LiV2PO7 crystallizes in the monoclinic P2_1 space group. Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(4), one O(6), and one O(7) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(6) atom to form VO5 trigonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent V(2)O5 trigonal bipyramids, and  an edgeedge with one V(2)O5 trigonal bipyramid. In the second V site, V(2) is bonded to one O(1), one O(2), one O(4), one O(5), and one O(6) atom to form VO5 trigonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent V(1)O5 trigonal bipyramids, and  an edgeedge with one V(1)O5 trigonal bipyramid. P(1) is bonded to one O(2), one O(3), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O5 trigonal bipyramids and corners with two equivalent V(2)O5 trigonal bipyramids. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), one V(2), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one V(2) and one P(1) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Li(1) and one P(1) atom.
LiV2PO7 crystallizes in the monoclinic P2_1 space group. Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(4), one O(6), and one O(7) atom. The Li(1)-O(1) bond length is 2.08 Å. The Li(1)-O(2) bond length is 2.41 Å. The Li(1)-O(4) bond length is 2.18 Å. The Li(1)-O(6) bond length is 2.01 Å. The Li(1)-O(7) bond length is 1.88 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(6) atom to form VO5 trigonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent V(2)O5 trigonal bipyramids, and  an edgeedge with one V(2)O5 trigonal bipyramid. The V(1)-O(1) bond length is 1.80 Å. The V(1)-O(2) bond length is 2.15 Å. The V(1)-O(3) bond length is 1.90 Å. The V(1)-O(4) bond length is 1.93 Å. The V(1)-O(6) bond length is 1.81 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(4), one O(5), and one O(6) atom to form VO5 trigonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent V(1)O5 trigonal bipyramids, and  an edgeedge with one V(1)O5 trigonal bipyramid. The V(2)-O(1) bond length is 1.88 Å. The V(2)-O(2) bond length is 2.16 Å. The V(2)-O(4) bond length is 1.78 Å. The V(2)-O(5) bond length is 1.94 Å. The V(2)-O(6) bond length is 1.87 Å. P(1) is bonded to one O(2), one O(3), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O5 trigonal bipyramids and corners with two equivalent V(2)O5 trigonal bipyramids. The P(1)-O(2) bond length is 1.60 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.56 Å. The P(1)-O(7) bond length is 1.50 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), one V(2), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one V(2) and one P(1) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Li(1) and one P(1) atom.