Li2VP2O7 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(6), and one O(7) atom to form LiO4 tetrahedra that share corners with four equivalent V(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 57-72°. In the second Li site, Li(2) is bonded to one O(1), one O(3), and two equivalent O(5) atoms to form distorted LiO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 67-80°. V(1) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(7) atom to form VO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. 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(6) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, and corners with three equivalent Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 27-61°. In the second P site, P(2) is bonded to one O(2), one O(3), one O(4), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra, and corners with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-56°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted tetrahedral geometry to one Li(1), one Li(2), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one P(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to two equivalent Li(2), one V(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one P(2) atom.
Li2VP2O7 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(6), and one O(7) atom to form LiO4 tetrahedra that share corners with four equivalent V(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 57-72°. The Li(1)-O(1) bond length is 2.39 Å. The Li(1)-O(2) bond length is 2.02 Å. The Li(1)-O(6) bond length is 2.05 Å. The Li(1)-O(7) bond length is 2.03 Å. In the second Li site, Li(2) is bonded to one O(1), one O(3), and two equivalent O(5) atoms to form distorted LiO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 67-80°. The Li(2)-O(1) bond length is 2.04 Å. The Li(2)-O(3) bond length is 1.94 Å. There is one shorter (2.02 Å) and one longer (2.09 Å) Li(2)-O(5) bond length. V(1) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(7) atom to form VO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The V(1)-O(1) bond length is 2.19 Å. The V(1)-O(2) bond length is 2.12 Å. The V(1)-O(3) bond length is 2.14 Å. The V(1)-O(5) bond length is 2.18 Å. The V(1)-O(6) bond length is 2.29 Å. The V(1)-O(7) bond length is 2.18 Å. 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(6) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, and corners with three equivalent Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 27-61°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.61 Å. The P(1)-O(5) bond length is 1.53 Å. The P(1)-O(6) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(2), one O(3), one O(4), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra, and corners with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-56°. The P(2)-O(2) bond length is 1.53 Å. The P(2)-O(3) bond length is 1.53 Å. The P(2)-O(4) bond length is 1.63 Å. The P(2)-O(7) bond length is 1.53 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted tetrahedral geometry to one Li(1), one Li(2), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one P(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to two equivalent Li(2), one V(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one P(2) atom.