(1)-O(6) bond length. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-46°. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.58 Å. The P(1)-O(5) bond length is 1.54 Å. The P(1)-O(7) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(2), one O(3), one O(4), and one O(6) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-57°. The P(2)-O(2) bond length is 1.47 Å. The P(2)-O(3) bond length is 1.54 Å. The P(2)-O(4) bond length is 1.63 Å. The P(2)-O(6) bond length is 1.61 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees 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 two equivalent V(1) and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one V(1) and one P(1) atom.