Li5Mn2Fe3(PO4)6 crystallizes in the triclinic P1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(10), one O(14), one O(20), one O(3), one O(4), and one O(8) atom. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(11), one O(15), one O(22), and one O(5) atom. In the third Li site, Li(3) is bonded in a distorted rectangular see-saw-like geometry to one O(13), one O(18), one O(19), and one O(22) atom. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(11), one O(16), one O(17), and one O(18) atom. In the fifth Li site, Li(5) is bonded in a 6-coordinate geometry to one O(11), one O(13), one O(16), one O(18), one O(22), and one O(5) atom. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(11), one O(14), one O(18), one O(22), one O(3), and one O(7) atom to form distorted MnO6 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,  a cornercorner with one P(6)O4 tetrahedra, and  a faceface with one Fe(1)O6 octahedra. In the second Mn site, Mn(2) is bonded in a 6-coordinate geometry to one O(10), one O(15), one O(17), one O(19), one O(6), and one O(8) atom. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(12), one O(14), one O(20), one O(3), one O(7), 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,  a cornercorner with one P(6)O4 tetrahedra, and  a faceface with one Mn(1)O6 octahedra. In the second Fe site, Fe(2) is bonded to one O(1), one O(10), one O(2), one O(4), one O(6), 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 third Fe site, Fe(3) is bonded to one O(15), one O(17), one O(19), one O(21), one O(23), and one O(24) atom to form distorted 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(24), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)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 28-50°. In the second P site, P(2) is bonded to one O(13), one O(21), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)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 29-50°. In the third P site, P(3) is bonded to one O(10), one O(14), one O(16), and one O(23) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)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 29-51°. In the fourth P site, P(4) is bonded to one O(11), one O(15), one O(2), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)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 28-52°. In the fifth P site, P(5) is bonded to one O(12), one O(17), one O(18), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)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 19-51°. In the sixth P site, P(6) is bonded to one O(1), one O(19), one O(20), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)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 18-48°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Fe(2) and one P(6) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Fe(2) and one P(4) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(1), 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(1), one Fe(2), and one P(5) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Li(2), one Li(5), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Mn(2), one Fe(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Mn(1), one Fe(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(1), one Mn(2), one Fe(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(2), one Fe(2), and one P(3) atom. In the eleventh O site, O(11) is bonded in a 5-coordinate geometry to one Li(2), one Li(4), one Li(5), one Mn(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a distorted T-shaped geometry to one Li(3), one Li(5), and one P(2) atom. In the fourteenth O site, O(14) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), one Fe(1), and one P(3) atom. In the fifteenth O site, O(15) is bonded to one Li(2), one Mn(2), one Fe(3), and one P(4) atom to form distorted edge-sharing OLiMnFeP trigonal pyramids. In the sixteenth O site, O(16) is bonded in a distorted T-shaped geometry to one Li(4), one Li(5), and one P(3) atom. In the seventeenth O site, O(17) is bonded to one Li(4), one Mn(2), one Fe(3), and one P(5) atom to form distorted edge-sharing OLiMnFeP trigonal pyramids. In the eighteenth O site, O(18) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one Li(5), one Mn(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded to one Li(3), one Mn(2), one Fe(3), and one P(6) atom to form distorted edge-sharing OLiMnFeP trigonal pyramids. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(1), one Fe(1), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a bent 150 degrees geometry to one Fe(3) and one P(2) atom. In the twenty-second O site, O(22) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Li(5), one Mn(1), and one P(6) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one Fe(3) and one P(3) atom. In the twenty-fourth O site, O(24) is bonded in a bent 150 degrees geometry to one Fe(3) and one P(1) atom.
