Li3Fe3(PO4)4 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(12), one O(15), one O(7), and one O(9) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one P(1)O4 tetrahedra, and  an edgeedge with one Fe(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 59°. In the second Li site, Li(2) is bonded to one O(11), one O(14), one O(3), one O(4), and one O(6) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one Fe(3)O6 octahedra,  an edgeedge with one P(3)O4 tetrahedra, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 57°. In the third Li site, Li(3) is bonded to one O(10), one O(11), one O(13), one O(3), 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(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  an edgeedge with one Fe(3)O6 octahedra,  an edgeedge with one P(2)O4 tetrahedra, and  an edgeedge with one Li(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 58°. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(15), one O(16), one O(2), one O(5), and one O(9) atom to form distorted FeO5 trigonal bipyramids that share  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one P(4)O4 tetrahedra, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 58°. In the second Fe site, Fe(2) is bonded to one O(1), one O(12), one O(14), one O(2), one O(5), and one O(7) atom to form FeO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid,  a cornercorner with one Li(2)O5 trigonal bipyramid,  an edgeedge with one Li(1)O5 trigonal bipyramid, and  an edgeedge with one Fe(1)O5 trigonal bipyramid. In the third Fe site, Fe(3) is bonded to one O(10), one O(13), one O(16), one O(4), one O(6), and one O(8) atom to form distorted FeO6 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,  a cornercorner with one Li(3)O5 trigonal bipyramid,  a cornercorner with one Fe(1)O5 trigonal bipyramid,  an edgeedge with one Li(2)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O5 trigonal bipyramid. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(12), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(3)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid,  a cornercorner with one Li(3)O5 trigonal bipyramid,  a cornercorner with one Fe(1)O5 trigonal bipyramid, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 29-50°. In the second P site, P(2) is bonded to one O(1), one O(11), one O(13), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid,  a cornercorner with one Li(2)O5 trigonal bipyramid,  a cornercorner with one Li(3)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 40-53°. In the third P site, P(3) is bonded to one O(14), one O(15), one O(2), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(3)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid, corners with two equivalent Fe(1)O5 trigonal bipyramids, and  an edgeedge with one Li(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 27-53°. In the fourth P site, P(4) is bonded to one O(16), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra,  a cornercorner with one Li(3)O5 trigonal bipyramid, corners with two equivalent Li(2)O5 trigonal bipyramids, and  an edgeedge with one Fe(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 33-52°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(2), and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Fe(1), one Fe(2), and one P(3) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to 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(2), one Fe(3), and one P(4) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Fe(1), one Fe(2), and one P(4) atom. In the sixth O site, O(6) is bonded in a T-shaped geometry to one Li(2), one Fe(3), and one P(3) atom. In the seventh O site, O(7) is bonded in a T-shaped geometry to one Li(1), one Fe(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(3), one Fe(3), and one P(2) 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. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(3), one Fe(3), and one P(1) atom. In the eleventh O site, O(11) is bonded in a distorted T-shaped geometry to one Li(2), one Li(3), and one P(2) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(2), and one P(1) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Li(3), one Fe(3), and one P(2) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Li(2), one Fe(2), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(1), and one P(3) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Fe(1), one Fe(3), and one P(4) atom.
