LiV4(PO4)3 crystallizes in the tetragonal I-42d space group. Li(1) is bonded to four equivalent O(3) atoms to form LiO4 tetrahedra that share corners with four equivalent V(1)O6 octahedra, corners with four equivalent V(2)O6 octahedra, and corners with four equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 78-79°. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent V(2)O6 octahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 61°. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 61°. There are two inequivalent P sites. In the first P site, P(1) is bonded to four equivalent O(1) atoms to form PO4 tetrahedra that share corners with four equivalent V(1)O6 octahedra and corners with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 47°. In the second P site, P(2) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-47°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one P(2) atom. In the third O site, O(3) is bonded to one Li(1), one V(1), one V(2), and one P(2) atom to form a mixture of distorted corner and edge-sharing OLiV2P tetrahedra.
LiV4(PO4)3 crystallizes in the tetragonal I-42d space group. Li(1) is bonded to four equivalent O(3) atoms to form LiO4 tetrahedra that share corners with four equivalent V(1)O6 octahedra, corners with four equivalent V(2)O6 octahedra, and corners with four equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 78-79°. All Li(1)-O(3) bond lengths are 2.26 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent V(2)O6 octahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 61°. Both V(1)-O(1) bond lengths are 2.12 Å. Both V(1)-O(2) bond lengths are 2.18 Å. Both V(1)-O(3) bond lengths are 2.17 Å. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 61°. Both V(2)-O(1) bond lengths are 2.18 Å. Both V(2)-O(2) bond lengths are 2.29 Å. Both V(2)-O(3) bond lengths are 2.18 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to four equivalent O(1) atoms to form PO4 tetrahedra that share corners with four equivalent V(1)O6 octahedra and corners with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 47°. All P(1)-O(1) bond lengths are 1.56 Å. In the second P site, P(2) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-47°. Both P(2)-O(2) bond lengths are 1.55 Å. Both P(2)-O(3) bond lengths are 1.59 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one P(2) atom. In the third O site, O(3) is bonded to one Li(1), one V(1), one V(2), and one P(2) atom to form a mixture of distorted corner and edge-sharing OLiV2P tetrahedra.