Li5Mn2Fe3(PO4)6 crystallizes in the triclinic P1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(10), one O(14), one O(20), one O(3), one O(4), and one O(8) atom. The Li(1)-O(10) bond length is 2.10 Å. The Li(1)-O(14) bond length is 2.11 Å. The Li(1)-O(20) bond length is 2.22 Å. The Li(1)-O(3) bond length is 2.40 Å. The Li(1)-O(4) bond length is 2.29 Å. The Li(1)-O(8) bond length is 2.52 Å. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(11), one O(15), one O(22), and one O(5) atom. The Li(2)-O(11) bond length is 2.06 Å. The Li(2)-O(15) bond length is 2.29 Å. The Li(2)-O(22) bond length is 2.27 Å. The Li(2)-O(5) bond length is 1.92 Å. In the third Li site, Li(3) is bonded in a distorted rectangular see-saw-like geometry to one O(13), one O(18), one O(19), and one O(22) atom. The Li(3)-O(13) bond length is 1.93 Å. The Li(3)-O(18) bond length is 2.29 Å. The Li(3)-O(19) bond length is 2.29 Å. The Li(3)-O(22) bond length is 2.06 Å. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(11), one O(16), one O(17), and one O(18) atom. The Li(4)-O(11) bond length is 2.28 Å. The Li(4)-O(16) bond length is 1.92 Å. The Li(4)-O(17) bond length is 2.33 Å. The Li(4)-O(18) bond length is 2.03 Å. In the fifth Li site, Li(5) is bonded in a 6-coordinate geometry to one O(11), one O(13), one O(16), one O(18), one O(22), and one O(5) atom. The Li(5)-O(11) bond length is 2.33 Å. The Li(5)-O(13) bond length is 1.97 Å. The Li(5)-O(16) bond length is 1.96 Å. The Li(5)-O(18) bond length is 2.35 Å. The Li(5)-O(22) bond length is 2.36 Å. The Li(5)-O(5) bond length is 2.00 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(11), one O(14), one O(18), one O(22), one O(3), and one O(7) atom to form distorted MnO6 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,  a cornercorner with one P(6)O4 tetrahedra, and  a faceface with one Fe(1)O6 octahedra. The Mn(1)-O(11) bond length is 2.20 Å. The Mn(1)-O(14) bond length is 2.27 Å. The Mn(1)-O(18) bond length is 2.25 Å. The Mn(1)-O(22) bond length is 2.22 Å. The Mn(1)-O(3) bond length is 2.27 Å. The Mn(1)-O(7) bond length is 2.18 Å. In the second Mn site, Mn(2) is bonded in a 6-coordinate geometry to one O(10), one O(15), one O(17), one O(19), one O(6), and one O(8) atom. The Mn(2)-O(10) bond length is 2.25 Å. The Mn(2)-O(15) bond length is 2.24 Å. The Mn(2)-O(17) bond length is 2.26 Å. The Mn(2)-O(19) bond length is 2.29 Å. The Mn(2)-O(6) bond length is 2.17 Å. The Mn(2)-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(12), one O(14), one O(20), one O(3), one O(7), 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,  a cornercorner with one P(6)O4 tetrahedra, and  a faceface with one Mn(1)O6 octahedra. The Fe(1)-O(12) bond length is 1.93 Å. The Fe(1)-O(14) bond length is 2.10 Å. The Fe(1)-O(20) bond length is 2.05 Å. The Fe(1)-O(3) bond length is 2.13 Å. The Fe(1)-O(7) bond length is 2.07 Å. The Fe(1)-O(9) bond length is 1.94 Å. In the second Fe site, Fe(2) is bonded to one O(1), one O(10), one O(2), one O(4), one O(6), 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(2)-O(1) bond length is 1.91 Å. The Fe(2)-O(10) bond length is 2.09 Å. The Fe(2)-O(2) bond length is 1.92 Å. The Fe(2)-O(4) bond length is 2.01 Å. The Fe(2)-O(6) bond length is 2.06 Å. The Fe(2)-O(8) bond length is 2.10 Å. In the third Fe site, Fe(3) is bonded to one O(15), one O(17), one O(19), one O(21), one O(23), and one O(24) atom to form distorted 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(15) bond length is 2.17 Å. The Fe(3)-O(17) bond length is 2.20 Å. The Fe(3)-O(19) bond length is 2.20 Å. The Fe(3)-O(21) bond length is 1.95 Å. The