Li3Fe(PO4)2 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form distorted LiO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 67-80°. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent P(1)O4 tetrahedra, and edges with two equivalent Fe(1)O6 octahedra. Fe(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form FeO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent P(1)O4 tetrahedra, and edges with two equivalent Li(2)O6 octahedra. 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 Fe(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-55°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(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(1), one Li(2), one Fe(1), and one P(1) atom to form a mixture of distorted corner and edge-sharing OLi2FeP trigonal pyramids.
Li3Fe(PO4)2 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form distorted LiO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 67-80°. The Li(1)-O(1) bond length is 2.04 Å. The Li(1)-O(2) bond length is 1.94 Å. Both Li(1)-O(3) bond lengths are 2.13 Å. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent P(1)O4 tetrahedra, and edges with two equivalent Fe(1)O6 octahedra. Both Li(2)-O(2) bond lengths are 2.06 Å. All Li(2)-O(3) bond lengths are 2.26 Å. Fe(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form FeO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent P(1)O4 tetrahedra, and edges with two equivalent Li(2)O6 octahedra. Both Fe(1)-O(1) bond lengths are 2.00 Å. All Fe(1)-O(3) bond lengths are 2.09 Å. 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 Fe(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-55°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.51 Å. Both P(1)-O(3) bond lengths are 1.58 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(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(1), one Li(2), one Fe(1), and one P(1) atom to form a mixture of distorted corner and edge-sharing OLi2FeP trigonal pyramids.