Li4Mn5Cu(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 4-coordinate geometry to one O(10), one O(14), one O(20), one O(24), and one O(8) atom. In the second Li site, Li(2) is bonded in a 5-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), and one O(21) atom. In the fourth Li site, Li(4) is bonded in a distorted rectangular see-saw-like geometry to one O(11), one O(16), one O(17), and one O(18) atom. There are five inequivalent Mn sites. In the first Mn site, Mn(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 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 Mn(4)O6 octahedra. In the second Mn site, Mn(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 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 Mn(3)O6 octahedra. In the third Mn site, Mn(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 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 Mn(2)O6 octahedra. In the fourth Mn site, Mn(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 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 Mn(1)O6 octahedra. In the fifth Mn site, Mn(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. Cu(1) is bonded in a 4-coordinate geometry to one O(11), one O(13), one O(16), one O(21), and one O(5) 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 Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-52°. 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 Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-48°. 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 Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-53°. 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 Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-33°. 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 Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-44°. 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 Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-47°. 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 Mn(5), and one P(2) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Mn(5) and one P(3) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mn(5) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(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 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 Mn(3), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(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 Mn(2), one Mn(3), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Mn(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 Mn(2), one Mn(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 Mn(1), one Cu(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a linear geometry to one Mn(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 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 Mn(4), 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 Mn(5), 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 to one Li(4), one Mn(3), one Mn(5), and one P(5) atom to form distorted edge-sharing OLiMn2P trigonal pyramids. In the eighteenth O site, O(18) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one Mn(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded to one Li(3), one Mn(3), one Mn(5), and one P(6) atom to form distorted OLiMn2P trigonal pyramids that share  an edgeedge with one O(21)Li2MnCuP trigonal bipyramid and  an edgeedge with one O(17)LiMn2P trigonal pyramid. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(1), one Mn(4), and one P(6) atom. In the twenty-first O site, O(21) is bonded to one Li(2), one Li(3), one Mn(1), one Cu(1), and one P(6) atom to form distorted edge-sharing OLi2MnCuP trigonal bipyramids. In the twenty-second O site, O(22) is bonded in a distorted linear geometry to one Mn(2) and one P(6) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(4) atom. In the twenty-fourth O site, O(24) is bonded in a distorted T-shaped geometry to one Li(1), one Mn(2), and one P(5) atom.
Li4Mn5Cu(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 4-coordinate geometry to one O(10), one O(14), one O(20), one O(24), and one O(8) atom. The Li(1)-O(10) bond length is 2.04 Å. The Li(1)-O(14) bond length is 2.14 Å. The Li(1)-O(20) bond length is 2.02 Å. The Li(1)-O(24) bond length is 2.13 Å. The Li(1)-O(8) bond length is 2.53 Å. In the second Li site, Li(2) is bonded in a 5-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 2.31 Å. The Li(2)-O(11) bond length is 2.18 Å. The Li(2)-O(15) bond length is 2.11 Å. The Li(2)-O(21) bond length is 2.44 Å. The Li(2)-O(5) bond length is 2.08 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), and one O(21) atom. The Li(3)-O(13) bond length is 2.07 Å. The Li(3)-O(18) bond length is 2.26 Å. The Li(3)-O(19) bond length is 2.13 Å. The Li(3)-O(21) bond length is 2.20 Å. In the fourth Li site, Li(4) is bonded in a distorted rectangular see-saw-like geometry to one O(11), one O(16), one O(17), and one O(18) atom. The Li(4)-O(11) bond length is 2.22 Å. The Li(4)-O(16) bond length is 2.05 Å. The Li(4)-O(17) bond length is 2.33 Å. The Li(4)-O(18) bond length is 2.06 Å. There are five inequivalent Mn sites. In the first Mn site, Mn(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 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 Mn(4)O6 octahedra. The Mn(1)-O(11) bond length is 2.20 Å. The Mn(1)-O(14) bond length is 2.28 Å. The Mn(1)-O(18) bond