Li7Fe4(PO4)6 crystallizes in the triclinic P1 space group. There are seven inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one O(12), one O(2), one O(5), and one O(7) atom. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(1), one O(13), one O(3), and one O(4) atom. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(11), one O(17), one O(19), one O(23), and one O(24) atom. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(10), one O(17), one O(18), and one O(4) atom. In the fifth Li site, Li(5) is bonded in a 4-coordinate geometry to one O(14), one O(2), one O(6), and one O(8) atom. In the sixth Li site, Li(6) is bonded in a distorted rectangular see-saw-like geometry to one O(12), one O(21), one O(22), and one O(24) atom. In the seventh Li site, Li(7) is bonded in a 4-coordinate geometry to one O(13), one O(18), one O(20), and one O(23) atom. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(15), one O(16), one O(2), one O(22), one O(24), and one O(8) atom to form FeO6 octahedra 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,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. In the second Fe site, Fe(2) is bonded to one O(11), one O(13), one O(18), one O(20), one O(4), and one O(6) atom to form FeO6 octahedra 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,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. In the third Fe site, Fe(3) is bonded to one O(12), one O(14), one O(19), one O(21), one O(5), and one O(7) atom to form FeO6 octahedra 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,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. In the fourth Fe site, Fe(4) is bonded to one O(1), one O(10), one O(17), one O(23), one O(3), and one O(9) atom to form FeO6 octahedra 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,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(14), one O(16), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, and  a cornercorner with one Fe(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-51°. In the second P site, P(2) is bonded to one O(20), one O(3), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, and  a cornercorner with one Fe(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-49°. In the third P site, P(3) is bonded to one O(10), one O(12), one O(2), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, and  a cornercorner with one Fe(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-43°. In the fourth P site, P(4) is bonded to one O(13), one O(15), one O(19), and one O(23) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, and  a cornercorner with one Fe(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-44°. In the fifth P site, P(5) is bonded to one O(17), one O(18), one O(22), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, and  a cornercorner with one Fe(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-52°. In the sixth P site, P(6) is bonded to one O(11), one O(21), one O(24), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, and  a cornercorner with one Fe(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-49°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(2), one Fe(4), and one P(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(5), one Fe(1), and one P(3) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(2), one Fe(4), and one P(2) atom. In the fourth O site, O(4) is bonded to one Li(2), one Li(4), one Fe(2), and one P(1) atom to form distorted corner-sharing OLi2FeP trigonal pyramids. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(1), one Fe(3), and one P(5) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(5), one Fe(2), and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(3), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(5), one Fe(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a linear geometry to one Fe(4) and one P(6) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(4), one Fe(4), and one P(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(3), one Fe(2), and one P(6) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(1), one Li(6), one Fe(3), and one P(3) atom. In the thirteenth O site, O(13) is bonded in a 4-coordinate geometry to one Li(2), one Li(7), one Fe(2), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Li(5), one Fe(3), and one P(1) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(4) atom. In the sixteenth O site, O(16) is bonded in a linear geometry to one Fe(1) and one P(1) atom. In the seventeenth O site, O(17) is bonded to one Li(3), one Li(4), one Fe(4), and one P(5) atom to form a mixture of edge and corner-sharing OLi2FeP trigonal pyramids. In the eighteenth O site, O(18) is