Li4Mn3Ni2Cu(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 5-coordinate geometry to one O(10), one O(14), one O(20), one O(4), and one O(8) atom. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(11), one O(15), one O(21), one O(22), and one O(5) atom. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(13), one O(18), one O(19), one O(22), and one O(23) 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(24) atom. There are three inequivalent Mn sites. In the first Mn site, Mn(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 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 Ni(1)O6 octahedra. In the second Mn site, Mn(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 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 Ni(2)O6 octahedra. In the third Mn site, Mn(3) is bonded in a 6-coordinate geometry to one O(15), one O(17), one O(19), one O(21), one O(23), and one O(24) atom. There are two inequivalent Ni sites. In the first Ni site, Ni(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 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 Mn(1)O6 octahedra. In the second Ni site, Ni(2) 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 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 Mn(2)O6 octahedra. Cu(1) 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 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 Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-48°. 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 Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-51°. 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 Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-52°. 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 Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-37°. 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 Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-39°. 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 Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-42°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(6) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(4) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Mn(1), one Ni(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one Mn(2), and one P(5) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(2), one Cu(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Mn(2), one Ni(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 Ni(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 Ni(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Mn(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 Ni(2), and one P(3) atom. In the eleventh O site, O(11) is bonded to one Li(2), one Li(4), one Ni(1), one Cu(1), and one P(4) atom to form distorted face-sharing OLi2CuNiP trigonal bipyramids. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Mn(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 Cu(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 Mn(1), one Ni(1), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Mn(3), one Ni(2), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a distorted T-shaped geometry to one Li(4), one Cu(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 Mn(3), one Ni(2), 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 Ni(1), one Cu(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a rectangular see-saw-like geometry to one Li(3), one Mn(3), one Ni(2), and one P(6) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Li(2), one Mn(3), and one P(2) atom. In the twenty-second O site, O(22) is bonded to one Li(2), one Li(3), one Ni(1), one Cu(1), and one P(6) atom to form distorted face-sharing OLi2CuNiP trigonal bipyramids. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Li(3), one Mn(3), and one P(3) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Li(4), one Mn(3), and one P(1) atom.
Li4Mn3Ni2Cu(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 5-coordinate geometry to one O(10), one O(14), one O(20), one O(4), and one O(8) atom. The Li(1)-O(10) bond length is 2.05 Å. The Li(1)-O(14) bond length is 2.15 Å. The Li(1)-O(20) bond length is 2.05 Å. The Li(1)-O(4) bond length is 2.16 Å. The Li(1)-O(8) bond length is 2.49 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(11), one O(15), one O(21), one O(22), and one O(5) atom. The Li(2)-O(11) bond length is 2.15 Å. The Li(2)-O(15) bond length is 2.12 Å. The Li(2)-O(21) bond length is 2.30 Å. The Li(2)-O(22) bond length is 2.51 Å. The Li(2)-O(5) bond length is 2.09 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(13), one O(18), one O(19), one O(22), and one O(23) atom. The Li(3)-O(13) bond length is 2.11 Å. The Li(3)-O(18) bond length is 2.47 Å. The Li(3)-O(19) bond length is 2.15 Å. The Li(3)-O(22) bond length is 2.14 Å. The Li(3)-O(23) bond length is 2.35 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(24) atom. The Li(4)-O(11) bond length is 2.46 Å. The Li(4)-O(16) bond length is 2.18 Å. The Li(4)-O(17) bond length is 2.24 Å. The Li(4)-O(18) bond length is 2.06 Å. The Li(4)-O(24) bond length is 2.39 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(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 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 Ni(1)O6 octahedra. The Mn(1)-O(12) bond length is 1.95 Å. The Mn(1)-O(14) bond length is 2.04 Å. The Mn(1)-O(20) bond