Li2V(PO3)4 crystallizes in the monoclinic C2/c space group. Li(1) is bonded in a 3-coordinate geometry to one O(4) and two equivalent O(5) atoms. V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra and corners with four equivalent P(1)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-50°. In the second P site, P(2) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 60°. There are seven inequivalent O sites. In the first O site, O(3) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the second O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(2) atom. In the third O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one P(2) atom. In the fourth O site, O(6) is bonded in a bent 150 degrees geometry to two equivalent P(2) atoms. In the fifth O site, O(7) is bonded in a bent 150 degrees geometry to two equivalent P(1) atoms. In the sixth O site, O(1) is bonded in a 2-coordinate geometry to one V(1) and one P(1) atom. In the seventh O site, O(2) is bonded in a distorted bent 120 degrees geometry to one V(1) and one P(1) atom.
Li2V(PO3)4 crystallizes in the monoclinic C2/c space group. Li(1) is bonded in a 3-coordinate geometry to one O(4) and two equivalent O(5) atoms. The Li(1)-O(4) bond length is 2.00 Å. There is one shorter (1.96 Å) and one longer (2.07 Å) Li(1)-O(5) bond length. V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra and corners with four equivalent P(1)O4 tetrahedra. Both V(1)-O(1) bond lengths are 2.11 Å. Both V(1)-O(2) bond lengths are 2.16 Å. Both V(1)-O(4) bond lengths are 2.18 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-50°. The P(1)-O(1) bond length is 1.51 Å. The P(1)-O(2) bond length is 1.50 Å. The P(1)-O(3) bond length is 1.61 Å. The P(1)-O(7) bond length is 1.61 Å. In the second P site, P(2) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 60°. The P(2)-O(3) bond length is 1.59 Å. The P(2)-O(4) bond length is 1.51 Å. The P(2)-O(5) bond length is 1.50 Å. The P(2)-O(6) bond length is 1.61 Å. There are seven inequivalent O sites. In the first O site, O(3) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the second O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(2) atom. In the third O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one P(2) atom. In the fourth O site, O(6) is bonded in a bent 150 degrees geometry to two equivalent P(2) atoms. In the fifth O site, O(7) is bonded in a bent 150 degrees geometry to two equivalent P(1) atoms. In the sixth O site, O(1) is bonded in a 2-coordinate geometry to one V(1) and one P(1) atom. In the seventh O site, O(2) is bonded in a distorted bent 120 degrees geometry to one V(1) and one P(1) atom.