bonded in a 4-coordinate geometry to one Li(4), one Li(7), one Fe(2), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a distorted trigonal planar geometry to one Li(3), one Fe(3), and one P(4) atom. In the twentieth O site, O(20) is bonded in a distorted trigonal planar geometry to one Li(7), one Fe(2), and one P(2) atom. In the twenty-first O site, O(21) is bonded in a distorted T-shaped geometry to one Li(6), one Fe(3), and one P(6) atom. In the twenty-second O site, O(22) is bonded in a distorted trigonal planar geometry to one Li(6), one Fe(1), and one P(5) atom. In the twenty-third O site, O(23) is bonded to one Li(3), one Li(7), one Fe(4), and one P(4) atom to form distorted edge-sharing OLi2FeP tetrahedra. In the twenty-fourth O site, O(24) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(6), one Fe(1), and one P(6) atom.
Li7Fe4(PO4)6 crystallizes in the triclinic P1 space group. There are seven inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one O(12), one O(2), one O(5), and one O(7) atom. The Li(1)-O(12) bond length is 2.52 Å. The Li(1)-O(2) bond length is 1.98 Å. The Li(1)-O(5) bond length is 2.13 Å. The Li(1)-O(7) bond length is 1.95 Å. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(1), one O(13), one O(3), and one O(4) atom. The Li(2)-O(1) bond length is 2.12 Å. The Li(2)-O(13) bond length is 2.02 Å. The Li(2)-O(3) bond length is 2.05 Å. The Li(2)-O(4) bond length is 2.22 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(11), one O(17), one O(19), one O(23), and one O(24) atom. The Li(3)-O(11) bond length is 2.09 Å. The Li(3)-O(17) bond length is 2.02 Å. The Li(3)-O(19) bond length is 2.08 Å. The Li(3)-O(23) bond length is 2.19 Å. The Li(3)-O(24) bond length is 2.42 Å. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(10), one O(17), one O(18), and one O(4) atom. The Li(4)-O(10) bond length is 2.00 Å. The Li(4)-O(17) bond length is 2.08 Å. The Li(4)-O(18) bond length is 2.34 Å. The Li(4)-O(4) bond length is 1.96 Å. In the fifth Li site, Li(5) is bonded in a 4-coordinate geometry to one O(14), one O(2), one O(6), and one O(8) atom. The Li(5)-O(14) bond length is 1.98 Å. The Li(5)-O(2) bond length is 2.37 Å. The Li(5)-O(6) bond length is 2.01 Å. The Li(5)-O(8) bond length is 1.92 Å. In the sixth Li site, Li(6) is bonded in a distorted rectangular see-saw-like geometry to one O(12), one O(21), one O(22), and one O(24) atom. The Li(6)-O(12) bond length is 2.01 Å. The Li(6)-O(21) bond length is 2.19 Å. The Li(6)-O(22) bond length is 2.10 Å. The Li(6)-O(24) bond length is 2.06 Å. In the seventh Li site, Li(7) is bonded in a 4-coordinate geometry to one O(13), one O(18), one O(20), and one O(23) atom. The Li(7)-O(13) bond length is 2.35 Å. The Li(7)-O(18) bond length is 1.99 Å. The Li(7)-O(20) bond length is 2.10 Å. The Li(7)-O(23) bond length is 1.96 Å. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(15), one O(16), one O(2), one O(22), one O(24), and one O(8) atom to form FeO6 octahedra 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,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The Fe(1)-O(15) bond length is 1.95 Å. The Fe(1)-O(16) bond length is 1.97 Å. The Fe(1)-O(2) bond length is 2.14 Å. The Fe(1)-O(22) bond length is 2.05 Å. The Fe(1)-O(24) bond length is 2.07 Å. The Fe(1)-O(8) bond length is 2.09 Å. In the second Fe site, Fe(2) is bonded to one O(11), one O(13), one O(18), one O(20), one O(4), and one O(6) atom to form FeO6 octahedra 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,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The Fe(2)-O(11) bond length is 2.01 Å. The Fe(2)-O(13) bond length is 2.16 Å. The Fe(2)-O(18) bond length is 2.18 Å. The Fe(2)-O(20) bond length is 2.03 Å. The Fe(2)-O(4) bond length is 2.16 Å. The Fe(2)-O(6) bond length is 2.00 Å. In the third Fe site, Fe(3) is bonded to one O(12), one O(14), one O(19), one O(21), one O(5), and one O(7) atom to form FeO6 octahedra 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,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The Fe(3)-O(12) bond length is 2.11 Å. The Fe(3)-O(14) bond length is 2.02 Å. The Fe(3)-O(19) bond length is 2.01 Å. The Fe(3)-O(21) bond length is 2.03 Å. The Fe(3)-O(5) bond length is 2.08 Å. The Fe(3)-O(7) bond length is 2.06 Å. In the fourth Fe site, Fe(4) is bonded to one O(1), one O(10), one O(17), one O(23), one O(3), and one O(9) atom to form FeO6 octahedra 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,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The Fe(4)-O(1) bond length is 2.04 Å. The Fe(4)-O(10) bond length is 2.07 Å. The Fe(4)-O(17) bond length is 2.16 Å. The Fe(4)-O(23) bond length is 2.14 Å. The