Li3Fe3(PO4)4 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(12), one O(15), one O(7), and one O(9) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one P(1)O4 tetrahedra, and  an edgeedge with one Fe(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 59°. The Li(1)-O(1) bond length is 2.00 Å. The Li(1)-O(12) bond length is 2.08 Å. The Li(1)-O(15) bond length is 2.09 Å. The Li(1)-O(7) bond length is 2.19 Å. The Li(1)-O(9) bond length is 1.95 Å. In the second Li site, Li(2) is bonded to one O(11), one O(14), one O(3), one O(4), and one O(6) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one Fe(3)O6 octahedra,  an edgeedge with one P(3)O4 tetrahedra, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 57°. The Li(2)-O(11) bond length is 1.94 Å. The Li(2)-O(14) bond length is 2.20 Å. The Li(2)-O(3) bond length is 1.89 Å. The Li(2)-O(4) bond length is 2.01 Å. The Li(2)-O(6) bond length is 2.27 Å. In the third Li site, Li(3) is bonded to one O(10), one O(11), one O(13), one O(3), 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(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  an edgeedge with one Fe(3)O6 octahedra,  an edgeedge with one P(2)O4 tetrahedra, and  an edgeedge with one Li(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 58°. The Li(3)-O(10) bond length is 2.02 Å. The Li(3)-O(11) bond length is 1.90 Å. The Li(3)-O(13) bond length is 2.14 Å. The Li(3)-O(3) bond length is 1.94 Å. The Li(3)-O(8) bond length is 2.24 Å. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(15), one O(16), one O(2), one O(5), and one O(9) atom to form distorted FeO5 trigonal bipyramids that share  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one P(4)O4 tetrahedra, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 58°. The Fe(1)-O(15) bond length is 1.91 Å. The Fe(1)-O(16) bond length is 1.98 Å. The Fe(1)-O(2) bond length is 1.96 Å. The Fe(1)-O(5) bond length is 2.16 Å. The Fe(1)-O(9) bond length is 1.92 Å. In the second Fe site, Fe(2) is bonded to one O(1), one O(12), one O(14), one O(2), one O(5), and one O(7) atom to form FeO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid,  a cornercorner with one Li(2)O5 trigonal bipyramid,  an edgeedge with one Li(1)O5 trigonal bipyramid, and  an edgeedge with one Fe(1)O5 trigonal bipyramid. The Fe(2)-O(1) bond length is 1.96 Å. The Fe(2)-O(12) bond length is 2.13 Å. The Fe(2)-O(14) bond length is 2.11 Å. The Fe(2)-O(2) bond length is 2.38 Å. The Fe(2)-O(5) bond length is 1.98 Å. The Fe(2)-O(7) bond length is 1.94 Å. In the third Fe site, Fe(3) is bonded to one O(10), one O(13), one O(16), one O(4), one O(6), and one O(8) atom to form distorted FeO6 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,  a cornercorner with one Li(3)O5 trigonal bipyramid,  a cornercorner with one Fe(1)O5 trigonal bipyramid,  an edgeedge with one Li(2)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The Fe(3)-O(10) bond length is 2.12 Å. The Fe(3)-O(13) bond length is 1.96 Å. The Fe(3)-O(16) bond length is 2.53 Å. The Fe(3)-O(4) bond length is 2.07 Å. The Fe(3)-O(6) bond length is 2.00 Å. The Fe(3)-O(8) bond length is 1.94 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(12), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(3)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid,  a cornercorner with one Li(3)O5 trigonal bipyramid,  a cornercorner with one Fe(1)O5 trigonal bipyramid, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 29-50°. The P(1)-O(10) bond length is 1.54 Å. The P(1)-O(12) bond length is 1.55 Å. The P(1)-O(7) bond length is 1.56 Å. The P(1)-O(9) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(1), one O(11), one O(13), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid,  a cornercorner with one Li(2)O5 trigonal bipyramid,  a cornercorner with one Li(3)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 40-53°. The P(2)-O(1) bond length is 1.57 Å. The P(2)-O(11) bond length is 1.50 Å. The P(2)-O(13) bond length is 1.57 Å. The P(2)-O(8) bond length is 1.56 Å. In the third P site, P(3) is bonded to one O(14), one O(15), one O(2), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(3)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid, corners with two equivalent Fe(1)O5 trigonal bipyramids, and  an edgeedge with one Li(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 27-53°. The P(3)-O(14) bond length is 1.54 Å. The P(3)-O(15) bond length is 1.56 Å. The P(3)-O(2) bond length is 1.57 Å. The P(3)-O(6) bond length is 1.54 Å. In the fourth P site, P(4) is bonded to one O(16), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra,  a cornercorner with one Li(3)O5 trigonal bipyramid, corners with two equivalent Li(2)O5 trigonal bipyramids, and  an edgeedge with one Fe(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 33-52°. The P(4)-O(16) bond length is 1.60 Å. The P(4)-O(3) bond length is 1.50 Å. The P(4)-O(4) bond length is 1.54 Å. The P(4)-O(5) bond length is 1.60 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(2), and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Fe(1), one Fe(2), and one P(3) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to 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(2), one Fe(3), and one P(4) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Fe(1), one Fe(2), and one P(4) atom. In the sixth O site, O(6) is bonded in a T-shaped geometry to one Li(2), one Fe(3), and one P(3) atom. In the seventh O site, O(7) is bonded in a T-shaped geometry to one Li(1), one Fe(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(3), one Fe(3), and one P(2) 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. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(3), one Fe(3), and one P(1) atom. In the eleventh O site, O(11) is bonded in a distorted T-shaped geometry to one Li(2), one Li(3), and one P(2) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(2), and one P(1) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Li(3), one Fe(3), and one P(2) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Li(2), one Fe(2), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(1), and one P(3) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Fe(1), one Fe(3), and one P(4) atom.