Li3Fe(PO4)2 crystallizes in the trigonal R3 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(3), one O(4), one O(8), and two equivalent O(2) atoms. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(5), one O(6), and two equivalent O(1) atoms. In the third Li site, Li(3) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form distorted LiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Fe(2)O6 octahedra. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent O(6) atoms. In the fifth Li site, Li(5) is bonded to three equivalent O(5) and three equivalent O(8) atoms to form distorted LiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one Fe(1)O6 octahedra, and  a faceface with one Fe(3)O6 octahedra. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to three equivalent O(5) and three equivalent O(7) atoms to form FeO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Li(5)O6 octahedra. In the second Fe site, Fe(2) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form FeO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Li(3)O6 octahedra. In the third Fe site, Fe(3) is bonded to three equivalent O(3) and three equivalent O(8) atoms to form FeO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Li(5)O6 octahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-46°. In the second P site, P(2) is bonded to one O(2), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-47°. There are eight inequivalent O sites. In the first O site, O(6) is bonded in a 3-coordinate geometry to one Li(2), one Li(4), and one P(2) atom. In the second O site, O(7) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(2) atom. In the third O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(5), one Fe(3), and one P(2) atom. In the fourth O site, O(1) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), two equivalent Li(2), and one P(1) atom. In the fifth O site, O(2) is bonded to one Li(3), two equivalent Li(1), one Fe(2), and one P(2) atom to form distorted face-sharing OLi3FeP trigonal bipyramids. In the sixth O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Fe(3), and one P(1) atom. In the seventh O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Fe(2), and one P(1) atom. In the eighth O site, O(5) is bonded to one Li(2), one Li(5), one Fe(1), and one P(1) atom to form distorted edge-sharing OLi2FeP trigonal pyramids.
Li3Fe(PO4)2 crystallizes in the trigonal R3 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(3), one O(4), one O(8), and two equivalent O(2) atoms. The Li(1)-O(3) bond length is 2.40 Å. The Li(1)-O(4) bond length is 2.34 Å. The Li(1)-O(8) bond length is 2.08 Å. There is one shorter (2.13 Å) and one longer (2.52 Å) Li(1)-O(2) bond length. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(5), one O(6), and two equivalent O(1) atoms. The Li(2)-O(5) bond length is 2.29 Å. The Li(2)-O(6) bond length is 1.94 Å. There is one shorter (2.03 Å) and one longer (2.13 Å) Li(2)-O(1) bond length. In the third Li site, Li(3) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form distorted LiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Fe(2)O6 octahedra. All Li(3)-O(1) bond lengths are 2.11 Å. All Li(3)-O(2) bond lengths are 2.34 Å. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent O(6) atoms. All Li(4)-O(1) bond lengths are 2.30 Å. All Li(4)-O(6) bond lengths are 1.96 Å. In the fifth Li site, Li(5) is bonded to three equivalent O(5) and three equivalent O(8) atoms to form distorted LiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one Fe(1)O6 octahedra, and  a faceface with one Fe(3)O6 octahedra. All Li(5)-O(5) bond lengths are 2.20 Å. All Li(5)-O(8) bond lengths are 2.28 Å. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to three equivalent O(5) and three equivalent O(7) atoms to form FeO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Li(5)O6 octahedra. All Fe(1)-O(5) bond lengths are 2.09 Å. All Fe(1)-O(7) bond lengths are 1.98 Å. In the second Fe site, Fe(2) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form FeO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Li(3)O6 octahedra. All Fe(2)-O(2) bond lengths are 2.07 Å. All Fe(2)-O(4) bond lengths are 1.98 Å. In the third Fe site, Fe(3) is bonded to three equivalent O(3) and three equivalent O(8) atoms to form FeO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Li(5)O6 octahedra. All Fe(3)-O(3) bond lengths are 1.95 Å. All Fe(3)-O(8) bond lengths are 2.06 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-46°. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(2), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Li(5)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-47°. The P(2)-O(2) bond length is 1.58 Å. The P(2)-O(6) bond length is 1.51 Å. The P(2)-O(7) bond length is 1.54 Å. The P(2)-O(8) bond length is 1.58 Å. There are eight inequivalent O sites. In the first O site, O(6) is bonded in a 3-coordinate geometry to one Li(2), one Li(4), and one P(2) atom. In the second O site, O(7) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(2) atom. In the third O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(5), one Fe(3), and one P(2) atom. In the fourth O site, O(1) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), two equivalent Li(2), and one P(1) atom. In the fifth O site, O(2) is bonded to one Li(3), two equivalent Li(1), one Fe(2), and one P(2) atom to form distorted face-sharing OLi3FeP trigonal bipyramids. In the sixth O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Fe(3), and one P(1) atom. In the seventh O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Fe(2), and one P(1) atom. In the eighth O site, O(5) is bonded to one Li(2), one Li(5), one Fe(1), and one P(1) atom to form distorted edge-sharing OLi2FeP trigonal pyramids.