LiFe4(PO4)4 crystallizes in the orthorhombic Imm2 space group. Li(1) is bonded in a 4-coordinate geometry to two equivalent O(4) and two equivalent O(6) atoms. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(2), one O(4), two equivalent O(5), and two equivalent O(7) atoms to form FeO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)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. In the second Fe site, Fe(2) is bonded to one O(1), one O(3), two equivalent O(6), and two equivalent O(7) atoms 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 two equivalent O(1) and two equivalent O(5) 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 47-53°. In the second P site, P(2) is bonded to two equivalent O(2) and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra and corners with four equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. In the third P site, P(3) is bonded to one O(3), one O(4), and two equivalent O(7) atoms to form PO4 tetrahedra that share corners with three equivalent Fe(1)O6 octahedra and corners with three equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-53°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Fe(2) and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Fe(1) and one P(2) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Fe(2) and one P(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(1), and one P(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to two equivalent Fe(1) and one P(1) atom. In the sixth O site, O(6) is bonded to one Li(1), two equivalent Fe(2), and one P(2) atom to form distorted edge-sharing OLiFe2P tetrahedra. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(2), and one P(3) atom.
LiFe4(PO4)4 crystallizes in the orthorhombic Imm2 space group. Li(1) is bonded in a 4-coordinate geometry to two equivalent O(4) and two equivalent O(6) atoms. Both Li(1)-O(4) bond lengths are 2.01 Å. Both Li(1)-O(6) bond lengths are 2.09 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(2), one O(4), two equivalent O(5), and two equivalent O(7) atoms to form FeO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)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(1)-O(2) bond length is 1.93 Å. The Fe(1)-O(4) bond length is 2.01 Å. Both Fe(1)-O(5) bond lengths are 2.18 Å. Both Fe(1)-O(7) bond lengths are 2.07 Å. In the second Fe site, Fe(2) is bonded to one O(1), one O(3), two equivalent O(6), and two equivalent O(7) atoms 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(2)-O(1) bond length is 1.97 Å. The Fe(2)-O(3) bond length is 1.96 Å. Both Fe(2)-O(6) bond lengths are 2.15 Å. Both Fe(2)-O(7) bond lengths are 2.18 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to two equivalent O(1) and two equivalent O(5) 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 47-53°. Both P(1)-O(1) bond lengths are 1.52 Å. Both P(1)-O(5) bond lengths are 1.59 Å. In the second P site, P(2) is bonded to two equivalent O(2) and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra and corners with four equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. Both P(2)-O(2) bond lengths are 1.52 Å. Both P(2)-O(6) bond lengths are 1.58 Å. In the third P site, P(3) is bonded to one O(3), one O(4), and two equivalent O(7) atoms to form PO4 tetrahedra that share corners with three equivalent Fe(1)O6 octahedra and corners with three equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-53°. The P(3)-O(3) bond length is 1.51 Å. The P(3)-O(4) bond length is 1.56 Å. Both P(3)-O(7) bond lengths are 1.58 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Fe(2) and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Fe(1) and one P(2) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Fe(2) and one P(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(1), and one P(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to two equivalent Fe(1) and one P(1) atom. In the sixth O site, O(6) is bonded to one Li(1), two equivalent Fe(2), and one P(2) atom to form distorted edge-sharing OLiFe2P tetrahedra. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(2), and one P(3) atom.