Li3Cr2(PO4)3 crystallizes in the monoclinic Cc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(12), one O(2), one O(4), and one O(6) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(11), one O(3), one O(5), and one O(8) atom. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(1), one O(10), one O(12), one O(6), and one O(8) atom. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(1), one O(11), one O(12), one O(4), one O(5), and one O(7) atom to form CrO6 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 Cr site, Cr(2) is bonded to one O(10), one O(2), one O(3), one O(6), one O(8), and one O(9) atom to form CrO6 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(12), one O(3), one O(4), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra and corners with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-49°. In the second P site, P(2) is bonded to one O(1), one O(5), one O(6), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra and corners with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-47°. In the third P site, P(3) is bonded to one O(10), one O(11), one O(2), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra and corners with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-47°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(3), one Cr(1), and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Cr(2), and one P(3) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(2), one Cr(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one Cr(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Li(2), one Cr(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Cr(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Cr(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Cr(2) and one P(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(3), one Cr(2), and one P(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(2), one Cr(1), and one P(3) atom. In the twelfth O site, O(12) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Cr(1), and one P(1) atom.
Li3Cr2(PO4)3 crystallizes in the monoclinic Cc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(12), one O(2), one O(4), and one O(6) atom. The Li(1)-O(12) bond length is 2.09 Å. The Li(1)-O(2) bond length is 2.01 Å. The Li(1)-O(4) bond length is 2.17 Å. The Li(1)-O(6) bond length is 1.99 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(11), one O(3), one O(5), and one O(8) atom. The Li(2)-O(11) bond length is 1.97 Å. The Li(2)-O(3) bond length is 2.13 Å. The Li(2)-O(5) bond length is 2.02 Å. The Li(2)-O(8) bond length is 2.13 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(1), one O(10), one O(12), one O(6), and one O(8) atom. The Li(3)-O(1) bond length is 2.11 Å. The Li(3)-O(10) bond length is 2.13 Å. The Li(3)-O(12) bond length is 2.31 Å. The Li(3)-O(6) bond length is 2.47 Å. The Li(3)-O(8) bond length is 2.23 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(1), one O(11), one O(12), one O(4), one O(5), and one O(7) atom to form CrO6 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 Cr(1)-O(1) bond length is 2.02 Å. The Cr(1)-O(11) bond length is 2.02 Å. The Cr(1)-O(12) bond length is 2.05 Å. The Cr(1)-O(4) bond length is 2.01 Å. The Cr(1)-O(5) bond length is 2.01 Å. The Cr(1)-O(7) bond length is 1.95 Å. In the second Cr site, Cr(2) is bonded to one O(10), one O(2), one O(3), one O(6), one O(8), and one O(9) atom to form CrO6 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 Cr(2)-O(10) bond length is 2.01 Å. The Cr(2)-O(2) bond length is 2.01 Å. The Cr(2)-O(3) bond length is 2.00 Å. The Cr(2)-O(6) bond length is 2.02 Å. The Cr(2)-O(8) bond length is 2.05 Å. The Cr(2)-O(9) bond length is 1.95 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(12), one O(3), one O(4), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra and corners with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-49°. The P(1)-O(12) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.54 Å. The P(1)-O(8) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(1), one O(5), one O(6), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra and corners with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-47°. The P(2)-O(1) bond length is 1.56 Å. The P(2)-O(5) bond length is 1.54 Å. The P(2)-O(6) bond length is 1.56 Å. The P(2)-O(9) bond length is 1.52 Å. In the third P site, P(3) is bonded to one O(10), one O(11), one O(2), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra and corners with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-47°. The P(3)-O(10) bond length is 1.56 Å. The P(3)-O(11) bond length is 1.56 Å. The P(3)-O(2) bond length is 1.55 Å. The P(3)-O(7) bond length is 1.52 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(3), one Cr(1), and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Cr(2), and one P(3) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(2), one Cr(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one Cr(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Li(2), one Cr(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Cr(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Cr(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Cr(2) and one P(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(3), one Cr(2), and one P(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(2), one Cr(1), and one P(3) atom. In the twelfth O site, O(12) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Cr(1), and one P(1) atom.