Li2VOP2O7 crystallizes in the orthorhombic P2_12_12_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 2-coordinate geometry to one O(2), one O(3), and one O(4) atom. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(5), one O(6), and one O(7) atom. V(1) is bonded to one O(1), one O(4), one O(5), one O(6), and one O(7) atom to form distorted VO5 trigonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent P(2)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one P(2)O4 tetrahedra and corners with two equivalent V(1)O5 trigonal bipyramids. In the second P site, P(2) is bonded to one O(1), one O(2), one O(5), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra and corners with two equivalent V(1)O5 trigonal bipyramids. There are eight 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(2) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one P(1) 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(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Li(2) and one V(1) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom.
Li2VOP2O7 crystallizes in the orthorhombic P2_12_12_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 2-coordinate geometry to one O(2), one O(3), and one O(4) atom. The Li(1)-O(2) bond length is 2.00 Å. The Li(1)-O(3) bond length is 1.98 Å. The Li(1)-O(4) bond length is 2.56 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(5), one O(6), and one O(7) atom. The Li(2)-O(1) bond length is 2.47 Å. The Li(2)-O(3) bond length is 2.07 Å. The Li(2)-O(5) bond length is 2.04 Å. The Li(2)-O(6) bond length is 2.37 Å. The Li(2)-O(7) bond length is 2.03 Å. V(1) is bonded to one O(1), one O(4), one O(5), one O(6), and one O(7) atom to form distorted VO5 trigonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent P(2)O4 tetrahedra. The V(1)-O(1) bond length is 1.96 Å. The V(1)-O(4) bond length is 1.99 Å. The V(1)-O(5) bond length is 2.01 Å. The V(1)-O(6) bond length is 2.07 Å. The V(1)-O(7) bond length is 1.63 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one P(2)O4 tetrahedra and corners with two equivalent V(1)O5 trigonal bipyramids. The P(1)-O(3) bond length is 1.52 Å. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(6) bond length is 1.54 Å. The P(1)-O(8) bond length is 1.61 Å. In the second P site, P(2) is bonded to one O(1), one O(2), one O(5), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra and corners with two equivalent V(1)O5 trigonal bipyramids. The P(2)-O(1) bond length is 1.54 Å. The P(2)-O(2) bond length is 1.51 Å. The P(2)-O(5) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.63 Å. There are eight 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(2) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one P(1) 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(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Li(2) and one V(1) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom.