(VO)2P2O7 crystallizes in the orthorhombic Pbcn space group. V(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form distorted VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 16°. P(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with four equivalent V(1)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-51°. There are five inequivalent O sites. In the first O site, O(5) is bonded in a bent 150 degrees geometry to two equivalent P(1) atoms. In the second O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the third O site, O(2) is bonded in a distorted linear geometry to two equivalent V(1) atoms. In the fourth O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent V(1) and one P(1) atom. In the fifth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom.
(VO)2P2O7 crystallizes in the orthorhombic Pbcn space group. V(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form distorted VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 16°. The V(1)-O(1) bond length is 1.96 Å. The V(1)-O(4) bond length is 1.98 Å. There is one shorter (1.68 Å) and one longer (2.12 Å) V(1)-O(2) bond length. There is one shorter (2.12 Å) and one longer (2.14 Å) V(1)-O(3) bond length. P(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with four equivalent V(1)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-51°. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.51 Å. The P(1)-O(5) bond length is 1.59 Å. There are five inequivalent O sites. In the first O site, O(5) is bonded in a bent 150 degrees geometry to two equivalent P(1) atoms. In the second O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the third O site, O(2) is bonded in a distorted linear geometry to two equivalent V(1) atoms. In the fourth O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent V(1) and one P(1) atom. In the fifth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom.