Li5Mn2Co2(PO4)4 crystallizes in the triclinic P1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(14), one O(15), one O(16), one O(2), and one O(3) atom to form distorted LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent Li(2)O4 trigonal pyramids, corners with two equivalent Li(5)O4 trigonal pyramids,  an edgeedge with one P(1)O4 tetrahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-70°. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Li(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-76°. In the third Li site, Li(3) is bonded to one O(10), one O(12), one O(5), one O(7), one O(8), and one O(9) atom to form distorted LiO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one Li(2)O4 trigonal pyramid,  a cornercorner with one Li(5)O4 trigonal pyramid,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra,  an edgeedge with one P(2)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. In the fourth Li site, Li(4) is bonded to one O(10), one O(11), one O(6), one O(7), one O(8), and one O(9) atom to form LiO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra,  an edgeedge with one P(2)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. In the fifth Li site, Li(5) is bonded to one O(12), one O(13), one O(15), and one O(16) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Li(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  an edgeedge with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-76°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form distorted MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 trigonal pyramid,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one P(2)O4 tetrahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 60-66°. In the second Mn site, Mn(2) is bonded to one O(10), one O(11), one O(12), one O(13), one O(14), and one O(16) atom to form distorted MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  a cornercorner with one Li(5)O4 trigonal pyramid,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one P(3)O4 tetrahedra, and  an edgeedge with one Li(5)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 53-70°. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(8) atom. In the second Co site, Co(2) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(13), one O(14), one O(15), and one O(9) atom. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(16), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one Li(5)O4 trigonal pyramid, corners with two equivalent Li(2)O4 trigonal pyramids, and  an edgeedge with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Li(2)O4 trigonal pyramid,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, and  an edgeedge with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-59°. In the third P site, P(3) is bonded to one O(10), one O(11), one O(12), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Li(5)O4 trigonal pyramid,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, and  an edgeedge with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-59°. In the fourth P site, P(4) is bonded to one O(1), one O(13), one O(14), and one O(15) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra,  a cornercorner with one Li(2)O4 trigonal pyramid, corners with two equivalent Li(5)O4 trigonal pyramids, and  an edgeedge with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-54°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(1), and one P(4) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Co(1), and one P(1) 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 Co(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(2), one Mn(1), one Co(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Mn(1), one Co(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one Mn(1), one Co(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(4), one Mn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(4), one Co(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one Li(3), one Li(4), one Co(2), and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(4), one Mn(2), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one Mn(2), one Co(2), and one P(3) atom. In the twelfth O site, O(12) is bonded in a 5-coordinate geometry to one Li(3), one Li(5), one Mn(2), one Co(2), and one P(3) atom. In the thirteenth O site, O(13) is bonded in a 4-coordinate geometry to one Li(5), one Mn(2), one Co(2), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a distorted tetrahedral geometry to one Li(1), one Mn(2), one Co(2), and one P(4) atom. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one Li(1), one Li(5), one Co(2), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a 4-coordinate geometry to one Li(1), one Li(5), one Mn(2), and one P(1) atom.
Li5Mn2Co2(PO4)4 crystallizes in the triclinic P1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(14), one O(15), one O(16), one O(2), and one O(3) atom to form distorted LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent Li(2)O4 trigonal pyramids, corners with two equivalent Li(5)O4 trigonal pyramids,  an edgeedge with one P(1)O4 tetrahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-70°. The Li(1)-O(1) bond length is 2.13 Å. The Li(1)-O(14) bond length is 2.09 Å. The Li(1)-O(15) bond length is 2.52 Å. The Li(1)-O(16) bond length is 2.21 Å. The Li(1)-O(2) bond length is 2.22 Å. The Li(1)-O(3) bond length is 2.08 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Li(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-76°. The Li(2)-O(1) bond length is 1.91 Å. The Li(2)-O(2) bond length is 1.93 Å. The Li(2)-O(4) bond length is 1.94 Å. The Li(2)-O(5) bond length is 2.09 Å. In the third Li site, Li(3) is bonded to one O(10), one O(12), one O(5), one O(7), one O(8), and one O(9) atom to form distorted LiO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one Li(2)O4 trigonal pyramid,  a cornercorner with one Li(5)O4 trigonal pyramid,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra,  an edgeedge with