Li3V(PO4)2 crystallizes in the monoclinic P2_1/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a trigonal non-coplanar geometry to one O(2) and two equivalent O(5) atoms. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(2), one O(3), and two equivalent O(6) atoms. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to one O(3) and two equivalent O(5) atoms. V(1) is bonded to one O(1), one O(4), two equivalent O(5), and two equivalent O(6) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-48°. In the second P site, P(2) is bonded to one O(3), one O(4), and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-29°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), and one P(2) atom. In the fourth O site, O(4) is bonded in a linear geometry to one V(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one V(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(2), one V(1), and one P(2) atom.
Li3V(PO4)2 crystallizes in the monoclinic P2_1/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a trigonal non-coplanar geometry to one O(2) and two equivalent O(5) atoms. The Li(1)-O(2) bond length is 1.85 Å. Both Li(1)-O(5) bond lengths are 1.97 Å. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(2), one O(3), and two equivalent O(6) atoms. The Li(2)-O(2) bond length is 2.08 Å. The Li(2)-O(3) bond length is 2.20 Å. Both Li(2)-O(6) bond lengths are 2.05 Å. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to one O(3) and two equivalent O(5) atoms. The Li(3)-O(3) bond length is 1.90 Å. Both Li(3)-O(5) bond lengths are 2.10 Å. V(1) is bonded to one O(1), one O(4), two equivalent O(5), and two equivalent O(6) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. The V(1)-O(1) bond length is 1.97 Å. The V(1)-O(4) bond length is 1.97 Å. Both V(1)-O(5) bond lengths are 2.11 Å. Both V(1)-O(6) bond lengths are 2.06 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-48°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(2) bond length is 1.53 Å. Both P(1)-O(5) bond lengths are 1.57 Å. In the second P site, P(2) is bonded to one O(3), one O(4), and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-29°. The P(2)-O(3) bond length is 1.54 Å. The P(2)-O(4) bond length is 1.55 Å. Both P(2)-O(6) bond lengths are 1.56 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), and one P(2) atom. In the fourth O site, O(4) is bonded in a linear geometry to one V(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one V(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(2), one V(1), and one P(2) atom.