Li2VOP2O7 crystallizes in the trigonal P-3 space group. Li(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-70°. There are two inequivalent V sites. In the first V site, V(1) is bonded to six equivalent O(1) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra and corners with six equivalent P(1)O4 tetrahedra. In the second V site, V(2) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra and corners with six equivalent P(1)O4 tetrahedra. 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  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with four equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 21-51°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to two equivalent Li(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom.
Li2VOP2O7 crystallizes in the trigonal P-3 space group. Li(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-70°. The Li(1)-O(1) bond length is 2.33 Å. The Li(1)-O(3) bond length is 2.12 Å. There is one shorter (1.93 Å) and one longer (2.02 Å) Li(1)-O(2) bond length. There are two inequivalent V sites. In the first V site, V(1) is bonded to six equivalent O(1) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra and corners with six equivalent P(1)O4 tetrahedra. All V(1)-O(1) bond lengths are 1.93 Å. In the second V site, V(2) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra and corners with six equivalent P(1)O4 tetrahedra. All V(2)-O(3) bond lengths are 2.03 Å. All V(2)-O(4) bond lengths are 1.88 Å. 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  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with four equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 21-51°. The P(1)-O(1) bond length is 1.58 Å. The P(1)-O(2) 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 1.54 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to two equivalent Li(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom.