Li3Fe3(PO4)4 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(4), one O(7), and one O(9) atom. In the second Li site, Li(2) is bonded to one O(15), one O(2), one O(3), one O(6), and one O(8) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Fe(1)O5 trigonal bipyramid, and  a cornercorner with one Fe(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 73°. In the third Li site, Li(3) is bonded in a see-saw-like geometry to one O(10), one O(2), one O(3), and one O(7) atom. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(12), one O(13), one O(14), one O(5), and one O(8) atom to form FeO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid, and  a cornercorner with one Fe(2)O5 trigonal bipyramid. In the second Fe site, Fe(2) is bonded to one O(13), one O(4), one O(6), and two equivalent O(16) atoms to form FeO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid,  a cornercorner with one Fe(1)O5 trigonal bipyramid, and  an edgeedge with one Fe(2)O5 trigonal bipyramid. In the third Fe site, Fe(3) is bonded to one O(1), one O(10), one O(11), one O(15), one O(7), and one O(9) atom to form FeO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  a cornercorner with one Li(2)O5 trigonal bipyramid. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Fe(3)O6 octahedra,  a cornercorner with one Fe(1)O5 trigonal bipyramid, and  a cornercorner with one Fe(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 21-53°. In the second P site, P(2) is bonded to one O(1), one O(12), one O(15), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Fe(3)O6 octahedra,  a cornercorner with one Fe(1)O5 trigonal bipyramid,  a cornercorner with one Fe(2)O5 trigonal bipyramid, and corners with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 46-50°. In the third P site, P(3) is bonded to one O(10), one O(16), one O(2), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Fe(1)O5 trigonal bipyramid, corners with two equivalent Li(2)O5 trigonal bipyramids, and corners with two equivalent Fe(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 28°. In the fourth P site, P(4) is bonded to one O(13), one O(14), one O(3), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid,  a cornercorner with one Fe(2)O5 trigonal bipyramid, and corners with two equivalent Fe(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 45°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Fe(3), and one P(2) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(2), one Li(3), and one P(3) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), 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 Fe(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Fe(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(2), one Fe(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Fe(3), and one P(1) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Li(2), one Fe(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(1), one Fe(3), and one P(4) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(3), one Fe(3), and one P(3) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one Fe(3) and one P(1) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one Fe(1) and one P(2) atom. In the thirteenth O site, O(13) is bonded in a trigonal planar geometry to one Fe(1), one Fe(2), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(4) atom. In the fifteenth O site, O(15) is bonded in a distorted trigonal planar geometry to one Li(2), one Fe(3), and one P(2) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to two equivalent Fe(2) and one P(3) atom.
Li3Fe3(PO4)4 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(4), one O(7), and one O(9) atom. The Li(1)-O(1) bond length is 2.27 Å. The Li(1)-O(3) bond length is 2.10 Å. The Li(1)-O(4) bond length is 2.12 Å. The Li(1)-O(7) bond length is 2.36 Å. The Li(1)-O(9) bond length is 2.04 Å. In the second Li site, Li(2) is bonded to one O(15), one O(2), one O(3), one O(6), and one O(8) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Fe(1)O5 trigonal bipyramid, and  a cornercorner with one Fe(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 73°. The Li(2)-O(15) bond length is 2.32 Å. The Li(2)-O(2) bond length is 1.98 Å. The Li(2)-O(3) bond length is 2.39 Å. The Li(2)-O(6) bond length is 2.10 Å. The Li(2)-O(8) bond length is 2.22 Å. In the third Li site, Li(3) is bonded in a see-saw-like geometry to one O(10), one O(2), one O(3), and one O(7) atom. The Li(3)-O(10) bond length is 2.05 Å. The Li(3)-O(2) bond length is 1.98 Å. The Li(3)-O(3) bond length is 2.04 Å. The Li(3)-O(7) bond length is 2.09 Å. