Li4NbFe5(PO4)6 crystallizes in the triclinic P1 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(10), one O(14), one O(20), one O(24), one O(4), and one O(8) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1), one O(11), one O(15), and one O(17) atom. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(15), one O(19), one O(2), and one O(21) atom. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(17), one O(18), one O(19), and one O(3) atom. Nb(1) is bonded to one O(11), one O(13), one O(16), one O(18), one O(21), and one O(5) atom to form distorted NbO6 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. There are five inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(11), one O(14), one O(18), one O(21), one O(4), and one O(7) 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,  a cornercorner with one P(6)O4 tetrahedra,  a faceface with one Nb(1)O6 octahedra, and  a faceface with one Fe(4)O6 octahedra. In the second Fe site, Fe(2) is bonded to one O(10), one O(22), one O(23), one O(24), 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(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(3)O6 octahedra. In the third Fe site, Fe(3) is bonded to one O(10), one O(15), one O(17), one O(19), 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(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(2)O6 octahedra. In the fourth Fe site, Fe(4) is bonded to one O(12), one O(14), one O(20), one O(4), one O(7), and one O(9) 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,  a cornercorner with one P(6)O4 tetrahedra, and  a faceface with one Fe(1)O6 octahedra. In the fifth Fe site, Fe(5) is bonded in a 6-coordinate geometry to one O(1), one O(15), one O(17), one O(19), one O(2), and one O(3) atom. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  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 26-53°. In the second P site, P(2) is bonded to one O(1), one O(13), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  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 28-53°. In the third P site, P(3) is bonded to one O(10), one O(14), one O(16), and one O(2) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  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 28-55°. In the fourth P site, P(4) is bonded to one O(11), one O(15), one O(23), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  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 fifth P site, P(5) is bonded to one O(12), one O(17), one O(18), and one O(24) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  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 24-48°. In the sixth P site, P(6) is bonded to one O(19), one O(20), one O(21), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  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 22-50°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one Fe(5), and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(3), one Fe(5), and one P(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(4), one Fe(5), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Fe(1), one Fe(4), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Nb(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Fe(2), one Fe(3), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Fe(1), one Fe(4), and one P(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(1), one Fe(2), one Fe(3), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Fe(4) 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 Fe(2), one Fe(3), and one P(3) atom. In the eleventh O site, O(11) is bonded to one Li(2), one Nb(1), one Fe(1), and one P(4) atom to form distorted edge-sharing OLiNbFeP trigonal pyramids. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Fe(4) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Nb(1) and one P(2) atom. In the fourteenth O site, O(14) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Fe(1), one Fe(4), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Fe(3), one Fe(5), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one Nb(1) and one P(3) atom. In the seventeenth O site, O(17) is bonded in a 5-coordinate geometry to one Li(2), one Li(4), one Fe(3), one Fe(5), and one P(5) atom. In the eighteenth O site, O(18) is bonded to one Li(4), one Nb(1), one Fe(1), and one P(5) atom to form distorted edge-sharing OLiNbFeP trigonal pyramids. In the nineteenth O site, O(19) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one Fe(3), one Fe(5), and one P(6) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(1), one Fe(4), and one P(6) atom. In the twenty-first O site, O(21) is bonded to one Li(3), one Nb(1), one Fe(1), and one P(6) atom to form distorted edge-sharing OLiNbFeP trigonal pyramids. In the twenty-second O site, O(22) is bonded in a bent 150 degrees geometry to one Fe(2) and one P(6) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one Fe(2) and one P(4) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Li(1), one Fe(2), and one P(5) atom.
Li4NbFe5(PO4)6 crystallizes in the triclinic P1 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(10), one O(14), one O(20), one O(24), one O(4), and one O(8) atom. The Li(1)-O(10) bond length is 2.16 Å. The Li(1)-O(14) bond length is 2.10 Å. The Li(1)-O(20) bond length is 2.09 Å. The Li(1)-O(24) bond length is 2.08 Å. The Li(1)-O(4) bond length is 2.58 Å. The Li(1)-O(8) bond length is 2.46 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1), one O(11), one O(15), and one O(17) atom. The Li(2)-O(1) bond length is 1.96 Å. The Li(2)-O(11) bond length is 2.15 Å. The Li(2)-O(15) bond length is 2.09 Å. The Li(2)-O(17) bond length is 2.37 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(15), one O(19), one O(2), and one O(21) atom. The Li(3)-O(15) bond length is 2.36 Å. The Li(3)-O(19) bond length is 2.06 Å. The Li(3)-O(2) bond length is 1.97 Å. The Li(3)-O(21) bond length is 2.25 Å. