Li2VP3O10 crystallizes in the monoclinic C2/c 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 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 38°. V(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form distorted VO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra,  an edgeedge with one P(2)O4 tetrahedra, and edges with two equivalent Li(1)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with three equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-41°. In the second P site, P(2) is bonded to two equivalent O(1) and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(2) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Li(1) and one P(1) 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 non-coplanar 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 120 degrees geometry to one P(1) and one P(2) atom.
Li2VP3O10 crystallizes in the monoclinic C2/c 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 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 38°. The Li(1)-O(1) bond length is 2.02 Å. The Li(1)-O(2) bond length is 1.90 Å. The Li(1)-O(3) bond length is 2.06 Å. The Li(1)-O(4) bond length is 2.01 Å. V(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form distorted VO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra,  an edgeedge with one P(2)O4 tetrahedra, and edges with two equivalent Li(1)O4 tetrahedra. Both V(1)-O(1) bond lengths are 2.20 Å. Both V(1)-O(3) bond lengths are 2.08 Å. Both V(1)-O(4) bond lengths are 1.96 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with three equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-41°. The P(1)-O(2) bond length is 1.49 Å. The P(1)-O(3) bond length is 1.52 Å. The P(1)-O(4) bond length is 1.56 Å. The P(1)-O(5) bond length is 1.68 Å. In the second P site, P(2) is bonded to two equivalent O(1) and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. Both P(2)-O(1) bond lengths are 1.53 Å. Both P(2)-O(5) bond lengths are 1.60 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(2) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Li(1) and one P(1) 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 non-coplanar 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 120 degrees geometry to one P(1) and one P(2) atom.