V(PO3)4 crystallizes in the monoclinic C2/c space group. V(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra and corners with four equivalent P(1)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 16-26°. 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(1)O6 octahedra and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 23°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the third O site, O(3) is bonded in a linear geometry to one P(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a single-bond geometry to one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom.
V(PO3)4 crystallizes in the monoclinic C2/c space group. V(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra and corners with four equivalent P(1)O4 tetrahedra. Both V(1)-O(1) bond lengths are 1.96 Å. Both V(1)-O(4) bond lengths are 2.01 Å. Both V(1)-O(6) bond lengths are 1.89 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 16-26°. The P(1)-O(1) bond length is 1.50 Å. The P(1)-O(2) bond length is 1.58 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.50 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(1)O6 octahedra and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 23°. The P(2)-O(2) bond length is 1.61 Å. The P(2)-O(3) bond length is 1.61 Å. The P(2)-O(5) bond length is 1.46 Å. The P(2)-O(6) bond length is 1.54 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the third O site, O(3) is bonded in a linear geometry to one P(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a single-bond geometry to one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom.