LiV(PO4)2 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded in a distorted trigonal planar geometry to one O(2) and two equivalent O(8) atoms. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form distorted VO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra and corners with three 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(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 35-41°. In the second P site, P(2) is bonded to one O(3), one O(5), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-44°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one V(1) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one P(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to 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 V(1) and one P(2) atom. In the eighth O site, O(8) is bonded in a trigonal non-coplanar geometry to two equivalent Li(1) and one P(2) atom.
LiV(PO4)2 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded in a distorted trigonal planar geometry to one O(2) and two equivalent O(8) atoms. The Li(1)-O(2) bond length is 2.10 Å. Both Li(1)-O(8) bond lengths are 1.93 Å. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form distorted VO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra and corners with three equivalent P(1)O4 tetrahedra. The V(1)-O(1) bond length is 1.97 Å. The V(1)-O(2) bond length is 1.65 Å. The V(1)-O(3) bond length is 2.13 Å. The V(1)-O(4) bond length is 1.96 Å. The V(1)-O(6) bond length is 1.92 Å. The V(1)-O(7) bond length is 1.88 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 35-41°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.52 Å. The P(1)-O(5) bond length is 1.59 Å. The P(1)-O(6) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(3), one O(5), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-44°. The P(2)-O(3) bond length is 1.51 Å. The P(2)-O(5) bond length is 1.65 Å. The P(2)-O(7) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.52 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one V(1) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one P(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to 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 V(1) and one P(2) atom. In the eighth O site, O(8) is bonded in a trigonal non-coplanar geometry to two equivalent Li(1) and one P(2) atom.