LiV2(PO4)3 crystallizes in the monoclinic Cc space group. Li(1) is bonded in a 3-coordinate geometry to one O(1), one O(10), and one O(4) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(11), one O(12), one O(3), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. In the second V site, V(2) is bonded to one O(10), one O(2), one O(4), one O(7), one O(8), and one O(9) atom to form VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(6), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-43°. In the second P site, P(2) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-41°. In the third P site, P(3) is bonded to one O(10), one O(11), one O(12), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-43°. There are twelve inequivalent O sites. In the first O site, O(6) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(7) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the third O site, O(8) is bonded in a bent 150 degrees geometry to one V(2) and one P(3) atom. In the fourth O site, O(9) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the fifth O site, O(10) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one P(3) atom. In the sixth O site, O(11) is bonded in a 2-coordinate geometry to one V(1) and one P(3) atom. In the seventh O site, O(12) is bonded in a bent 150 degrees geometry to one V(1) and one P(3) atom. In the eighth 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 ninth O site, O(2) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the tenth O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the eleventh O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one P(2) atom. In the twelfth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(2) atom.
LiV2(PO4)3 crystallizes in the monoclinic Cc space group. Li(1) is bonded in a 3-coordinate geometry to one O(1), one O(10), and one O(4) atom. The Li(1)-O(1) bond length is 2.03 Å. The Li(1)-O(10) bond length is 2.07 Å. The Li(1)-O(4) bond length is 2.09 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(11), one O(12), one O(3), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The V(1)-O(1) bond length is 2.02 Å. The V(1)-O(11) bond length is 1.96 Å. The V(1)-O(12) bond length is 1.94 Å. The V(1)-O(3) bond length is 1.92 Å. The V(1)-O(5) bond length is 1.92 Å. The V(1)-O(6) bond length is 1.90 Å. In the second V site, V(2) is bonded to one O(10), one O(2), one O(4), one O(7), one O(8), and one O(9) atom to form VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The V(2)-O(10) bond length is 2.00 Å. The V(2)-O(2) bond length is 1.92 Å. The V(2)-O(4) bond length is 2.01 Å. The V(2)-O(7) bond length is 1.94 Å. The V(2)-O(8) bond length is 1.88 Å. The V(2)-O(9) bond length is 1.91 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(6), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-43°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(6) bond length is 1.55 Å. The P(1)-O(7) bond length is 1.53 Å. The P(1)-O(9) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-41°. The P(2)-O(2) bond length is 1.54 Å. The P(2)-O(3) bond length is 1.53 Å. The P(2)-O(4) bond length is 1.55 Å. The P(2)-O(5) bond length is 1.55 Å. In the third P site, P(3) is bonded to one O(10), one O(11), one O(12), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-43°. The P(3)-O(10) bond length is 1.55 Å. The P(3)-O(11) bond length is 1.54 Å. The P(3)-O(12) bond length is 1.53 Å. The P(3)-O(8) bond length is 1.56 Å. There are twelve inequivalent O sites. In the first O site, O(6) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(7) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the third O site, O(8) is bonded in a bent 150 degrees geometry to one V(2) and one P(3) atom. In the fourth O site, O(9) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the fifth O site, O(10) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one P(3) atom. In the sixth O site, O(11) is bonded in a 2-coordinate geometry to one V(1) and one P(3) atom. In the seventh O site, O(12) is bonded in a bent 150 degrees geometry to one V(1) and one P(3) atom. In the eighth 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 ninth O site, O(2) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the tenth O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the eleventh O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one P(2) atom. In the twelfth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(2) atom.