LiFe4(PO4)3 crystallizes in the monoclinic Cc space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent O(11) and two equivalent O(2) atoms. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(10), one O(12), one O(2), one O(5), and one O(6) atom to form FeO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra, and  an edgeedge with one Fe(4)O6 octahedra. In the second Fe site, Fe(2) is bonded to one O(10), one O(3), one O(4), one O(6), one O(7), and one O(9) atom to form distorted FeO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Fe(4)O6 octahedra. In the third Fe site, Fe(3) is bonded in a 6-coordinate geometry to one O(8), one O(9), two equivalent O(4), and two equivalent O(5) atoms. In the fourth Fe site, Fe(4) is bonded to one O(1), one O(11), one O(12), one O(3), one O(7), and one O(8) atom to form FeO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Fe(2)O6 octahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), one O(2), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(4)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and corners with three equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-61°. 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 Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and corners with two equivalent Fe(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-62°. In the third P site, P(3) is bonded to one O(11), one O(12), one O(3), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and corners with three equivalent Fe(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-58°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Fe(1), one Fe(4), and one P(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Li(1), one Fe(1), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Fe(2), one Fe(4), and one P(3) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Fe(2), two equivalent Fe(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Fe(1), two equivalent Fe(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Fe(2), one Fe(4), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Fe(3), one Fe(4), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Fe(2), one Fe(3), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(2), and one P(1) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one Fe(4), and one P(3) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Fe(1), one Fe(4), and one P(3) atom.
LiFe4(PO4)3 crystallizes in the monoclinic Cc space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent O(11) and two equivalent O(2) atoms. There is one shorter (2.19 Å) and one longer (2.40 Å) Li(1)-O(11) bond length. There is one shorter (2.15 Å) and one longer (2.53 Å) Li(1)-O(2) bond length. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(10), one O(12), one O(2), one O(5), and one O(6) atom to form FeO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra, and  an edgeedge with one Fe(4)O6 octahedra. The Fe(1)-O(1) bond length is 2.12 Å. The Fe(1)-O(10) bond length is 2.11 Å. The Fe(1)-O(12) bond length is 2.18 Å. The Fe(1)-O(2) bond length is 2.16 Å. The Fe(1)-O(5) bond length is 2.05 Å. The Fe(1)-O(6) bond length is 2.05 Å. In the second Fe site, Fe(2) is bonded to one O(10), one O(3), one O(4), one O(6), one O(7), and one O(9) atom to form distorted FeO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Fe(4)O6 octahedra. The Fe(2)-O(10) bond length is 2.12 Å. The Fe(2)-O(3) bond length is 2.11 Å. The Fe(2)-O(4) bond length is 2.35 Å. The Fe(2)-O(6) bond length is 2.22 Å. The Fe(2)-O(7) bond length is 2.21 Å. The Fe(2)-O(9) bond length is 2.19 Å. In the third Fe site, Fe(3) is bonded in a 6-coordinate geometry to one O(8), one O(9), two equivalent O(4), and two equivalent O(5) atoms. The Fe(3)-O(8) bond length is 2.14 Å. The Fe(3)-O(9) bond length is 2.20 Å. There is one shorter (2.23 Å) and one longer (2.36 Å) Fe(3)-O(4) bond length. There is one shorter (2.14 Å) and one longer (2.61 Å) Fe(3)-O(5) bond length. In the fourth Fe site, Fe(4) is bonded to one O(1), one O(11), one O(12), one O(3), one O(7), and one O(8) atom to form FeO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Fe(2)O6 octahedra. The Fe(4)-O(1) bond length is 2.30 Å. The Fe(4)-O(11) bond length is 2.14 Å. The Fe(4)-O(12) bond length is 2.15 Å. The Fe(4)-O(3) bond length is 2.14 Å. The Fe(4)-O(7) bond length is 2.06 Å. The Fe(4)-O(8) bond length is 2.04 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), one O(2), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(4)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and corners with three equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-61°. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(10) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.60 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 Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and corners with two equivalent Fe(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-62°. The P(2)-O(5) bond length is 1.59 Å. The P(2)-O(6) bond length is 1.53 Å. The P(2)-O(7) bond length is 1.54 Å. The P(2)-O(8) bond length is 1.58 Å. In the third P site, P(3) is bonded to one O(11), one O(12), one O(3), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and corners with three equivalent Fe(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-58°. The P(3)-O(11) bond length is 1.56 Å. The P(3)-O(12) bond length is 1.54 Å. The P(3)-O(3) bond length is 1.57 Å. The P(3)-O(9) bond length is 1.59 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Fe(1), one Fe(4), and one P(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Li(1), one Fe(1), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Fe(2), one Fe(4), and one P(3) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Fe(2), two equivalent Fe(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Fe(1), two equivalent Fe(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Fe(2), one Fe(4), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Fe(3), one Fe(4), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Fe(2), one Fe(3), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(2), and one P(1) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one Fe(4), and one P(3) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Fe(1), one Fe(4), and one P(3) atom.