LiV(PO4)2 crystallizes in the orthorhombic Pmc2_1 space group. Li(1) is bonded to one O(5), one O(6), two equivalent O(1), and two equivalent O(4) atoms to form distorted LiO6 octahedra that share corners with four equivalent V(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-56°. V(1) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form VO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-56°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-63°. In the second P site, P(2) is bonded to one O(5), one O(6), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and  an edgeedge with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-55°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Li(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one Li(1) and one P(2) atom.
LiV(PO4)2 crystallizes in the orthorhombic Pmc2_1 space group. Li(1) is bonded to one O(5), one O(6), two equivalent O(1), and two equivalent O(4) atoms to form distorted LiO6 octahedra that share corners with four equivalent V(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-56°. The Li(1)-O(5) bond length is 1.89 Å. The Li(1)-O(6) bond length is 1.94 Å. Both Li(1)-O(1) bond lengths are 2.10 Å. Both Li(1)-O(4) bond lengths are 2.50 Å. V(1) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form VO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-56°. The V(1)-O(2) bond length is 1.97 Å. The V(1)-O(3) bond length is 1.85 Å. Both V(1)-O(1) bond lengths are 1.99 Å. Both V(1)-O(4) bond lengths are 1.85 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-63°. The P(1)-O(2) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.55 Å. Both P(1)-O(1) bond lengths are 1.57 Å. In the second P site, P(2) is bonded to one O(5), one O(6), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and  an edgeedge with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-55°. The P(2)-O(5) bond length is 1.49 Å. The P(2)-O(6) bond length is 1.50 Å. Both P(2)-O(4) bond lengths are 1.64 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Li(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one Li(1) and one P(2) atom.