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(17), one O(18), one O(19), and one O(3) atom. The Li(4)-O(17) bond length is 2.10 Å. The Li(4)-O(18) bond length is 2.20 Å. The Li(4)-O(19) bond length is 2.37 Å. The Li(4)-O(3) bond length is 1.96 Å. Nb(1) is bonded to one O(11), one O(13), one O(16), one O(18), one O(21), and one O(5) atom to form distorted NbO6 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 Nb(1)-O(11) bond length is 2.14 Å. The Nb(1)-O(13) bond length is 2.00 Å. The Nb(1)-O(16) bond length is 2.01 Å. The Nb(1)-O(18) bond length is 2.18 Å. The Nb(1)-O(21) bond length is 2.15 Å. The Nb(1)-O(5) bond length is 2.01 Å. There are five inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(11), one O(14), one O(18), one O(21), one O(4), and one O(7) 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,  a cornercorner with one P(6)O4 tetrahedra,  a faceface with one Nb(1)O6 octahedra, and  a faceface with one Fe(4)O6 octahedra. The Fe(1)-O(11) bond length is 2.37 Å. The Fe(1)-O(14) bond length is 2.19 Å. The Fe(1)-O(18) bond length is 2.32 Å. The Fe(1)-O(21) bond length is 2.37 Å. The Fe(1)-O(4) bond length is 2.18 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(22), one O(23), one O(24), 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(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(3)O6 octahedra. The Fe(2)-O(10) bond length is 2.17 Å. The Fe(2)-O(22) bond length is 2.04 Å. The Fe(2)-O(23) bond length is 2.06 Å. The Fe(2)-O(24) bond length is 2.22 Å. The Fe(2)-O(6) bond length is 2.23 Å. The Fe(2)-O(8) bond length is 2.26 Å. In the third Fe site, Fe(3) is bonded to one O(10), one O(15), one O(17), one O(19), 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(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(2)O6 octahedra. The Fe(3)-O(10) bond length is 2.22 Å. The Fe(3)-O(15) bond length is 2.23 Å. The Fe(3)-O(17) bond length is 2.27 Å. The Fe(3)-O(19) bond length is 2.27 Å. The Fe(3)-O(6) bond length is 2.13 Å. The Fe(3)-O(8) bond length is 2.19 Å. In the fourth Fe site, Fe(4) is bonded to one O(12), one O(14), one O(20), one O(4), one O(7), and one O(9) 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,  a cornercorner with one P(6)O4 tetrahedra, and  a faceface with one Fe(1)O6 octahedra. The Fe(4)-O(12) bond length is 2.04 Å. The Fe(4)-O(14) bond length is 2.19 Å. The Fe(4)-O(20) bond length is 2.15 Å. The Fe(4)-O(4) bond length is 2.18 Å. The Fe(4)-O(7) bond length is 2.24 Å. The Fe(4)-O(9) bond length is 2.03 Å. In the fifth Fe site, Fe(5) is bonded in a 6-coordinate geometry to one O(1), one O(15), one O(17), one O(19), one O(2), and one O(3) atom. The Fe(5)-O(1) bond length is 2.06 Å. The Fe(5)-O(15) bond length is 2.23 Å. The Fe(5)-O(17) bond length is 2.28 Å. The Fe(5)-O(19) bond length is 2.27 Å. The Fe(5)-O(2) bond length is 2.05 Å. The Fe(5)-O(3) bond length is 2.03 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  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 26-53°. 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 1.59 Å. The P(1)-O(6) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(1), one O(13), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  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 28-53°. The P(2)-O(1) bond length is 1.54 Å. The P(2)-O(13) bond length is 1.58 Å. The P(2)-O(7) bond length is 1.54 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(14), one O(16), and one O(2) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  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 28-55°. The P(3)-O(10) bond length is 1.56 Å. The P(3)-O(14) bond length is 1.55 Å. The P(3)-O(16) bond length is 1.57 Å. The P(3)-O(2) bond length is 1.53 Å. In the fourth P site, P(4) is bonded to one O(11), one O(15), one O(23), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  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(4)-O(11) bond length is 1.62 Å. The P(4)-O(15) bond length is 1.59 Å. The P(4)-O(23) bond length is 1.51 Å. The P(4)-O(9) bond length is 1.51 Å. In the fifth P site, P(5) is bonded to one O(12), one O(17), one O(18), and one O(24) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  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 24-48°. The P(5)-O(12) bond length is 1.51 Å. The P(5)-O(17) bond length is 1.58 Å. The P(5)-O(18) bond length is 1.62 Å. The P(5)-O(24) bond length is 1.53 Å. In the sixth P site, P(6) is bonded to one O(19), one O(20), one O(21), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  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 22-50°. The P(6)-O(19) bond length is 1.58 Å. The P(6)-O(20) bond length is 1.53 Å. The P(6)-O(21) bond length is 1.61 Å. The P(6)-O(22) bond length is 1.51 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one Fe(5), and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(3), one Fe(5), and one P(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(4), one Fe(5), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Fe(1), one Fe(4), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Nb(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Fe(2), one Fe(3), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Fe(1), one Fe(4), and one P(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(1), one Fe(2), one Fe(3), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Fe(4) 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 Fe(2), one Fe(3), and one P(3) atom. In the eleventh O site, O(11) is bonded to one Li(2), one Nb(1), one Fe(1), and one P(4) atom to form distorted edge-sharing OLiNbFeP trigonal pyramids. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Fe(4) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Nb(1) and one P(2) atom. In the fourteenth O site, O(14) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Fe(1), one Fe(4), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Fe(3), one Fe(5), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one Nb(1) and one P(3) atom. In the seventeenth O site, O(17) is bonded in a 5-coordinate geometry to one Li(2), one Li(4), one Fe(3), one Fe(5), and one P(5) atom. In the eighteenth O site, O(18) is bonded to one Li(4), one Nb(1), one Fe(1), and one P(5) atom to form distorted edge-sharing OLiNbFeP trigonal pyramids. In the nineteenth O site, O(19) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one Fe(3), one Fe(5), and one P(6) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(1), one Fe(4), and one P(6) atom. In the twenty-first O site, O(21) is bonded to one Li(3), one Nb(1), one Fe(1), and one P(6) atom to form distorted edge-sharing OLiNbFeP trigonal pyramids. In the twenty-second O site, O(22) is bonded in a bent 150 degrees geometry to one Fe(2) and one P(6) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one Fe(2) and one P(4) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Li(1), one Fe(2), and one P(5) atom.