Li3Mn5OF11 is Ilmenite-derived structured and crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one F(1), one F(11), one F(2), one F(5), one F(8), and one F(9) atom. In the second Li site, Li(2) is bonded to one F(1), one F(10), one F(2), one F(4), one F(7), and one F(8) atom to form distorted LiF6 octahedra that share  a cornercorner with one Mn(3)F6 octahedra, corners with two equivalent Mn(1)OF5 octahedra, corners with three equivalent Mn(2)OF5 octahedra,  an edgeedge with one Mn(5)OF5 octahedra, edges with two equivalent Mn(4)F6 octahedra, and  a faceface with one Mn(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-64°. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(1), one F(11), one F(3), one F(6), and one F(9) atom. There are five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one F(1), one F(10), one F(2), one F(4), and one F(7) atom to form distorted MnOF5 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with three equivalent Mn(4)F6 octahedra, corners with three equivalent Mn(5)OF5 octahedra, edges with two equivalent Mn(2)OF5 octahedra, and  a faceface with one Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-64°. In the second Mn site, Mn(2) is bonded to one O(1), one F(10), one F(3), one F(4), one F(6), and one F(7) atom to form MnOF5 octahedra that share  a cornercorner with one Mn(4)F6 octahedra, corners with two equivalent Mn(5)OF5 octahedra, corners with three equivalent Li(2)F6 octahedra,  an edgeedge with one Mn(3)F6 octahedra, edges with two equivalent Mn(1)OF5 octahedra, and  a faceface with one Mn(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-64°. In the third Mn site, Mn(3) is bonded to one F(11), one F(3), one F(5), one F(6), one F(8), and one F(9) atom to form MnF6 octahedra that share  a cornercorner with one Li(2)F6 octahedra, corners with three equivalent Mn(4)F6 octahedra, corners with three equivalent Mn(5)OF5 octahedra, and  an edgeedge with one Mn(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 50-61°. In the fourth Mn site, Mn(4) is bonded to one F(1), one F(10), one F(11), one F(2), one F(5), and one F(8) atom to form MnF6 octahedra that share  a cornercorner with one Mn(2)OF5 octahedra, corners with three equivalent Mn(3)F6 octahedra, corners with three equivalent Mn(1)OF5 octahedra, and edges with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-57°. In the fifth Mn site, Mn(5) is bonded to one O(1), one F(3), one F(4), one F(6), one F(7), and one F(9) atom to form distorted MnOF5 octahedra that share corners with two equivalent Mn(2)OF5 octahedra, corners with three equivalent Mn(3)F6 octahedra, corners with three equivalent Mn(1)OF5 octahedra,  an edgeedge with one Li(2)F6 octahedra, and  a faceface with one Mn(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 46-64°. O(1) is bonded to one Li(3), one Mn(1), one Mn(2), and one Mn(5) atom to form distorted OLiMn3 trigonal pyramids that share  a cornercorner with one F(2)Li2Mn2 trigonal pyramid, corners with three equivalent F(6)LiMn3 trigonal pyramids, and  an edgeedge with one F(10)LiMn3 trigonal pyramid. There are eleven inequivalent F sites. In the first F site, F(1) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one Mn(1), and one Mn(4) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Mn(1), and one Mn(4) atom to form distorted FLi2Mn2 trigonal pyramids that share  a cornercorner with one O(1)LiMn3 trigonal pyramid,  a cornercorner with one F(8)Li2Mn2 trigonal pyramid, corners with three equivalent F(10)LiMn3 trigonal pyramids, and  an edgeedge with one F(8)Li2Mn2 trigonal pyramid. