LiCr2(PO4)2 crystallizes in the triclinic P-1 space group. Li(1) is bonded in a 4-coordinate geometry to one O(4), one O(6), and two equivalent O(5) atoms. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(6), and two equivalent O(1) atoms. In the second Cr site, Cr(2) is bonded to one O(2), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form distorted CrO6 pentagonal pyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one 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(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Cr(2)O6 pentagonal pyramids. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Cr(2)O6 pentagonal pyramids and  an edgeedge with one Cr(2)O6 pentagonal pyramid. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to two equivalent Cr(1) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Cr(1), one Cr(2), and one P(1) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Cr(1), one Cr(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Cr(1), and one P(1) atom. In the fifth O site, O(5) is bonded to two equivalent Li(1), one Cr(2), and one P(2) atom to form distorted OLi2CrP trigonal pyramids that share corners with two equivalent O(6)LiCr2P tetrahedra,  an edgeedge with one O(6)LiCr2P tetrahedra, and  an edgeedge with one O(5)Li2CrP trigonal pyramid. In the sixth O site, O(6) is bonded to one Li(1), one Cr(1), one Cr(2), and one P(2) atom to form a mixture of distorted corner and edge-sharing OLiCr2P tetrahedra. In the seventh O site, O(7) is bonded in a 2-coordinate geometry to one Cr(2) and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Cr(2) and one P(2) atom.
LiCr2(PO4)2 crystallizes in the triclinic P-1 space group. Li(1) is bonded in a 4-coordinate geometry to one O(4), one O(6), and two equivalent O(5) atoms. The Li(1)-O(4) bond length is 2.35 Å. The Li(1)-O(6) bond length is 2.32 Å. There is one shorter (2.05 Å) and one longer (2.33 Å) Li(1)-O(5) bond length. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(6), and two equivalent O(1) atoms. The Cr(1)-O(2) bond length is 2.48 Å. The Cr(1)-O(3) bond length is 2.64 Å. The Cr(1)-O(4) bond length is 2.02 Å. The Cr(1)-O(6) bond length is 2.12 Å. There is one shorter (2.07 Å) and one longer (2.08 Å) Cr(1)-O(1) bond length. In the second Cr site, Cr(2) is bonded to one O(2), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form distorted CrO6 pentagonal pyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The Cr(2)-O(2) bond length is 2.00 Å. The Cr(2)-O(3) bond length is 2.05 Å. The Cr(2)-O(5) bond length is 2.14 Å. The Cr(2)-O(6) bond length is 2.12 Å. The Cr(2)-O(7) bond length is 2.11 Å. The Cr(2)-O(8) bond length is 1.98 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(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Cr(2)O6 pentagonal pyramids. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Cr(2)O6 pentagonal pyramids and  an edgeedge with one Cr(2)O6 pentagonal pyramid. The P(2)-O(5) bond length is 1.58 Å. The P(2)-O(6) bond length is 1.60 Å. The P(2)-O(7) bond length is 1.54 Å. The P(2)-O(8) bond length is 1.53 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to two equivalent Cr(1) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Cr(1), one Cr(2), and one P(1) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Cr(1), one Cr(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Cr(1), and one P(1) atom. In the fifth O site, O(5) is bonded to two equivalent Li(1), one Cr(2), and one P(2) atom to form distorted OLi2CrP trigonal pyramids that share corners with two equivalent O(6)LiCr2P tetrahedra,  an edgeedge with one O(6)LiCr2P tetrahedra, and  an edgeedge with one O(5)Li2CrP trigonal pyramid. In the sixth O site, O(6) is bonded to one Li(1), one Cr(1), one Cr(2), and one P(2) atom to form a mixture of distorted corner and edge-sharing OLiCr2P tetrahedra. In the seventh O site, O(7) is bonded in a 2-coordinate geometry to one Cr(2) and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Cr(2) and one P(2) atom.