Li3Cr(PO4)2 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), and two equivalent O(1) atoms. In the second Li site, Li(2) is bonded in a distorted square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. Cr(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form CrO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra. 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 three equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-51°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), and one P(1) atom to form a mixture of distorted edge and corner-sharing OLi3P trigonal pyramids. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Cr(1), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Cr(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Cr(1), and one P(1) atom.
Li3Cr(PO4)2 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), and two equivalent O(1) atoms. The Li(1)-O(2) bond length is 2.26 Å. The Li(1)-O(3) bond length is 2.13 Å. The Li(1)-O(4) bond length is 2.22 Å. There is one shorter (2.02 Å) and one longer (2.32 Å) Li(1)-O(1) bond length. In the second Li site, Li(2) is bonded in a distorted square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Li(2)-O(1) bond lengths are 1.94 Å. Both Li(2)-O(2) bond lengths are 2.05 Å. Cr(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form CrO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra. Both Cr(1)-O(2) bond lengths are 2.07 Å. Both Cr(1)-O(3) bond lengths are 2.00 Å. Both Cr(1)-O(4) bond lengths are 2.01 Å. 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 three equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-51°. The P(1)-O(1) bond length is 1.51 Å. The P(1)-O(2) bond length is 1.58 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.57 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), and one P(1) atom to form a mixture of distorted edge and corner-sharing OLi3P trigonal pyramids. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Cr(1), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Cr(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Cr(1), and one P(1) atom.