length is 2.15 Å. The Mn(1)-O(3) bond length is 1.98 Å. The Mn(1)-O(7) bond length is 2.16 Å. The Mn(1)-O(9) bond length is 1.90 Å. In the second Mn site, Mn(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 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 Ni(2)O6 octahedra. The Mn(2)-O(1) bond length is 2.01 Å. The Mn(2)-O(10) bond length is 2.13 Å. The Mn(2)-O(2) bond length is 2.01 Å. The Mn(2)-O(4) bond length is 1.96 Å. The Mn(2)-O(6) bond length is 1.98 Å. The Mn(2)-O(8) bond length is 2.11 Å. In the third Mn site, Mn(3) is bonded in a 6-coordinate geometry to one O(15), one O(17), one O(19), one O(21), one O(23), and one O(24) atom. The Mn(3)-O(15) bond length is 2.29 Å. The Mn(3)-O(17) bond length is 2.29 Å. The Mn(3)-O(19) bond length is 2.20 Å. The Mn(3)-O(21) bond length is 2.05 Å. The Mn(3)-O(23) bond length is 2.07 Å. The Mn(3)-O(24) bond length is 2.09 Å. There are two inequivalent Ni sites. In the first Ni site, Ni(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 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 Mn(1)O6 octahedra. The Ni(1)-O(11) bond length is 2.14 Å. The Ni(1)-O(14) bond length is 2.18 Å. The Ni(1)-O(18) bond length is 2.14 Å. The Ni(1)-O(22) bond length is 2.19 Å. The Ni(1)-O(3) bond length is 2.21 Å. The Ni(1)-O(7) bond length is 2.07 Å. In the second Ni site, Ni(2) 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 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 Mn(2)O6 octahedra. The Ni(2)-O(10) bond length is 2.22 Å. The Ni(2)-O(15) bond length is 2.20 Å. The Ni(2)-O(17) bond length is 2.15 Å. The Ni(2)-O(19) bond length is 2.14 Å. The Ni(2)-O(6) bond length is 2.11 Å. The Ni(2)-O(8) bond length is 2.09 Å. Cu(1) 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 Cu(1)-O(11) bond length is 2.23 Å. The Cu(1)-O(13) bond length is 2.01 Å. The Cu(1)-O(16) bond length is 1.95 Å. The Cu(1)-O(18) bond length is 2.46 Å. The Cu(1)-O(22) bond length is 2.13 Å. The Cu(1)-O(5) bond length is 2.14 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 Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-48°. The P(1)-O(24) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.59 Å. The P(1)-O(5) bond length is 1.53 Å. The P(1)-O(6) bond length is 1.58 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 Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-51°. The P(2)-O(13) bond length is 1.55 Å. The P(2)-O(21) bond length is 1.53 Å. The P(2)-O(7) bond length is 1.55 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(23) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-52°. The P(3)-O(10) bond length is 1.57 Å. The P(3)-O(14) bond length is 1.59 Å. The P(3)-O(16) bond length is 1.54 Å. The P(3)-O(23) bond length is 1.52 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 Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-37°. The P(4)-O(11) bond length is 1.59 Å. The P(4)-O(15) bond length is 1.57 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 Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-39°. The P(5)-O(12) bond length is 1.52 Å. 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(4) bond length is 1.55 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 Mn(2)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, and  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-42°. The P(6)-O(1) bond length is 1.51 Å. The P(6)-O(19) bond length is 1.57 Å. The P(6)-O(20) bond length is 1.53 Å. The P(6)-O(22) bond length is 1.60 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 Mn(2) and one P(6) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(4) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Mn(1), one Ni(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one Mn(2), and one P(5) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(2), one Cu(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Mn(2), one Ni(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 Ni(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 Ni(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Mn(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 Ni(2), and one P(3) atom. In the eleventh O site, O(11) is bonded to one Li(2), one Li(4), one Ni(1), one Cu(1), and one P(4) atom to form distorted face-sharing OLi2CuNiP trigonal bipyramids. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Mn(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 Cu(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 Mn(1), one Ni(1), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Mn(3), one Ni(2), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a distorted T-shaped geometry to one Li(4), one Cu(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 Mn(3), one Ni(2), 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 Ni(1), one Cu(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a rectangular see-saw-like geometry to one Li(3), one Mn(3), one Ni(2), and one P(6) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Li(2), one Mn(3), and one P(2) atom. In the twenty-second O site, O(22) is bonded to one Li(2), one Li(3), one Ni(1), one Cu(1), and one P(6) atom to form distorted face-sharing OLi2CuNiP trigonal bipyramids. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Li(3), one Mn(3), and one P(3) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Li(4), one Mn(3), and one P(1) atom.