Li2VP2O7 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(3), one O(4), one O(7), and two equivalent O(5) atoms. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(1), one O(3), one O(5), and one O(6) atom. V(1) is bonded to one O(1), one O(3), one O(4), one O(6), and two equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)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 one O(1), one O(2), one O(6), and one O(7) 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 28-56°. In the second P site, P(2) is bonded to one O(3), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 22-56°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent V(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one V(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(1), one P(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 in a 5-coordinate geometry to one O(3), one O(4), one O(7), and two equivalent O(5) atoms. The Li(1)-O(3) bond length is 2.27 Å. The Li(1)-O(4) bond length is 2.06 Å. The Li(1)-O(7) bond length is 2.21 Å. There is one shorter (2.14 Å) and one longer (2.28 Å) Li(1)-O(5) bond length. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(1), one O(3), one O(5), and one O(6) atom. The Li(2)-O(1) bond length is 1.93 Å. The Li(2)-O(3) bond length is 2.04 Å. The Li(2)-O(5) bond length is 2.03 Å. The Li(2)-O(6) bond length is 2.25 Å. V(1) is bonded to one O(1), one O(3), one O(4), one O(6), and two equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The V(1)-O(1) bond length is 2.14 Å. The V(1)-O(3) bond length is 2.20 Å. The V(1)-O(4) bond length is 2.22 Å. The V(1)-O(6) bond length is 2.16 Å. There is one shorter (2.18 Å) and one longer (2.20 Å) V(1)-O(2) bond length. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(6), and one O(7) 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 28-56°. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(6) bond length is 1.52 Å. The P(1)-O(7) bond length is 1.64 Å. In the second P site, P(2) is bonded to one O(3), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 22-56°. The P(2)-O(3) bond length is 1.53 Å. The P(2)-O(4) bond length is 1.53 Å. The P(2)-O(5) bond length is 1.53 Å. The P(2)-O(7) bond length is 1.64 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent V(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one V(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(1), one P(1), and one P(2) atom.