Li2Cr(PO4)2 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), one O(4), and one O(6) atom to form distorted LiO4 tetrahedra that share corners with three equivalent Cr(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-63°. In the second Li site, Li(2) is bonded to one O(3), one O(5), and two equivalent O(8) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 57°. Cr(1) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(7) atom to form CrO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with three equivalent Li(1)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(2), 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, corners with two equivalent Li(1)O4 tetrahedra, and corners with two equivalent Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 28-54°. In the second P site, P(2) is bonded to one O(1), 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, corners with two equivalent Li(1)O4 tetrahedra, and corners with two equivalent Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-54°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one Cr(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 Li(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(1), one Cr(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Li(2), one Cr(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(1), one Cr(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to two equivalent Li(2) and one P(2) atom.
Li2Cr(PO4)2 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), one O(4), and one O(6) atom to form distorted LiO4 tetrahedra that share corners with three equivalent Cr(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-63°. The Li(1)-O(1) bond length is 2.11 Å. The Li(1)-O(3) bond length is 2.07 Å. The Li(1)-O(4) bond length is 2.22 Å. The Li(1)-O(6) bond length is 2.07 Å. In the second Li site, Li(2) is bonded to one O(3), one O(5), and two equivalent O(8) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 57°. The Li(2)-O(3) bond length is 2.02 Å. The Li(2)-O(5) bond length is 2.26 Å. There is one shorter (1.90 Å) and one longer (1.96 Å) Li(2)-O(8) bond length. Cr(1) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(7) atom to form CrO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with three equivalent Li(1)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 2.01 Å. The Cr(1)-O(2) bond length is 1.99 Å. The Cr(1)-O(4) bond length is 2.00 Å. The Cr(1)-O(5) bond length is 2.03 Å. The Cr(1)-O(6) bond length is 2.02 Å. The Cr(1)-O(7) bond length is 1.92 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), 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, corners with two equivalent Li(1)O4 tetrahedra, and corners with two equivalent Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 28-54°. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.60 Å. The P(1)-O(5) bond length is 1.56 Å. In the second P site, P(2) is bonded to one O(1), 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, corners with two equivalent Li(1)O4 tetrahedra, and corners with two equivalent Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-54°. The P(2)-O(1) bond length is 1.56 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 1.51 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one Cr(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 Li(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(1), one Cr(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Li(2), one Cr(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(1), one Cr(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to two equivalent Li(2) and one P(2) atom.