LiFe(PO3)3 crystallizes in the triclinic P-1 space group. Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(5), one O(9), and two equivalent O(8) atoms. Fe(1) is bonded to one O(3), one O(5), one O(8), one O(9), and two equivalent O(4) atoms to form FeO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one Fe(1)O6 octahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(5), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-58°. In the second P site, P(2) is bonded to one O(2), one O(3), one O(4), and one O(6) atom to form PO4 tetrahedra that share corners with three equivalent Fe(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 20-57°. In the third P site, P(3) is bonded to one O(1), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 52°. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Li(1) and one P(3) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to two equivalent Fe(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one P(2) and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one P(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to two equivalent Li(1), one Fe(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(1), and one P(1) atom.
LiFe(PO3)3 crystallizes in the triclinic P-1 space group. Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(5), one O(9), and two equivalent O(8) atoms. The Li(1)-O(1) bond length is 1.89 Å. The Li(1)-O(5) bond length is 2.08 Å. The Li(1)-O(9) bond length is 2.09 Å. There is one shorter (2.37 Å) and one longer (2.50 Å) Li(1)-O(8) bond length. Fe(1) is bonded to one O(3), one O(5), one O(8), one O(9), and two equivalent O(4) atoms to form FeO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one Fe(1)O6 octahedra. The Fe(1)-O(3) bond length is 2.03 Å. The Fe(1)-O(5) bond length is 2.37 Å. The Fe(1)-O(8) bond length is 2.22 Å. The Fe(1)-O(9) bond length is 2.20 Å. There is one shorter (2.20 Å) and one longer (2.23 Å) Fe(1)-O(4) bond length. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(5), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-58°. The P(1)-O(2) bond length is 1.62 Å. The P(1)-O(5) bond length is 1.51 Å. The P(1)-O(7) bond length is 1.61 Å. The P(1)-O(9) bond length is 1.51 Å. In the second P site, P(2) is bonded to one O(2), one O(3), one O(4), and one O(6) atom to form PO4 tetrahedra that share corners with three equivalent Fe(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 20-57°. The P(2)-O(2) bond length is 1.62 Å. The P(2)-O(3) bond length is 1.49 Å. The P(2)-O(4) bond length is 1.53 Å. The P(2)-O(6) bond length is 1.58 Å. In the third P site, P(3) is bonded to one O(1), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 52°. The P(3)-O(1) bond length is 1.47 Å. The P(3)-O(6) bond length is 1.62 Å. The P(3)-O(7) bond length is 1.63 Å. The P(3)-O(8) bond length is 1.52 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Li(1) and one P(3) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to two equivalent Fe(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one P(2) and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one P(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to two equivalent Li(1), one Fe(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(1), and one P(1) atom.