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(3), one Mn(2), one Mn(3), and one Mn(5) atom. In the fourth F site, F(4) is bonded in a distorted see-saw-like geometry to one Li(2), one Mn(1), one Mn(2), and one Mn(5) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(3), and one Mn(4) atom. In the sixth F site, F(6) is bonded to one Li(3), one Mn(2), one Mn(3), and one Mn(5) atom to form distorted FLiMn3 trigonal pyramids that share  a cornercorner with one F(8)Li2Mn2 trigonal pyramid,  a cornercorner with one F(10)LiMn3 trigonal pyramid, and corners with three equivalent O(1)LiMn3 trigonal pyramids. In the seventh F site, F(7) is bonded in a 4-coordinate geometry to one Li(2), one Mn(1), one Mn(2), and one Mn(5) atom. In the eighth F site, F(8) is bonded to one Li(1), one Li(2), one Mn(3), and one Mn(4) atom to form distorted FLi2Mn2 trigonal pyramids that share  a cornercorner with one F(2)Li2Mn2 trigonal pyramid,  a cornercorner with one F(6)LiMn3 trigonal pyramid,  an edgeedge with one F(2)Li2Mn2 trigonal pyramid, and  an edgeedge with one F(10)LiMn3 trigonal pyramid. In the ninth F site, F(9) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Mn(3), and one Mn(5) atom. In the tenth F site, F(10) is bonded to one Li(2), one Mn(1), one Mn(2), and one Mn(4) atom to form distorted FLiMn3 trigonal pyramids that share  a cornercorner with one F(6)LiMn3 trigonal pyramid, corners with three equivalent F(2)Li2Mn2 trigonal pyramids,  an edgeedge with one O(1)LiMn3 trigonal pyramid, and  an edgeedge with one F(8)Li2Mn2 trigonal pyramid. In the eleventh F site, F(11) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Mn(3), and one Mn(4) atom.
Li3Mn5OF11 is Ilmenite-derived structured and crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one F(1), one F(11), one F(2), one F(5), one F(8), and one F(9) atom. The Li(1)-F(1) bond length is 1.95 Å. The Li(1)-F(11) bond length is 2.48 Å. The Li(1)-F(2) bond length is 2.27 Å. The Li(1)-F(5) bond length is 1.94 Å. The Li(1)-F(8) bond length is 2.38 Å. The Li(1)-F(9) bond length is 1.97 Å. In the second Li site, Li(2) is bonded to one F(1), one F(10), one F(2), one F(4), one F(7), and one F(8) atom to form distorted LiF6 octahedra that share  a cornercorner with one Mn(3)F6 octahedra, corners with two equivalent Mn(1)OF5 octahedra, corners with three equivalent Mn(2)OF5 octahedra,  an edgeedge with one Mn(5)OF5 octahedra, edges with two equivalent Mn(4)F6 octahedra, and  a faceface with one Mn(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-64°. The Li(2)-F(1) bond length is 2.37 Å. The Li(2)-F(10) bond length is 2.15 Å. The Li(2)-F(2) bond length is 2.00 Å. The Li(2)-F(4) bond length is 2.40 Å. The Li(2)-F(7) bond length is 1.99 Å. The Li(2)-F(8) bond length is 1.98 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(1), one F(11), one F(3), one F(6), and one F(9) atom. The Li(3)-O(1) bond length is 1.93 Å. The Li(3)-F(11) bond length is 1.96 Å. The Li(3)-F(3) bond length is 1.95 Å. The Li(3)-F(6) bond length is 2.44 Å. The Li(3)-F(9) bond length is 2.52 Å. There are five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one F(1), one F(10), one F(2), one F(4), and one F(7) atom to form distorted MnOF5 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with three equivalent Mn(4)F6 octahedra, corners with three equivalent Mn(5)OF5 octahedra, edges with two equivalent Mn(2)OF5 octahedra, and  a faceface with one Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-64°. The Mn(1)-O(1) bond length is 2.03 Å. The Mn(1)-F(1) bond length is 2.21 Å. The Mn(1)-F(10) bond length is 2.35 Å. The Mn(1)-F(2) bond length is 2.14 Å. The Mn(1)-F(4) bond length is 2.36 Å. The Mn(1)-F(7) bond length is 2.12 Å. In the second Mn site, Mn(2) is bonded to one O(1), one F(10), one F(3), one F(4), one F(6), and one F(7) atom to form MnOF5 octahedra that share  a cornercorner with one Mn(4)F6 octahedra, corners with two equivalent Mn(5)OF5 octahedra, corners with three equivalent Li(2)F6 octahedra,  an edgeedge with one Mn(3)F6 octahedra, edges with two equivalent Mn(1)OF5 octahedra, and  a faceface with one Mn(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-64°. The Mn(2)-O(1) bond length is 2.06 Å. The Mn(2)-F(10) bond length is 2.14 Å. The Mn(2)-F(3) bond length is 2.26 Å. The Mn(2)-F(4) bond length is 2.12 Å. The Mn(2)-F(6) bond length is 2.17 Å. The Mn(2)-F(7) bond length is 2.39 Å. In the third Mn site, Mn(3) is bonded to one F(11), one F(3), one F(5), one F(6), one F(8), and one F(9) atom to form MnF6 octahedra that share  a cornercorner with one Li(2)F6 octahedra, corners with three equivalent