LiCr(PO3)4 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms to form distorted LiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent Cr(1)O6 octahedra. Cr(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms to form CrO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Li(1)O6 octahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 26-53°. In the second P site, P(2) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 24-65°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Cr(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Li(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 Cr(1), and one P(1) atom.
LiCr(PO3)4 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms to form distorted LiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent Cr(1)O6 octahedra. Both Li(1)-O(3) bond lengths are 2.40 Å. Both Li(1)-O(5) bond lengths are 1.94 Å. Both Li(1)-O(6) bond lengths are 2.34 Å. Cr(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms to form CrO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Li(1)O6 octahedra. Both Cr(1)-O(2) bond lengths are 2.01 Å. Both Cr(1)-O(3) bond lengths are 2.01 Å. Both Cr(1)-O(6) bond lengths are 2.03 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 26-53°. The P(1)-O(1) bond length is 1.60 Å. The P(1)-O(2) bond length is 1.49 Å. The P(1)-O(4) bond length is 1.60 Å. The P(1)-O(6) bond length is 1.52 Å. In the second P site, P(2) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 24-65°. The P(2)-O(1) bond length is 1.62 Å. The P(2)-O(3) bond length is 1.53 Å. The P(2)-O(4) bond length is 1.63 Å. The P(2)-O(5) bond length is 1.46 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Cr(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Li(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 Cr(1), and one P(1) atom.