Li3V(PO4)2 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(2), and two equivalent O(3) atoms. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and edges with two equivalent V(1)O6 octahedra. V(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and edges with two equivalent Li(2)O6 octahedra. P(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra and corners with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-55°. There are three 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 P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one V(1), and one P(1) atom to form a mixture of distorted corner and edge-sharing OLi2VP trigonal pyramids.
Li3V(PO4)2 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(2), and two equivalent O(3) atoms. The Li(1)-O(1) bond length is 2.04 Å. The Li(1)-O(2) bond length is 1.94 Å. Both Li(1)-O(3) bond lengths are 2.14 Å. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and edges with two equivalent V(1)O6 octahedra. Both Li(2)-O(2) bond lengths are 2.04 Å. All Li(2)-O(3) bond lengths are 2.27 Å. V(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and edges with two equivalent Li(2)O6 octahedra. Both V(1)-O(1) bond lengths are 1.98 Å. All V(1)-O(3) bond lengths are 2.08 Å. P(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra and corners with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-55°. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(2) bond length is 1.51 Å. Both P(1)-O(3) bond lengths are 1.57 Å. There are three 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 P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one V(1), and one P(1) atom to form a mixture of distorted corner and edge-sharing OLi2VP trigonal pyramids.