Mn(4)F6 octahedra, corners with three equivalent Mn(5)OF5 octahedra, and  an edgeedge with one Mn(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 50-61°. The Mn(3)-F(11) bond length is 2.13 Å. The Mn(3)-F(3) bond length is 2.17 Å. The Mn(3)-F(5) bond length is 2.14 Å. The Mn(3)-F(6) bond length is 2.24 Å. The Mn(3)-F(8) bond length is 2.10 Å. The Mn(3)-F(9) bond length is 2.17 Å. In the fourth Mn site, Mn(4) is bonded to one F(1), one F(10), one F(11), one F(2), one F(5), and one F(8) atom to form MnF6 octahedra that share  a cornercorner with one Mn(2)OF5 octahedra, corners with three equivalent Mn(3)F6 octahedra, corners with three equivalent Mn(1)OF5 octahedra, and edges with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-57°. The Mn(4)-F(1) bond length is 2.12 Å. The Mn(4)-F(10) bond length is 2.17 Å. The Mn(4)-F(11) bond length is 2.17 Å. The Mn(4)-F(2) bond length is 2.18 Å. The Mn(4)-F(5) bond length is 2.11 Å. The Mn(4)-F(8) bond length is 2.18 Å. In the fifth Mn site, Mn(5) is bonded to one O(1), one F(3), one F(4), one F(6), one F(7), and one F(9) atom to form distorted MnOF5 octahedra that share corners with two equivalent Mn(2)OF5 octahedra, corners with three equivalent Mn(3)F6 octahedra, corners with three equivalent Mn(1)OF5 octahedra,  an edgeedge with one Li(2)F6 octahedra, and  a faceface with one Mn(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 46-64°. The Mn(5)-O(1) bond length is 2.05 Å. The Mn(5)-F(3) bond length is 2.39 Å. The Mn(5)-F(4) bond length is 2.17 Å. The Mn(5)-F(6) bond length is 2.15 Å. The Mn(5)-F(7) bond length is 2.34 Å. The Mn(5)-F(9) bond length is 2.13 Å. O(1) is bonded to one Li(3), one Mn(1), one Mn(2), and one Mn(5) atom to form distorted OLiMn3 trigonal pyramids that share  a cornercorner with one F(2)Li2Mn2 trigonal pyramid, corners with three equivalent F(6)LiMn3 trigonal pyramids, and  an edgeedge with one F(10)LiMn3 trigonal pyramid. There are eleven inequivalent F sites. In the first F site, F(1) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one Mn(1), and one Mn(4) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Mn(1), and one Mn(4) atom to form distorted FLi2Mn2 trigonal pyramids that share  a cornercorner with one O(1)LiMn3 trigonal pyramid,  a cornercorner with one F(8)Li2Mn2 trigonal pyramid, corners with three equivalent F(10)LiMn3 trigonal pyramids, and  an edgeedge with one F(8)Li2Mn2 trigonal pyramid. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(3), one Mn(2), one Mn(3), and one Mn(5) atom. In the fourth F site, F(4) is bonded in a distorted see-saw-like geometry to one Li(2), one Mn(1), one Mn(2), and one Mn(5) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(3), and one Mn(4) atom. In the sixth F site, F(6) is bonded to one Li(3), one Mn(2), one Mn(3), and one Mn(5) atom to form distorted FLiMn3 trigonal pyramids that share  a cornercorner with one F(8)Li2Mn2 trigonal pyramid,  a cornercorner with one F(10)LiMn3 trigonal pyramid, and corners with three equivalent O(1)LiMn3 trigonal pyramids. In the seventh F site, F(7) is bonded in a 4-coordinate geometry to one Li(2), one Mn(1), one Mn(2), and one Mn(5) atom. In the eighth F site, F(8) is bonded to one Li(1), one Li(2), one Mn(3), and one Mn(4) atom to form distorted FLi2Mn2 trigonal pyramids that share  a cornercorner with one F(2)Li2Mn2 trigonal pyramid,  a cornercorner with one F(6)LiMn3 trigonal pyramid,  an edgeedge with one F(2)Li2Mn2 trigonal pyramid, and  an edgeedge with one F(10)LiMn3 trigonal pyramid. In the ninth F site, F(9) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Mn(3), and one Mn(5) atom. In the tenth F site, F(10) is bonded to one Li(2), one Mn(1), one Mn(2), and one Mn(4) atom to form distorted FLiMn3 trigonal pyramids that share  a cornercorner with one F(6)LiMn3 trigonal pyramid, corners with three equivalent F(2)Li2Mn2 trigonal pyramids,  an edgeedge with one O(1)LiMn3 trigonal pyramid, and  an edgeedge with one F(8)Li2Mn2 trigonal pyramid. In the eleventh F site, F(11) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Mn(3), and one Mn(4) atom.