Li3Fe2(PO4)3 crystallizes in the monoclinic C2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(3), one O(5), one O(7), and one O(8) atom. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to two equivalent O(3), two equivalent O(4), and two equivalent O(7) atoms. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to two equivalent O(11), two equivalent O(6), and two equivalent O(8) atoms. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(8), one O(9), and two equivalent O(12) atoms. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(3), one O(4), 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(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. In the second Fe site, Fe(2) is bonded to one O(10), one O(11), one O(12), one O(6), one O(8), and one O(9) atom to form FeO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(5), one O(6), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra and corners with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-45°. In the second P site, P(2) is bonded to two equivalent O(10) and two equivalent O(7) atoms to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra and corners with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-46°. In the third P site, P(3) is bonded to two equivalent O(2) and two equivalent O(8) atoms to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra and corners with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-46°. In the fourth P site, P(4) is bonded to one O(1), one O(11), one O(12), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra and corners with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-45°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(4) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(3) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Fe(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(2), one Fe(1), and one P(4) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(1), one Fe(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(3), one Fe(2), and one P(1) atom. In the seventh O site, O(7) is bonded to one Li(1), one Li(2), one Fe(1), and one P(2) atom to form OLi2FeP trigonal pyramids that share  a cornercorner with one O(11)Li3FeP trigonal bipyramid,  a cornercorner with one O(8)Li3FeP trigonal bipyramid, and  an edgeedge with one O(7)Li2FeP trigonal pyramid. In the eighth O site, O(8) is bonded to one Li(1), one Li(3), one Li(4), one Fe(2), and one P(3) atom to form distorted OLi3FeP trigonal bipyramids that share corners with two equivalent O(11)Li3FeP trigonal bipyramids,  a cornercorner with one O(7)Li2FeP trigonal pyramid,  an edgeedge with one O(8)Li3FeP trigonal bipyramid, and  a faceface with one O(11)Li3FeP trigonal bipyramid. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(4), one Fe(2), and one P(1) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(4), one Fe(2), and one P(2) atom. In the eleventh O site, O(11) is bonded to one Li(1), one Li(3), one Li(4), one Fe(2), and one P(4) atom to form distorted OLi3FeP trigonal bipyramids that share  a cornercorner with one O(11)Li3FeP trigonal bipyramid, corners with two equivalent O(8)Li3FeP trigonal bipyramids,  a cornercorner with one O(7)Li2FeP trigonal pyramid, and  a faceface with one O(8)Li3FeP trigonal bipyramid. In the twelfth O site, O(12) is bonded in a 5-coordinate geometry to one Li(1), two equivalent Li(4), one Fe(2), and one P(4) atom.
Li3Fe2(PO4)3 crystallizes in the monoclinic C2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(3), one O(5), one O(7), and one O(8) atom. The Li(1)-O(11) bond length is 2.41 Å. The Li(1)-O(12) bond length is 2.50 Å. The Li(1)-O(3) bond length is 2.17 Å. The Li(1)-O(5) bond length is 2.04 Å. The Li(1)-O(7) bond length is 2.18 Å. The Li(1)-O(8) bond length is 2.36 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to two equivalent O(3), two equivalent O(4), and two equivalent O(7) atoms. Both Li(2)-O(3) bond lengths are 2.38 Å. Both Li(2)-O(4) bond lengths are 2.26 Å. Both Li(2)-O(7) bond lengths are 2.12 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to two equivalent O(11), two equivalent O(6), and two equivalent O(8) atoms. Both Li(3)-O(11) bond lengths are 2.51 Å. Both Li(3)-O(6) bond lengths are 2.38 Å. Both Li(3)-O(8) bond lengths are 2.13 Å. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(8), one O(9), and two equivalent O(12) atoms. The Li(4)-O(10) bond length is 2.39 Å. The Li(4)-O(11) bond length is 2.13 Å. The Li(4)-O(8) bond length is 2.53 Å. The Li(4)-O(9) bond length is 2.42 Å. There is one shorter (2.11 Å) and one longer (2.55 Å) Li(4)-O(12) bond length. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(3), one O(4), 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(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The Fe(1)-O(1) bond length is 1.93 Å. The Fe(1)-O(2) bond length is 1.94 Å. The Fe(1)-O(3) bond length is 2.09 Å. The Fe(1)-O(4) bond length is 2.04 Å. The Fe(1)-O(5) bond length is 2.03 Å. The Fe(1)-O(7) bond length is 2.06 Å. In the second Fe site, Fe(2) is bonded to one O(10), one O(11), one O(12), one O(6), one O(8), and one O(9) atom to form FeO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The Fe(2)-O(10) bond length is 1.95 Å. The Fe(2)-O(11) bond length is 2.11 Å. The Fe(2)-O(12) bond length is 2.09 Å. The Fe(2)-O(6) bond length is 1.96 Å. The Fe(2)-O(8) bond length is 2.10 Å. The Fe(2)-O(9) bond length is 1.95 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(5), one O(6), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra and corners with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-45°. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.54 Å. The P(1)-O(6) bond length is 1.56 Å. The P(1)-O(9) bond length is 1.55 Å. In the second P site, P(2) is bonded to two equivalent O(10) and two equivalent O(7) atoms to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra and corners with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-46°. Both P(2)-O(10) bond lengths are 1.55 Å. Both P(2)-O(7) bond lengths are 1.55 Å. In the third P site, P(3) is bonded to two equivalent O(2) and two equivalent O(8) atoms to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra and corners with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-46°. Both P(3)-O(2) bond lengths are 1.53 Å. Both P(3)-O(8) bond lengths are 1.57 Å. In the fourth P site, P(4) is bonded to one O(1), one O(11), one O(12), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra and corners with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-45°. The P(4)-O(1) bond length is 1.53 Å. The P(4)-O(11) bond length is 1.57 Å. The P(4)-O(12) bond length is 1.56 Å. The P(4)-O(4) bond length is 1.54 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(4) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(3) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Fe(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(2), one Fe(1), and one P(4) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(1), one Fe(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(3), one Fe(2), and one P(1) atom. In the seventh O site, O(7) is bonded to one Li(1), one Li(2), one Fe(1), and one P(2) atom to form OLi2FeP trigonal pyramids that share  a cornercorner with one O(11)Li3FeP trigonal bipyramid,  a cornercorner with one O(8)Li3FeP trigonal bipyramid, and  an edgeedge with one O(7)Li2FeP trigonal pyramid. In the eighth O site, O(8) is bonded to one Li(1), one Li(3), one Li(4), one Fe(2), and one P(3) atom to form distorted OLi3FeP trigonal bipyramids that share corners with two equivalent O(11)Li3FeP trigonal bipyramids,  a cornercorner with one O(7)Li2FeP trigonal pyramid,  an edgeedge with one O(8)Li3FeP trigonal bipyramid, and  a faceface with one O(11)Li3FeP trigonal bipyramid. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(4), one Fe(2), and one P(1) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(4), one Fe(2), and one P(2) atom. In the eleventh O site, O(11) is bonded to one Li(1), one Li(3), one Li(4), one Fe(2), and one P(4) atom to form distorted OLi3FeP trigonal bipyramids that share  a cornercorner with one O(11)Li3FeP trigonal bipyramid, corners with two equivalent O(8)Li3FeP trigonal bipyramids,  a cornercorner with one O(7)Li2FeP trigonal pyramid, and  a faceface with one O(8)Li3FeP trigonal bipyramid. In the twelfth O site, O(12) is bonded in a 5-coordinate geometry to one Li(1), two equivalent Li(4), one Fe(2), and one P(4) atom.