LiV2(PO4)2 crystallizes in the orthorhombic Pmc2_1 space group. Li(1) is bonded in a 4-coordinate geometry to one O(2), two equivalent O(4), and two equivalent O(6) atoms. 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 three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(4), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-54°. In the second P site, P(2) is bonded to one O(3), one O(5), and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted tetrahedral geometry to one Li(1), two equivalent V(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent V(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to two equivalent V(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(2) atom.
LiV2(PO4)2 crystallizes in the orthorhombic Pmc2_1 space group. Li(1) is bonded in a 4-coordinate geometry to one O(2), two equivalent O(4), and two equivalent O(6) atoms. The Li(1)-O(2) bond length is 2.07 Å. There is one shorter (2.37 Å) and one longer (2.58 Å) Li(1)-O(4) bond length. Both Li(1)-O(6) bond lengths are 2.05 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 three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. The V(1)-O(1) bond length is 2.03 Å. The V(1)-O(2) bond length is 2.31 Å. The V(1)-O(3) bond length is 2.07 Å. The V(1)-O(4) bond length is 2.18 Å. The V(1)-O(5) bond length is 2.15 Å. The V(1)-O(6) bond length is 2.05 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(4), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-54°. The P(1)-O(2) bond length is 1.59 Å. The P(1)-O(4) bond length is 1.60 Å. Both P(1)-O(1) bond lengths are 1.52 Å. In the second P site, P(2) is bonded to one O(3), one O(5), and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. The P(2)-O(3) bond length is 1.57 Å. The P(2)-O(5) bond length is 1.57 Å. Both P(2)-O(6) bond lengths are 1.54 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted tetrahedral geometry to one Li(1), two equivalent V(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent V(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to two equivalent V(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(2) atom.