Li4V(PO4)2 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(4), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 66-70°. In the second Li site, Li(2) is bonded in a distorted see-saw-like geometry to one O(1), one O(2), one O(3), and one O(4) atom. V(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, and edges with two equivalent P(1)O4 tetrahedra. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with four equivalent Li(1)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 49°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(2), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), 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 distorted corner-sharing OLi2VP trigonal pyramids. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one P(1) atom.
Li4V(PO4)2 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(4), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 66-70°. The Li(1)-O(3) bond length is 2.01 Å. The Li(1)-O(4) bond length is 1.97 Å. There is one shorter (2.00 Å) and one longer (2.02 Å) Li(1)-O(2) bond length. In the second Li site, Li(2) is bonded in a distorted see-saw-like geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Li(2)-O(1) bond length is 1.94 Å. The Li(2)-O(2) bond length is 2.03 Å. The Li(2)-O(3) bond length is 2.25 Å. The Li(2)-O(4) bond length is 2.10 Å. V(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, and edges with two equivalent P(1)O4 tetrahedra. Both V(1)-O(1) bond lengths are 2.17 Å. Both V(1)-O(3) bond lengths are 2.21 Å. Both V(1)-O(4) bond lengths are 2.26 Å. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with four equivalent Li(1)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 49°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.57 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(2), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), 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 distorted corner-sharing OLi2VP trigonal pyramids. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one P(1) atom.