Li3Fe(PO3)8 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(11), one O(2), one O(3), one O(4), one O(8), and one O(9) atom to form distorted LiO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one Li(2)O6 octahedra, and  an edgeedge with one Fe(1)O6 octahedra. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 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, and edges with two equivalent Li(1)O6 octahedra. Fe(1) is bonded to two equivalent O(11), two equivalent O(7), and two equivalent O(9) atoms to form FeO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and edges with two equivalent Li(1)O6 octahedra. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), one O(12), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 20-67°. In the second P site, P(2) is bonded to one O(10), one O(4), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(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 19-58°. In the third P site, P(3) is bonded to one O(2), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 21-59°. In the fourth P site, P(4) is bonded to one O(11), one O(12), one O(3), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Li(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 16-66°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Li(2) 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(3) atom. In the third O site, O(3) is bonded in a linear geometry to one Li(1) and one P(4) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one P(3) and one P(4) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one P(2) and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Li(1) and one P(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(1), one Fe(1), and one P(1) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one P(1) and one P(4) atom.
Li3Fe(PO3)8 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(11), one O(2), one O(3), one O(4), one O(8), and one O(9) atom to form distorted LiO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one Li(2)O6 octahedra, and  an edgeedge with one Fe(1)O6 octahedra. The Li(1)-O(11) bond length is 2.30 Å. The Li(1)-O(2) bond length is 2.01 Å. The Li(1)-O(3) bond length is 2.00 Å. The Li(1)-O(4) bond length is 2.05 Å. The Li(1)-O(8) bond length is 2.03 Å. The Li(1)-O(9) bond length is 2.53 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 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, and edges with two equivalent Li(1)O6 octahedra. Both Li(2)-O(1) bond lengths are 2.01 Å. Both Li(2)-O(2) bond lengths are 2.16 Å. Both Li(2)-O(4) bond lengths are 2.16 Å. Fe(1) is bonded to two equivalent O(11), two equivalent O(7), and two equivalent O(9) atoms to form FeO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and edges with two equivalent Li(1)O6 octahedra. Both Fe(1)-O(11) bond lengths are 2.12 Å. Both Fe(1)-O(7) bond lengths are 1.89 Å. Both Fe(1)-O(9) bond lengths are 1.97 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), one O(12), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 20-67°. The P(1)-O(1) bond length is 1.47 Å. The P(1)-O(10) bond length is 1.60 Å. The P(1)-O(12) bond length is 1.60 Å. The P(1)-O(9) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(10), one O(4), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(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 19-58°. The P(2)-O(10) bond length is 1.62 Å. The P(2)-O(4) bond length is 1.50 Å. The P(2)-O(6) bond length is 1.63 Å. The P(2)-O(8) bond length is 1.49 Å. In the third P site, P(3) is bonded to one O(2), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 21-59°. The P(3)-O(2) bond length is 1.48 Å. The P(3)-O(5) bond length is 1.61 Å. The P(3)-O(6) bond length is 1.61 Å. The P(3)-O(7) bond length is 1.53 Å. In the fourth P site, P(4) is bonded to one O(11), one O(12), one O(3), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Li(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 16-66°. The P(4)-O(11) bond length is 1.52 Å. The P(4)-O(12) bond length is 1.61 Å. The P(4)-O(3) bond length is 1.48 Å. The P(4)-O(5) bond length is 1.63 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Li(2) 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(3) atom. In the third O site, O(3) is bonded in a linear geometry to one Li(1) and one P(4) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one P(3) and one P(4) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one P(2) and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Li(1) and one P(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(1), one Fe(1), and one P(1) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one P(1) and one P(4) atom.