LiCr(PO3)3 crystallizes in the monoclinic Cc space group. Li(1) is bonded in a 3-coordinate geometry to one O(1), one O(2), and one O(3) atom. Cr(1) is bonded to one O(1), one O(2), one O(3), one O(4), 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(1), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 47°. In the second P site, P(2) is bonded to one O(3), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-60°. In the third P site, P(3) is bonded to one O(2), 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,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 39-62°. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Cr(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Cr(1), and one P(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Cr(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Cr(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one P(1) and one P(3) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one P(2) and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Cr(1) and one P(3) atom.
LiCr(PO3)3 crystallizes in the monoclinic Cc space group. Li(1) is bonded in a 3-coordinate geometry to one O(1), one O(2), and one O(3) atom. The Li(1)-O(1) bond length is 2.54 Å. The Li(1)-O(2) bond length is 2.02 Å. The Li(1)-O(3) bond length is 1.96 Å. Cr(1) is bonded to one O(1), one O(2), one O(3), one O(4), 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(1)-O(1) bond length is 2.14 Å. The Cr(1)-O(2) bond length is 2.55 Å. The Cr(1)-O(3) bond length is 2.53 Å. The Cr(1)-O(4) bond length is 2.12 Å. The Cr(1)-O(8) bond length is 2.07 Å. The Cr(1)-O(9) bond length is 2.08 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 47°. The P(1)-O(1) bond length is 1.51 Å. The P(1)-O(4) bond length is 1.50 Å. The P(1)-O(5) bond length is 1.60 Å. The P(1)-O(7) bond length is 1.60 Å. In the second P site, P(2) is bonded to one O(3), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-60°. The P(2)-O(3) bond length is 1.50 Å. The P(2)-O(6) bond length is 1.61 Å. The P(2)-O(7) bond length is 1.60 Å. The P(2)-O(8) bond length is 1.50 Å. In the third P site, P(3) is bonded to one O(2), 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,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 39-62°. The P(3)-O(2) bond length is 1.50 Å. The P(3)-O(5) bond length is 1.61 Å. The P(3)-O(6) bond length is 1.61 Å. The P(3)-O(9) bond length is 1.50 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Cr(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Cr(1), and one P(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Cr(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Cr(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one P(1) and one P(3) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one P(2) and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Cr(1) and one P(3) atom.