Li2Cr(PO4)2 crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(4), and one O(8) atom. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), and one O(8) atom to form distorted LiO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with three equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 61-79°. Cr(1) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(7) atom to form CrO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and corners with three equivalent P(2)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with three equivalent Cr(1)O6 octahedra and corners with three equivalent Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-61°. In the second P site, P(2) is bonded to one O(2), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with three equivalent Cr(1)O6 octahedra and  a cornercorner with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-56°. There are eight inequivalent O sites. In the first O site, O(8) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one P(2) atom. In the second O site, O(1) is bonded in a trigonal planar geometry to one Li(2), one Cr(1), and one P(1) atom. In the third O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one Cr(1), and one P(2) atom. In the fourth O site, O(3) is bonded in a distorted trigonal pyramidal geometry to one Li(1), one Li(2), one Cr(1), and one P(1) atom. In the fifth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Li(1), one Li(2), and one P(1) atom. In the sixth O site, O(5) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the seventh O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Cr(1) and one P(2) atom. In the eighth O site, O(7) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(2) atom.
Li2Cr(PO4)2 crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(4), and one O(8) atom. The Li(1)-O(2) bond length is 2.09 Å. The Li(1)-O(3) bond length is 2.37 Å. The Li(1)-O(4) bond length is 1.99 Å. The Li(1)-O(8) bond length is 2.00 Å. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), and one O(8) atom to form distorted LiO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with three equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 61-79°. The Li(2)-O(1) bond length is 2.12 Å. The Li(2)-O(3) bond length is 2.17 Å. The Li(2)-O(4) bond length is 2.03 Å. The Li(2)-O(8) bond length is 1.94 Å. Cr(1) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(7) atom to form CrO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and corners with three equivalent P(2)O4 tetrahedra. The Cr(1)-O(1) bond length is 2.00 Å. The Cr(1)-O(2) bond length is 1.95 Å. The Cr(1)-O(3) bond length is 2.15 Å. The Cr(1)-O(5) bond length is 1.87 Å. The Cr(1)-O(6) bond length is 1.95 Å. The Cr(1)-O(7) bond length is 1.90 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with three equivalent Cr(1)O6 octahedra and corners with three equivalent Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-61°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.52 Å. The P(1)-O(5) bond length is 1.56 Å. In the second P site, P(2) is bonded to one O(2), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with three equivalent Cr(1)O6 octahedra and  a cornercorner with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-56°. The P(2)-O(2) bond length is 1.58 Å. The P(2)-O(6) bond length is 1.55 Å. The P(2)-O(7) bond length is 1.57 Å. The P(2)-O(8) bond length is 1.51 Å. There are eight inequivalent O sites. In the first O site, O(8) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one P(2) atom. In the second O site, O(1) is bonded in a trigonal planar geometry to one Li(2), one Cr(1), and one P(1) atom. In the third O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one Cr(1), and one P(2) atom. In the fourth O site, O(3) is bonded in a distorted trigonal pyramidal geometry to one Li(1), one Li(2), one Cr(1), and one P(1) atom. In the fifth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Li(1), one Li(2), and one P(1) atom. In the sixth O site, O(5) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the seventh O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Cr(1) and one P(2) atom. In the eighth O site, O(7) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(2) atom.