Li3Cr(PO4)2 crystallizes in the monoclinic P2_1/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), and two equivalent O(4) atoms to form distorted LiO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Cr(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 66-81°. In the second Li site, Li(2) is bonded to one O(2), one O(5), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and edges with two equivalent Cr(1)O6 octahedra. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(5), one O(6), and two equivalent O(3) atoms. Cr(1) is bonded to one O(1), one O(6), two equivalent O(3), and two equivalent O(4) atoms to form CrO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and edges with two equivalent Li(2)O6 octahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Cr(1)O6 octahedra, and corners with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-55°. In the second P site, P(2) is bonded to one O(5), one O(6), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Cr(1)O6 octahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-55°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Cr(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom. In the third O site, O(3) is bonded to one Li(2), one Li(3), one Cr(1), and one P(1) atom to form a mixture of distorted edge and corner-sharing OLi2CrP trigonal pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Cr(1), and one P(2) atom to form a mixture of distorted edge and corner-sharing OLi2CrP trigonal pyramids. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(3), one Cr(1), and one P(2) atom.
Li3Cr(PO4)2 crystallizes in the monoclinic P2_1/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), and two equivalent O(4) atoms to form distorted LiO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Cr(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 66-81°. The Li(1)-O(1) bond length is 2.02 Å. The Li(1)-O(2) bond length is 1.94 Å. Both Li(1)-O(4) bond lengths are 2.11 Å. In the second Li site, Li(2) is bonded to one O(2), one O(5), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and edges with two equivalent Cr(1)O6 octahedra. The Li(2)-O(2) bond length is 2.07 Å. The Li(2)-O(5) bond length is 2.07 Å. Both Li(2)-O(3) bond lengths are 2.23 Å. Both Li(2)-O(4) bond lengths are 2.27 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(5), one O(6), and two equivalent O(3) atoms. The Li(3)-O(5) bond length is 1.94 Å. The Li(3)-O(6) bond length is 2.02 Å. Both Li(3)-O(3) bond lengths are 2.13 Å. Cr(1) is bonded to one O(1), one O(6), two equivalent O(3), and two equivalent O(4) atoms to form CrO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and edges with two equivalent Li(2)O6 octahedra. The Cr(1)-O(1) bond length is 2.00 Å. The Cr(1)-O(6) bond length is 2.00 Å. Both Cr(1)-O(3) bond lengths are 2.06 Å. Both Cr(1)-O(4) bond lengths are 2.05 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Cr(1)O6 octahedra, and corners with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-55°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(2) bond length is 1.51 Å. Both P(1)-O(3) bond lengths are 1.58 Å. In the second P site, P(2) is bonded to one O(5), one O(6), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Cr(1)O6 octahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-55°. The P(2)-O(5) bond length is 1.51 Å. The P(2)-O(6) bond length is 1.55 Å. Both P(2)-O(4) bond lengths are 1.58 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Cr(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom. In the third O site, O(3) is bonded to one Li(2), one Li(3), one Cr(1), and one P(1) atom to form a mixture of distorted edge and corner-sharing OLi2CrP trigonal pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Cr(1), and one P(2) atom to form a mixture of distorted edge and corner-sharing OLi2CrP trigonal pyramids. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(3), one Cr(1), and one P(2) atom.