Li4V2(PO4)3 crystallizes in the trigonal R-3c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent O(1) and two equivalent O(2) atoms. In the second Li site, Li(2) is bonded to six equivalent O(2) atoms to form distorted LiO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and faces with two equivalent V(1)O6 octahedra. V(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and  a faceface with one Li(2)O6 octahedra. P(1) is bonded to two equivalent O(1) and two equivalent O(2) 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 33-44°. There are two 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(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one P(1) atom.
Li4V2(PO4)3 crystallizes in the trigonal R-3c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Li(1)-O(1) bond lengths are 2.25 Å. Both Li(1)-O(2) bond lengths are 2.10 Å. In the second Li site, Li(2) is bonded to six equivalent O(2) atoms to form distorted LiO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and faces with two equivalent V(1)O6 octahedra. All Li(2)-O(2) bond lengths are 2.22 Å. V(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and  a faceface with one Li(2)O6 octahedra. All V(1)-O(1) bond lengths are 2.08 Å. All V(1)-O(2) bond lengths are 2.10 Å. P(1) is bonded to two equivalent O(1) and two equivalent O(2) 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 33-44°. Both P(1)-O(1) bond lengths are 1.53 Å. Both P(1)-O(2) bond lengths are 1.56 Å. There are two 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(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one P(1) atom.