V2P3O11 crystallizes in the monoclinic C2/c space group. V(1) is bonded to one O(1), one O(2), one O(3), one O(5), and two equivalent O(4) atoms to form VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four 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 two equivalent O(1) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-35°. In the second P site, P(2) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with four equivalent V(1)O6 octahedra and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-54°. There are six 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 bent 150 degrees geometry to one V(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one V(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to two equivalent V(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one V(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to two equivalent P(2) atoms.
V2P3O11 crystallizes in the monoclinic C2/c space group. V(1) is bonded to one O(1), one O(2), one O(3), one O(5), and two equivalent O(4) atoms to form VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The V(1)-O(1) bond length is 1.85 Å. The V(1)-O(2) bond length is 1.88 Å. The V(1)-O(3) bond length is 1.96 Å. The V(1)-O(5) bond length is 1.96 Å. There is one shorter (2.04 Å) and one longer (2.14 Å) V(1)-O(4) bond length. There are two inequivalent P sites. In the first P site, P(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-35°. Both P(1)-O(1) bond lengths are 1.53 Å. Both P(1)-O(2) bond lengths are 1.52 Å. In the second P site, P(2) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with four equivalent V(1)O6 octahedra and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-54°. The P(2)-O(3) bond length is 1.50 Å. The P(2)-O(4) bond length is 1.55 Å. The P(2)-O(5) bond length is 1.51 Å. The P(2)-O(6) bond length is 1.59 Å. There are six 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 bent 150 degrees geometry to one V(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one V(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to two equivalent V(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one V(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to two equivalent P(2) atoms.