Fe(4)-O(3) bond length is 2.05 Å. The Fe(4)-O(9) bond length is 1.93 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(14), one O(16), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, and  a cornercorner with one Fe(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-51°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(14) bond length is 1.56 Å. The P(1)-O(16) bond length is 1.52 Å. The P(1)-O(4) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(20), one O(3), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, and  a cornercorner with one Fe(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-49°. The P(2)-O(20) bond length is 1.56 Å. The P(2)-O(3) bond length is 1.55 Å. The P(2)-O(7) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.55 Å. In the third P site, P(3) is bonded to one O(10), one O(12), one O(2), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, and  a cornercorner with one Fe(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-43°. The P(3)-O(10) bond length is 1.55 Å. The P(3)-O(12) bond length is 1.55 Å. The P(3)-O(2) bond length is 1.56 Å. The P(3)-O(6) bond length is 1.55 Å. In the fourth P site, P(4) is bonded to one O(13), one O(15), one O(19), and one O(23) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, and  a cornercorner with one Fe(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-44°. The P(4)-O(13) bond length is 1.55 Å. The P(4)-O(15) bond length is 1.53 Å. The P(4)-O(19) bond length is 1.56 Å. The P(4)-O(23) bond length is 1.57 Å. In the fifth P site, P(5) is bonded to one O(17), one O(18), one O(22), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, and  a cornercorner with one Fe(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-52°. The P(5)-O(17) bond length is 1.57 Å. The P(5)-O(18) bond length is 1.56 Å. The P(5)-O(22) bond length is 1.55 Å. The P(5)-O(5) bond length is 1.54 Å. In the sixth P site, P(6) is bonded to one O(11), one O(21), one O(24), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, and  a cornercorner with one Fe(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-49°. The P(6)-O(11) bond length is 1.57 Å. The P(6)-O(21) bond length is 1.54 Å. The P(6)-O(24) bond length is 1.56 Å. The P(6)-O(9) bond length is 1.53 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(2), one Fe(4), and one P(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(5), one Fe(1), and one P(3) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(2), one Fe(4), and one P(2) atom. In the fourth O site, O(4) is bonded to one Li(2), one Li(4), one Fe(2), and one P(1) atom to form distorted corner-sharing OLi2FeP trigonal pyramids. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(1), one Fe(3), and one P(5) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(5), one Fe(2), and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(3), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(5), one Fe(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a linear geometry to one Fe(4) and one P(6) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(4), one Fe(4), and one P(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(3), one Fe(2), and one P(6) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(1), one Li(6), one Fe(3), and one P(3) atom. In the thirteenth O site, O(13) is bonded in a 4-coordinate geometry to one Li(2), one Li(7), one Fe(2), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Li(5), one Fe(3), and one P(1) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(4) atom. In the sixteenth O site, O(16) is bonded in a linear geometry to one Fe(1) and one P(1) atom. In the seventeenth O site, O(17) is bonded to one Li(3), one Li(4), one Fe(4), and one P(5) atom to form a mixture of edge and corner-sharing OLi2FeP trigonal pyramids. In the eighteenth O site, O(18) is bonded in a 4-coordinate geometry to one Li(4), one Li(7), one Fe(2), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a distorted trigonal planar geometry to one Li(3), one Fe(3), and one P(4) atom. In the twentieth O site, O(20) is bonded in a distorted trigonal planar geometry to one Li(7), one Fe(2), and one P(2) atom. In the twenty-first O site, O(21) is bonded in a distorted T-shaped geometry to one Li(6), one Fe(3), and one P(6) atom. In the twenty-second O site, O(22) is bonded in a distorted trigonal planar geometry to one Li(6), one Fe(1), and one P(5) atom. In the twenty-third O site, O(23) is bonded to one Li(3), one Li(7), one Fe(4), and one P(4) atom to form distorted edge-sharing OLi2FeP tetrahedra. In the twenty-fourth O site, O(24) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(6), one Fe(1), and one P(6) atom.