one P(2)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The Li(3)-O(10) bond length is 2.51 Å. The Li(3)-O(12) bond length is 2.43 Å. The Li(3)-O(5) bond length is 2.33 Å. The Li(3)-O(7) bond length is 2.20 Å. The Li(3)-O(8) bond length is 2.03 Å. The Li(3)-O(9) bond length is 2.08 Å. In the fourth Li site, Li(4) is bonded to one O(10), one O(11), one O(6), one O(7), one O(8), and one O(9) atom to form LiO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra,  an edgeedge with one P(2)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The Li(4)-O(10) bond length is 2.13 Å. The Li(4)-O(11) bond length is 2.14 Å. The Li(4)-O(6) bond length is 2.18 Å. The Li(4)-O(7) bond length is 2.33 Å. The Li(4)-O(8) bond length is 2.24 Å. The Li(4)-O(9) bond length is 2.17 Å. In the fifth Li site, Li(5) is bonded to one O(12), one O(13), one O(15), and one O(16) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Li(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  an edgeedge with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-76°. The Li(5)-O(12) bond length is 2.05 Å. The Li(5)-O(13) bond length is 1.92 Å. The Li(5)-O(15) bond length is 1.91 Å. The Li(5)-O(16) bond length is 1.91 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form distorted MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 trigonal pyramid,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one P(2)O4 tetrahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 60-66°. The Mn(1)-O(1) bond length is 2.21 Å. The Mn(1)-O(3) bond length is 2.14 Å. The Mn(1)-O(4) bond length is 2.20 Å. The Mn(1)-O(5) bond length is 2.40 Å. The Mn(1)-O(6) bond length is 2.25 Å. The Mn(1)-O(7) bond length is 2.22 Å. In the second Mn site, Mn(2) is bonded to one O(10), one O(11), one O(12), one O(13), one O(14), and one O(16) atom to form distorted MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  a cornercorner with one Li(5)O4 trigonal pyramid,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one P(3)O4 tetrahedra, and  an edgeedge with one Li(5)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 53-70°. The Mn(2)-O(10) bond length is 2.21 Å. The Mn(2)-O(11) bond length is 2.24 Å. The Mn(2)-O(12) bond length is 2.39 Å. The Mn(2)-O(13) bond length is 2.20 Å. The Mn(2)-O(14) bond length is 2.15 Å. The Mn(2)-O(16) bond length is 2.22 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(8) atom. The Co(1)-O(2) bond length is 2.35 Å. The Co(1)-O(3) bond length is 2.26 Å. The Co(1)-O(4) bond length is 2.48 Å. The Co(1)-O(5) bond length is 2.19 Å. The Co(1)-O(6) bond length is 2.10 Å. The Co(1)-O(8) bond length is 2.10 Å. In the second Co site, Co(2) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(13), one O(14), one O(15), and one O(9) atom. The Co(2)-O(11) bond length is 2.11 Å. The Co(2)-O(12) bond length is 2.20 Å. The Co(2)-O(13) bond length is 2.45 Å. The Co(2)-O(14) bond length is 2.25 Å. The Co(2)-O(15) bond length is 2.31 Å. The Co(2)-O(9) bond length is 2.12 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(16), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one Li(5)O4 trigonal pyramid, corners with two equivalent Li(2)O4 trigonal pyramids, and  an edgeedge with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. The P(1)-O(16) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.56 Å. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Li(2)O4 trigonal pyramid,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, and  an edgeedge with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-59°. The P(2)-O(5) bond length is 1.58 Å. The P(2)-O(6) bond length is 1.57 Å. The P(2)-O(7) bond length is 1.55 Å. The P(2)-O(9) bond length is 1.55 Å. In the third P site, P(3) is bonded to one O(10), one O(11), one O(12), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Li(5)O4 trigonal pyramid,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, and  an edgeedge with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-59°. The P(3)-O(10) bond length is 1.54 Å. The P(3)-O(11) bond length is 1.58 Å. The P(3)-O(12) bond length is 1.58 Å. The P(3)-O(8) bond length is 1.55 Å. In the fourth P site, P(4) is bonded to one O(1), one O(13), one O(14), and one O(15) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra,  a cornercorner with one Li(2)O4 trigonal pyramid, corners with two equivalent Li(5)O4 trigonal pyramids, and  an edgeedge with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-54°. The P(4)-O(1) bond length is 1.57 Å. The P(4)-O(13) bond length is 1.56 Å. The P(4)-O(14) bond length is 1.57 Å. The P(4)-O(15) bond length is 1.53 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(1), and one P(4) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Co(1), and one P(1) 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 Co(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(2), one Mn(1), one Co(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Mn(1), one Co(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one Mn(1), one Co(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(4), one Mn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(4), one Co(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one Li(3), one Li(4), one Co(2), and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(4), one Mn(2), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one Mn(2), one Co(2), and one P(3) atom. In the twelfth O site, O(12) is bonded in a 5-coordinate geometry to one Li(3), one Li(5), one Mn(2), one Co(2), and one P(3) atom. In the thirteenth O site, O(13) is bonded in a 4-coordinate geometry to one Li(5), one Mn(2), one Co(2), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a distorted tetrahedral geometry to one Li(1), one Mn(2), one Co(2), and one P(4) atom. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one Li(1), one Li(5), one Co(2), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a 4-coordinate geometry to one Li(1), one Li(5), one Mn(2), and one P(1) atom.