LiCr2(PO4)2 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(3), one O(7), 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(2), one O(3), one O(4), and one O(8) atom to form CrO5 trigonal bipyramids that share corners with two equivalent Cr(2)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with three equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-83°. In the second Cr site, Cr(2) is bonded to one O(1), one O(2), one O(6), one O(7), and two equivalent O(5) atoms to form distorted CrO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent Cr(1)O5 trigonal bipyramids,  an edgeedge with one Cr(2)O6 octahedra, and  an edgeedge with one 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(2), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Cr(2)O6 octahedra, corners with three equivalent Cr(1)O5 trigonal bipyramids, and  an edgeedge with one Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-62°. 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(2)O6 octahedra and corners with two equivalent Cr(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 35-46°. There are eight inequivalent O sites. In the first O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Cr(2), and one P(2) atom. In the second O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Cr(1), and one P(2) atom. In the third O site, O(1) is bonded in a distorted trigonal pyramidal geometry to one Li(1), one Cr(1), one Cr(2), and one P(1) atom. In the fourth O site, O(2) is bonded in a distorted trigonal planar geometry to one Cr(1), one Cr(2), and one P(1) atom. In the fifth 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 sixth O site, O(4) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the seventh O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent Cr(2) and one P(1) atom. In the eighth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one Cr(2) and one P(2) atom.
LiCr2(PO4)2 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(3), one O(7), and one O(8) atom. The Li(1)-O(1) bond length is 2.29 Å. The Li(1)-O(3) bond length is 2.22 Å. The Li(1)-O(7) bond length is 2.06 Å. The Li(1)-O(8) bond length is 2.43 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(8) atom to form CrO5 trigonal bipyramids that share corners with two equivalent Cr(2)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with three equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-83°. The Cr(1)-O(1) bond length is 2.16 Å. The Cr(1)-O(2) bond length is 2.05 Å. The Cr(1)-O(3) bond length is 2.08 Å. The Cr(1)-O(4) bond length is 1.96 Å. The Cr(1)-O(8) bond length is 2.02 Å. In the second Cr site, Cr(2) is bonded to one O(1), one O(2), one O(6), one O(7), and two equivalent O(5) atoms to form distorted CrO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent Cr(1)O5 trigonal bipyramids,  an edgeedge with one Cr(2)O6 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The Cr(2)-O(1) bond length is 2.37 Å. The Cr(2)-O(2) bond length is 2.16 Å. The Cr(2)-O(6) bond length is 2.05 Å. The Cr(2)-O(7) bond length is 2.02 Å. There is one shorter (2.06 Å) and one longer (2.17 Å) Cr(2)-O(5) bond length. 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(5) atom to form PO4 tetrahedra that share corners with two equivalent Cr(2)O6 octahedra, corners with three equivalent Cr(1)O5 trigonal bipyramids, and  an edgeedge with one Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-62°. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(2) 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 1.54 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(2)O6 octahedra and corners with two equivalent Cr(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 35-46°. The P(2)-O(3) bond length is 1.59 Å. The P(2)-O(6) bond length is 1.56 Å. The P(2)-O(7) bond length is 1.55 Å. The P(2)-O(8) bond length is 1.56 Å. There are eight inequivalent O sites. In the first O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Cr(2), and one P(2) atom. In the second O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Cr(1), and one P(2) atom. In the third O site, O(1) is bonded in a distorted trigonal pyramidal geometry to one Li(1), one Cr(1), one Cr(2), and one P(1) atom. In the fourth O site, O(2) is bonded in a distorted trigonal planar geometry to one Cr(1), one Cr(2), and one P(1) atom. In the fifth 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 sixth O site, O(4) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the seventh O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent Cr(2) and one P(1) atom. In the eighth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one Cr(2) and one P(2) atom.