length is 2.23 Å. The Mn(1)-O(21) bond length is 2.27 Å. The Mn(1)-O(4) bond length is 2.33 Å. The Mn(1)-O(7) bond length is 2.12 Å. In the second Mn site, Mn(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 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 Mn(3)O6 octahedra. The Mn(2)-O(10) bond length is 2.26 Å. The Mn(2)-O(22) bond length is 2.06 Å. The Mn(2)-O(23) bond length is 1.92 Å. The Mn(2)-O(24) bond length is 2.01 Å. The Mn(2)-O(6) bond length is 2.03 Å. The Mn(2)-O(8) bond length is 2.00 Å. In the third Mn site, Mn(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 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 Mn(2)O6 octahedra. The Mn(3)-O(10) bond length is 2.27 Å. The Mn(3)-O(15) bond length is 2.32 Å. The Mn(3)-O(17) bond length is 2.20 Å. The Mn(3)-O(19) bond length is 2.22 Å. The Mn(3)-O(6) bond length is 2.18 Å. The Mn(3)-O(8) bond length is 2.24 Å. In the fourth Mn site, Mn(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 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 Mn(1)O6 octahedra. The Mn(4)-O(12) bond length is 1.94 Å. The Mn(4)-O(14) bond length is 2.03 Å. The Mn(4)-O(20) bond length is 2.18 Å. The Mn(4)-O(4) bond length is 1.98 Å. The Mn(4)-O(7) bond length is 2.22 Å. The Mn(4)-O(9) bond length is 1.89 Å. In the fifth Mn site, Mn(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 Mn(5)-O(1) bond length is 2.10 Å. The Mn(5)-O(15) bond length is 2.35 Å. The Mn(5)-O(17) bond length is 2.33 Å. The Mn(5)-O(19) bond length is 2.27 Å. The Mn(5)-O(2) bond length is 2.05 Å. The Mn(5)-O(3) bond length is 2.07 Å. Cu(1) is bonded in a 4-coordinate geometry to one O(11), one O(13), one O(16), one O(21), and one O(5) atom. The Cu(1)-O(11) bond length is 2.51 Å. The Cu(1)-O(13) bond length is 2.05 Å. The Cu(1)-O(16) bond length is 1.94 Å. The Cu(1)-O(21) bond length is 2.04 Å. The Cu(1)-O(5) bond length is 2.07 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 Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-52°. The P(1)-O(3) bond length is 1.52 Å. The P(1)-O(4) bond length is 1.58 Å. The P(1)-O(5) bond length is 1.54 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 Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-48°. 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 1.54 Å. The P(2)-O(8) bond length is 1.60 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 Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-53°. The P(3)-O(10) bond length is 1.56 Å. The P(3)-O(14) bond length is 1.60 Å. The P(3)-O(16) bond length is 1.54 Å. The P(3)-O(2) bond length is 1.52 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 Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-33°. The P(4)-O(11) bond length is 1.57 Å. The P(4)-O(15) bond length is 1.57 Å. The P(4)-O(23) bond length is 1.53 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(24) 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 Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-44°. 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 1.57 Å. The P(5)-O(24) bond length is 1.55 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 Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, and  a cornercorner with one Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-47°. 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(21) bond length is 1.60 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 Mn(5), and one P(2) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Mn(5) and one P(3) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mn(5) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(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 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 Mn(3), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(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 Mn(2), one Mn(3), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Mn(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 Mn(2), one Mn(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 Mn(1), one Cu(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a linear geometry to one Mn(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 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 Mn(4), 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 Mn(5), 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 to one Li(4), one Mn(3), one Mn(5), and one P(5) atom to form distorted edge-sharing OLiMn2P trigonal pyramids. In the eighteenth O site, O(18) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one Mn(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded to one Li(3), one Mn(3), one Mn(5), and one P(6) atom to form distorted OLiMn2P trigonal pyramids that share  an edgeedge with one O(21)Li2MnCuP trigonal bipyramid and  an edgeedge with one O(17)LiMn2P trigonal pyramid. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(1), one Mn(4), and one P(6) atom. In the twenty-first O site, O(21) is bonded to one Li(2), one Li(3), one Mn(1), one Cu(1), and one P(6) atom to form distorted edge-sharing OLi2MnCuP trigonal bipyramids. In the twenty-second O site, O(22) is bonded in a distorted linear geometry to one Mn(2) and one P(6) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(4) atom. In the twenty-fourth O site, O(24) is bonded in a distorted T-shaped geometry to one Li(1), one Mn(2), and one P(5) atom.