LiZr2(PO4)3 crystallizes in the monoclinic Cc space group. Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(11), one O(7), and one O(8) atom. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one O(11), one O(2), one O(3), one O(6), one O(7), and one O(9) atom to form ZrO6 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 Zr site, Zr(2) is bonded to one O(1), one O(10), one O(12), one O(4), one O(5), and one O(8) atom to form ZrO6 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(12), one O(2), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-40°. In the second P site, P(2) is bonded to one O(11), one O(4), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-42°. In the third P site, P(3) is bonded to one O(10), one O(3), one O(5), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-34°. There are twelve inequivalent O sites. In the first O site, O(9) is bonded in a bent 150 degrees geometry to one Zr(1) and one P(3) atom. In the second O site, O(10) is bonded in a bent 150 degrees geometry to one Zr(2) and one P(3) atom. In the third O site, O(11) is bonded in a 3-coordinate geometry to one Li(1), one Zr(1), and one P(2) atom. In the fourth O site, O(12) is bonded in a bent 150 degrees geometry to one Zr(2) and one P(1) atom. In the fifth O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Zr(2), and one P(1) atom. In the sixth O site, O(2) is bonded in a bent 150 degrees geometry to one Zr(1) and one P(1) atom. In the seventh O site, O(3) is bonded in a bent 150 degrees geometry to one Zr(1) and one P(3) atom. In the eighth O site, O(4) is bonded in a bent 150 degrees geometry to one Zr(2) and one P(2) atom. In the ninth O site, O(5) is bonded in a bent 150 degrees geometry to one Zr(2) and one P(3) atom. In the tenth O site, O(6) is bonded in a bent 150 degrees geometry to one Zr(1) and one P(1) atom. In the eleventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(1), one Zr(1), and one P(2) atom. In the twelfth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(1), one Zr(2), and one P(2) atom.
LiZr2(PO4)3 crystallizes in the monoclinic Cc space group. Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(11), one O(7), and one O(8) atom. The Li(1)-O(1) bond length is 2.11 Å. The Li(1)-O(11) bond length is 2.50 Å. The Li(1)-O(7) bond length is 2.12 Å. The Li(1)-O(8) bond length is 2.05 Å. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one O(11), one O(2), one O(3), one O(6), one O(7), and one O(9) atom to form ZrO6 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 Zr(1)-O(11) bond length is 2.18 Å. The Zr(1)-O(2) bond length is 2.07 Å. The Zr(1)-O(3) bond length is 2.07 Å. The Zr(1)-O(6) bond length is 2.07 Å. The Zr(1)-O(7) bond length is 2.16 Å. The Zr(1)-O(9) bond length is 2.07 Å. In the second Zr site, Zr(2) is bonded to one O(1), one O(10), one O(12), one O(4), one O(5), and one O(8) atom to form ZrO6 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 Zr(2)-O(1) bond length is 2.15 Å. The Zr(2)-O(10) bond length is 2.07 Å. The Zr(2)-O(12) bond length is 2.09 Å. The Zr(2)-O(4) bond length is 2.08 Å. The Zr(2)-O(5) bond length is 2.05 Å. The Zr(2)-O(8) bond length is 2.16 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(12), one O(2), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-40°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(12) bond length is 1.54 Å. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(6) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(11), one O(4), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-42°. The P(2)-O(11) bond length is 1.54 Å. The P(2)-O(4) bond length is 1.53 Å. The P(2)-O(7) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.56 Å. In the third P site, P(3) is bonded to one O(10), one O(3), one O(5), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-34°. The P(3)-O(10) bond length is 1.54 Å. The P(3)-O(3) bond length is 1.54 Å. The P(3)-O(5) bond length is 1.54 Å. The P(3)-O(9) bond length is 1.54 Å. There are twelve inequivalent O sites. In the first O site, O(9) is bonded in a bent 150 degrees geometry to one Zr(1) and one P(3) atom. In the second O site, O(10) is bonded in a bent 150 degrees geometry to one Zr(2) and one P(3) atom. In the third O site, O(11) is bonded in a 3-coordinate geometry to one Li(1), one Zr(1), and one P(2) atom. In the fourth O site, O(12) is bonded in a bent 150 degrees geometry to one Zr(2) and one P(1) atom. In the fifth O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Zr(2), and one P(1) atom. In the sixth O site, O(2) is bonded in a bent 150 degrees geometry to one Zr(1) and one P(1) atom. In the seventh O site, O(3) is bonded in a bent 150 degrees geometry to one Zr(1) and one P(3) atom. In the eighth O site, O(4) is bonded in a bent 150 degrees geometry to one Zr(2) and one P(2) atom. In the ninth O site, O(5) is bonded in a bent 150 degrees geometry to one Zr(2) and one P(3) atom. In the tenth O site, O(6) is bonded in a bent 150 degrees geometry to one Zr(1) and one P(1) atom. In the eleventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(1), one Zr(1), and one P(2) atom. In the twelfth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(1), one Zr(2), and one P(2) atom.