Li4Fe5Ni(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), one O(21), and one O(5) atom. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(13), one O(18), one O(19), one O(2), and one O(21) atom. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one O(11), one O(16), one O(17), one O(18), and one O(3) atom. 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 Fe(4)O6 octahedra, and  a faceface with one Ni(1)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 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 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. Ni(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 NiO6 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 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 Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Fe(4)O6 octahedra, and  a cornercorner with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-48°. 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 Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Fe(4)O6 octahedra, and  a cornercorner with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-47°. 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 Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Fe(4)O6 octahedra, and  a cornercorner with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-50°. 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 Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Fe(4)O6 octahedra, and  a cornercorner with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-51°. 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 Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Fe(4)O6 octahedra, and  a cornercorner with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-47°. 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 Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Fe(4)O6 octahedra, and  a cornercorner with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-51°. 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 3-coordinate geometry to one Li(2), one Ni(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 in a 5-coordinate geometry to one Li(2), one Li(4), one Fe(1), one Ni(1), and one P(4) atom. 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 3-coordinate geometry to one Li(3), one Ni(1), and one P(2) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal pyramidal 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 4-coordinate geometry to one Li(2), one Fe(3), one Fe(5), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Li(4), one Ni(1), and one P(3) atom. In the seventeenth O site, O(17) is bonded in a 4-coordinate geometry to one Li(4), one Fe(3), one Fe(5), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one Fe(1), one Ni(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a 4-coordinate geometry to one Li(3), 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 in a 5-coordinate geometry to one Li(2), one Li(3), one Fe(1), one Ni(1), and one P(6) atom. 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.
Li4Fe5Ni(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 2.07 Å. The Li(1)-O(14) bond length is 2.09 Å. The Li(1)-O(20) bond length is 2.13 Å. The Li(1)-O(24) bond length is 2.13 Å. The Li(1)-O(4) bond length is 2.58 Å. The Li(1)-O(8) bond length is 2.52 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), one O(21), and one O(5) atom. The Li(2)-O(1) bond length is 2.23 Å. The Li(2)-O(11) bond length is 2.15 Å. The Li(2)-O(15) bond length is 2.10 Å. The Li(2)-O(21) bond length is 2.55 Å. The Li(2)-O(5) bond length is 2.21 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(13), one O(18), one O(19), one O(2), and one O(21) atom. The Li(3)-O(13) bond length is 2.24 Å. The Li(3)-O(18) bond length is 2.54 Å. The Li(3)-O(19) bond length is 2.13 Å. The Li(3)-O(2) bond length is 2.26 Å. The Li(3)-O(21) bond length is 2.14 Å. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one O(11), one O(16), one O(17), one O(18), and one O(3) atom. The Li(4)-O(11) bond length is 2.51 Å. The Li(4)-O(16) bond length is 2.24 Å. The Li(4)-O(17) bond length is 2.15 Å. The Li(4)-O(18) bond length is 2.11 Å. The Li(4)-O(3) bond length is 2.27 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 Fe(4)O6 octahedra, and  a faceface with one Ni(1)O6 octahedra. The Fe(1)-O(11) bond length is 2.18 Å. The Fe(1)-O(14) bond length is 2.19 Å. The Fe(1)-O(18) bond length is 2.20 Å. The Fe(1)-O(21) bond length is 2.20 Å. The Fe(1)-O(4) bond length is 2.16 Å. The Fe(1)-O(7) bond length is 2.11 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 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 2.07 Å. The Fe(2)-O(22) bond length is 1.93 Å. The Fe(2)-O(23) bond length is 1.93 Å. The Fe(2)-O(24) bond length is 2.05 Å. The Fe(2)-O(6) bond length is 2.06 Å. The Fe(2)-O(8) bond length is 2.06 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 2.20 Å. The Fe(3)-O(15) bond length is 2.19 Å. The Fe(3)-O(17) bond length is 2.21 Å. The Fe(3)-O(19) bond length is 2.18 Å. The Fe(3)-O(6) bond length is 2.09 Å. The Fe(3)-O(8) bond length is 2.18 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 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 1.92 Å. The Fe(4)-O(14) bond length is 2.05 Å. The Fe(4)-O(20) bond length is 2.05 Å. The Fe(4)-O(4) bond length is 2.07 Å. The Fe(4)-O(7) bond length is 2.05 Å. The Fe(4)-O(9) bond length is 1.93 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 2.05 Å. The Fe(5)-O(15) bond length is 2.24 Å. The Fe(5)-O(17) bond length is 2.24 Å. The Fe(5)-O(19) bond length is 2.26 Å. The Fe(5)-O(2) bond length is 2.02 Å. The Fe(5)-O(3) bond length is 2.05 Å. Ni(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 NiO6 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 Ni(1)-O(11) bond length is 2.14 Å. The Ni(1)-O(13) bond length is 2.01 Å. The Ni(1)-O(16) bond length is 2.01 Å. The Ni(1)-O(18) bond length is 2.17 Å. The Ni(1)-O(21) bond length is 2.18 Å. The Ni(1)-O(5) 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 Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Fe(4)O6 octahedra, and  a cornercorner with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-48°. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.58 Å. The P(1)-O(5) bond length is 1.53 Å. The P(1)-O(6) bond length is 1.57 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 Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Fe(4)O6 octahedra, and  a cornercorner with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-47°. The P(2)-O(1) bond length is 1.53 Å. The P(2)-O(13) bond length is 1.54 Å. The P(2)-O(7) bond length is 1.57 Å. The P(2)-O(8) bond length is 1.58 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 Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Fe(4)O6 octahedra, and  a cornercorner with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-50°. 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 1.52 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 Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Fe(4)O6 octahedra, and  a cornercorner with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-51°. The P(4)-O(11) bond length is 1.57 Å. The P(4)-O(15) bond length is 1.56 Å. The P(4)-O(23) bond length is 1.53 Å. The P(4)-O(9) bond length is 1.52 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 Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Fe(4)O6 octahedra, and  a cornercorner with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-47°. The P(5)-O(12) bond length is 1.52 Å. The P(5)-O(17) bond length is 1.56 Å. The P(5)-O(18) bond length is 1.57 Å. The P(5)-O(24) bond length is 1.54 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 Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Fe(4)O6 octahedra, and  a cornercorner with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-51°. The P(6)-O(19) bond length is 1.56 Å. The P(6)-O(20) bond length is 1.54 Å. The P(6)-O(21) bond length is 1.57 Å. The P(6)-O(22) bond length is 1.53 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 3-coordinate geometry to one Li(2), one Ni(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 in a 5-coordinate geometry to one Li(2), one Li(4), one Fe(1), one Ni(1), and one P(4) atom. 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 3-coordinate geometry to one Li(3), one Ni(1), and one P(2) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal pyramidal 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 4-coordinate geometry to one Li(2), one Fe(3), one Fe(5), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Li(4), one Ni(1), and one P(3) atom. In the seventeenth O site, O(17) is bonded in a 4-coordinate geometry to one Li(4), one Fe(3), one Fe(5), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a 5-coordinate geometry to one Li(3), one Li(4), one Fe(1), one Ni(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a 4-coordinate geometry to one Li(3), 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 in a 5-coordinate geometry to one Li(2), one Li(3), one Fe(1), one Ni(1), and one P(6) atom. 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.