Fe(3)-O(23) bond length is 1.93 Å. The Fe(3)-O(24) bond length is 1.93 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(24), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)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 28-50°. The P(1)-O(24) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.58 Å. The P(1)-O(5) bond length is 1.51 Å. The P(1)-O(6) bond length is 1.56 Å. In the second P site, P(2) is bonded to one O(13), one O(21), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)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 29-50°. The P(2)-O(13) bond length is 1.51 Å. The P(2)-O(21) bond length is 1.56 Å. The P(2)-O(7) bond length is 1.57 Å. The P(2)-O(8) bond length is 1.57 Å. In the third P site, P(3) is bonded to one O(10), one O(14), one O(16), and one O(23) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)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 29-51°. The P(3)-O(10) bond length is 1.58 Å. The P(3)-O(14) bond length is 1.58 Å. The P(3)-O(16) bond length is 1.51 Å. The P(3)-O(23) bond length is 1.55 Å. In the fourth P site, P(4) is bonded to one O(11), one O(15), one O(2), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)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 28-52°. The P(4)-O(11) bond length is 1.56 Å. The P(4)-O(15) bond length is 1.58 Å. The P(4)-O(2) bond length is 1.52 Å. The P(4)-O(9) bond length is 1.53 Å. In the fifth P site, P(5) is bonded to one O(12), one O(17), one O(18), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)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 19-51°. The P(5)-O(12) bond length is 1.54 Å. The P(5)-O(17) bond length is 1.58 Å. The P(5)-O(18) bond length is 1.56 Å. The P(5)-O(4) bond length is 1.53 Å. In the sixth P site, P(6) is bonded to one O(1), one O(19), one O(20), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)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 18-48°. The P(6)-O(1) bond length is 1.53 Å. The P(6)-O(19) bond length is 1.58 Å. The P(6)-O(20) bond length is 1.54 Å. The P(6)-O(22) bond length is 1.56 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Fe(2) and one P(6) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Fe(2) and one P(4) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(1), 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(1), one Fe(2), and one P(5) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Li(2), one Li(5), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Mn(2), one Fe(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Mn(1), one Fe(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(1), one Mn(2), one Fe(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(2), one Fe(2), and one P(3) atom. In the eleventh O site, O(11) is bonded in a 5-coordinate geometry to one Li(2), one Li(4), one Li(5), one Mn(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a distorted T-shaped geometry to one Li(3), one Li(5), and one P(2) atom. In the fourteenth O site, O(14) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), one Fe(1), and one P(3) atom. In the fifteenth O site, O(15) is bonded to one Li(2), one Mn(2), one Fe(3), and one P(4) atom to form distorted edge-sharing OLiMnFeP trigonal pyramids. In the sixteenth O site, O(16) is bonded in a distorted T-shaped geometry to one Li(4), one Li(5), and one P(3) atom. In the seventeenth O site, O(17) is bonded to one Li(4), one Mn(2), one Fe(3), and one P(5) atom to form distorted edge-sharing OLiMnFeP trigonal pyramids. In the eighteenth O site, O(18) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one Li(5), one Mn(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded to one Li(3), one Mn(2), one Fe(3), and one P(6) atom to form distorted edge-sharing OLiMnFeP trigonal pyramids. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(1), one Fe(1), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a bent 150 degrees geometry to one Fe(3) and one P(2) atom. In the twenty-second O site, O(22) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Li(5), one Mn(1), and one P(6) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one Fe(3) and one P(3) atom. In the twenty-fourth O site, O(24) is bonded in a bent 150 degrees geometry to one Fe(3) and one P(1) atom.