LiVP2O7 crystallizes in the monoclinic P2_1 space group. Li(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one V(1)O5 trigonal bipyramid, and  an edgeedge with one V(1)O5 trigonal bipyramid. V(1) is bonded to one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO5 trigonal bipyramids that share corners with three equivalent P(1)O4 tetrahedra,  a cornercorner with one Li(1)O4 trigonal pyramid,  an edgeedge with one P(2)O4 tetrahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent V(1)O5 trigonal bipyramids, and corners with two equivalent Li(1)O4 trigonal pyramids. In the second P site, P(2) is bonded to one O(1), one O(2), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent Li(1)O4 trigonal pyramids, and  an edgeedge with one V(1)O5 trigonal bipyramid. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Li(1) and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one V(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 V(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the sixth O site, O(6) is bonded in an L-shaped geometry to one V(1) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom.
LiVP2O7 crystallizes in the monoclinic P2_1 space group. Li(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one V(1)O5 trigonal bipyramid, and  an edgeedge with one V(1)O5 trigonal bipyramid. The Li(1)-O(1) bond length is 1.87 Å. The Li(1)-O(2) bond length is 1.90 Å. The Li(1)-O(3) bond length is 2.31 Å. The Li(1)-O(4) bond length is 2.15 Å. V(1) is bonded to one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO5 trigonal bipyramids that share corners with three equivalent P(1)O4 tetrahedra,  a cornercorner with one Li(1)O4 trigonal pyramid,  an edgeedge with one P(2)O4 tetrahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. The V(1)-O(2) bond length is 2.13 Å. The V(1)-O(3) bond length is 2.03 Å. The V(1)-O(4) bond length is 1.98 Å. The V(1)-O(5) bond length is 1.96 Å. The V(1)-O(6) bond length is 1.96 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(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent V(1)O5 trigonal bipyramids, and corners with two equivalent Li(1)O4 trigonal pyramids. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.56 Å. The P(1)-O(5) bond length is 1.53 Å. The P(1)-O(7) bond length is 1.59 Å. In the second P site, P(2) is bonded to one O(1), one O(2), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent Li(1)O4 trigonal pyramids, and  an edgeedge with one V(1)O5 trigonal bipyramid. The P(2)-O(1) bond length is 1.49 Å. The P(2)-O(2) bond length is 1.54 Å. The P(2)-O(6) bond length is 1.58 Å. The P(2)-O(7) bond length is 1.62 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Li(1) and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one V(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 V(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the sixth O site, O(6) is bonded in an L-shaped geometry to one V(1) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom.