LiFe4(PO4)3 crystallizes in the monoclinic C2/c space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to four equivalent O(1) atoms. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(3), one O(5), and two equivalent O(4) atoms to form FeO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Fe(2)O6 octahedra. In the second Fe site, Fe(2) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms to form FeO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent Fe(1)O6 octahedra. In the third Fe site, Fe(3) is bonded in a distorted square co-planar geometry to two equivalent O(2) and two equivalent O(6) atoms. There are two inequivalent P sites. In the first P site, P(1) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with two equivalent Fe(2)O6 octahedra and corners with four equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-57°. In the second P site, P(2) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Fe(2)O6 octahedra and corners with four equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-56°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one Fe(1), and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(3), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to two equivalent Fe(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Fe(1), one Fe(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Fe(2), one Fe(3), and one P(2) atom.
LiFe4(PO4)3 crystallizes in the monoclinic C2/c space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to four equivalent O(1) atoms. There are two shorter (2.25 Å) and two longer (2.45 Å) Li(1)-O(1) bond lengths. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(3), one O(5), and two equivalent O(4) atoms to form FeO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Fe(2)O6 octahedra. The Fe(1)-O(1) bond length is 2.21 Å. The Fe(1)-O(2) bond length is 2.06 Å. The Fe(1)-O(3) bond length is 2.14 Å. The Fe(1)-O(5) bond length is 2.10 Å. There is one shorter (2.14 Å) and one longer (2.34 Å) Fe(1)-O(4) bond length. In the second Fe site, Fe(2) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms to form FeO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent Fe(1)O6 octahedra. Both Fe(2)-O(3) bond lengths are 2.16 Å. Both Fe(2)-O(5) bond lengths are 2.15 Å. Both Fe(2)-O(6) bond lengths are 2.29 Å. In the third Fe site, Fe(3) is bonded in a distorted square co-planar geometry to two equivalent O(2) and two equivalent O(6) atoms. Both Fe(3)-O(2) bond lengths are 2.05 Å. Both Fe(3)-O(6) bond lengths are 1.98 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with two equivalent Fe(2)O6 octahedra and corners with four equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-57°. Both P(1)-O(2) bond lengths are 1.57 Å. Both P(1)-O(3) bond lengths are 1.54 Å. In the second P site, P(2) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Fe(2)O6 octahedra and corners with four equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-56°. The P(2)-O(1) bond length is 1.55 Å. The P(2)-O(4) bond length is 1.54 Å. The P(2)-O(5) bond length is 1.56 Å. The P(2)-O(6) bond length is 1.59 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one Fe(1), and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(3), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to two equivalent Fe(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Fe(1), one Fe(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Fe(2), one Fe(3), and one P(2) atom.