Li3V2(PO4)3 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one O(6) atom. In the second Li site, Li(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms to form distorted LiO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and faces with two equivalent V(1)O6 octahedra. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and  a faceface with one Li(2)O6 octahedra. 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 Li(2)O6 octahedra and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-48°. In the second P site, P(2) is bonded to two equivalent O(1) and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with two equivalent Li(2)O6 octahedra and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-47°. There are six 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 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one P(1) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to one V(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one P(2) atom.
Li3V2(PO4)3 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one O(6) atom. The Li(1)-O(1) bond length is 2.33 Å. The Li(1)-O(2) bond length is 2.11 Å. The Li(1)-O(3) bond length is 2.16 Å. The Li(1)-O(4) bond length is 2.11 Å. The Li(1)-O(6) bond length is 2.31 Å. In the second Li site, Li(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms to form distorted LiO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and faces with two equivalent V(1)O6 octahedra. Both Li(2)-O(2) bond lengths are 2.30 Å. Both Li(2)-O(3) bond lengths are 2.18 Å. Both Li(2)-O(6) bond lengths are 2.25 Å. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and  a faceface with one Li(2)O6 octahedra. The V(1)-O(1) bond length is 2.00 Å. The V(1)-O(2) bond length is 2.04 Å. The V(1)-O(3) bond length is 2.02 Å. The V(1)-O(4) bond length is 2.01 Å. The V(1)-O(5) bond length is 1.93 Å. The V(1)-O(6) bond length is 2.06 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 Li(2)O6 octahedra and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-48°. The P(1)-O(2) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.52 Å. In the second P site, P(2) is bonded to two equivalent O(1) and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with two equivalent Li(2)O6 octahedra and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-47°. Both P(2)-O(1) bond lengths are 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 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 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one P(1) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to one V(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one P(2) atom.