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(12), one O(13), one O(14), one O(5), and one O(8) atom to form FeO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid, and  a cornercorner with one Fe(2)O5 trigonal bipyramid. The Fe(1)-O(12) bond length is 1.99 Å. The Fe(1)-O(13) bond length is 2.09 Å. The Fe(1)-O(14) bond length is 1.97 Å. The Fe(1)-O(5) bond length is 1.95 Å. The Fe(1)-O(8) bond length is 1.97 Å. In the second Fe site, Fe(2) is bonded to one O(13), one O(4), one O(6), and two equivalent O(16) atoms to form FeO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid,  a cornercorner with one Fe(1)O5 trigonal bipyramid, and  an edgeedge with one Fe(2)O5 trigonal bipyramid. The Fe(2)-O(13) bond length is 2.11 Å. The Fe(2)-O(4) bond length is 1.91 Å. The Fe(2)-O(6) bond length is 1.93 Å. There is one shorter (2.00 Å) and one longer (2.08 Å) Fe(2)-O(16) bond length. In the third Fe site, Fe(3) is bonded to one O(1), one O(10), one O(11), one O(15), one O(7), and one O(9) atom to form FeO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  a cornercorner with one Li(2)O5 trigonal bipyramid. The Fe(3)-O(1) bond length is 2.06 Å. The Fe(3)-O(10) bond length is 2.01 Å. The Fe(3)-O(11) bond length is 1.95 Å. The Fe(3)-O(15) bond length is 2.07 Å. The Fe(3)-O(7) bond length is 2.10 Å. The Fe(3)-O(9) bond length is 2.06 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Fe(3)O6 octahedra,  a cornercorner with one Fe(1)O5 trigonal bipyramid, and  a cornercorner with one Fe(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 21-53°. The P(1)-O(11) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.58 Å. The P(1)-O(5) bond length is 1.54 Å. The P(1)-O(7) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(1), one O(12), one O(15), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Fe(3)O6 octahedra,  a cornercorner with one Fe(1)O5 trigonal bipyramid,  a cornercorner with one Fe(2)O5 trigonal bipyramid, and corners with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 46-50°. The P(2)-O(1) bond length is 1.54 Å. The P(2)-O(12) bond length is 1.54 Å. The P(2)-O(15) bond length is 1.55 Å. The P(2)-O(6) bond length is 1.58 Å. In the third P site, P(3) is bonded to one O(10), one O(16), one O(2), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Fe(1)O5 trigonal bipyramid, corners with two equivalent Li(2)O5 trigonal bipyramids, and corners with two equivalent Fe(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 28°. The P(3)-O(10) bond length is 1.54 Å. The P(3)-O(16) bond length is 1.60 Å. The P(3)-O(2) bond length is 1.50 Å. The P(3)-O(8) bond length is 1.56 Å. In the fourth P site, P(4) is bonded to one O(13), one O(14), one O(3), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid,  a cornercorner with one Fe(2)O5 trigonal bipyramid, and corners with two equivalent Fe(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 45°. The P(4)-O(13) bond length is 1.61 Å. The P(4)-O(14) bond length is 1.53 Å. The P(4)-O(3) bond length is 1.53 Å. The P(4)-O(9) bond length is 1.55 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Fe(3), and one P(2) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(2), one Li(3), and one P(3) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), 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 Fe(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Fe(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(2), one Fe(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Fe(3), and one P(1) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Li(2), one Fe(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(1), one Fe(3), and one P(4) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(3), one Fe(3), and one P(3) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one Fe(3) and one P(1) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one Fe(1) and one P(2) atom. In the thirteenth O site, O(13) is bonded in a trigonal planar geometry to one Fe(1), one Fe(2), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(4) atom. In the fifteenth O site, O(15) is bonded in a distorted trigonal planar geometry to one Li(2), one Fe(3), and one P(2) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to two equivalent Fe(2) and one P(3) atom.