LiCr(PO3)4 crystallizes in the monoclinic C2/m space group. Li(1) is bonded in an L-shaped geometry to two equivalent O(5) atoms. Cr(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form CrO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra and corners with four equivalent P(1)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(4), one O(6), and one O(7) 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 45-48°. In the second P site, P(2) is bonded to one O(2), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one 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 are 43°. There are seven inequivalent O sites. In the first O site, O(5) is bonded in a bent 150 degrees geometry to one Li(1) and one P(2) atom. In the second O site, O(6) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the third O site, O(7) is bonded in a bent 150 degrees geometry to two equivalent P(1) atoms. In the fourth O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the fifth O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Cr(1) and one P(2) atom. In the sixth O site, O(3) is bonded in a bent 120 degrees geometry to two equivalent P(2) atoms. In the seventh O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Cr(1) and one P(1) atom.
LiCr(PO3)4 crystallizes in the monoclinic C2/m space group. Li(1) is bonded in an L-shaped geometry to two equivalent O(5) atoms. Both Li(1)-O(5) bond lengths are 1.88 Å. Cr(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form CrO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra and corners with four equivalent P(1)O4 tetrahedra. Both Cr(1)-O(1) bond lengths are 2.00 Å. Both Cr(1)-O(2) bond lengths are 1.98 Å. Both Cr(1)-O(4) bond lengths are 1.99 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(4), one O(6), and one O(7) 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 45-48°. 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(6) bond length is 1.59 Å. The P(1)-O(7) bond length is 1.60 Å. In the second P site, P(2) is bonded to one O(2), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one 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 are 43°. The P(2)-O(2) bond length is 1.51 Å. The P(2)-O(3) bond length is 1.61 Å. The P(2)-O(5) bond length is 1.48 Å. The P(2)-O(6) bond length is 1.62 Å. There are seven inequivalent O sites. In the first O site, O(5) is bonded in a bent 150 degrees geometry to one Li(1) and one P(2) atom. In the second O site, O(6) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the third O site, O(7) is bonded in a bent 150 degrees geometry to two equivalent P(1) atoms. In the fourth O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the fifth O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Cr(1) and one P(2) atom. In the sixth O site, O(3) is bonded in a bent 120 degrees geometry to two equivalent P(2) atoms. In the seventh O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Cr(1) and one P(1) atom.