Li4Mn3OF11 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(1), one F(10), one F(2), one F(4), one F(5), and one F(7) atom. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one F(10), one F(5), one F(6), one F(7), one F(8), and one F(9) atom. In the fourth Li site, Li(4) is bonded to one F(1), one F(11), one F(4), one F(6), one F(7), and one F(9) atom to form distorted LiF6 octahedra that share corners with two equivalent Mn(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-62°. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 7-coordinate geometry to one O(1), one F(11), one F(2), one F(3), one F(5), one F(7), and one F(9) atom. In the second Mn site, Mn(2) is bonded to one O(1), one F(1), one F(10), one F(11), one F(3), and one F(8) atom to form MnOF5 octahedra that share corners with two equivalent Li(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-62°. In the third Mn site, Mn(3) is bonded in a 7-coordinate geometry to one O(1), one F(11), one F(2), one F(4), one F(6), one F(8), and one F(9) atom. O(1) is bonded to one Li(1), one Mn(1), one Mn(2), and one Mn(3) atom to form distorted OLiMn3 trigonal pyramids that share  a cornercorner with one F(6)Li3Mn tetrahedra, corners with two equivalent F(4)Li3Mn tetrahedra, corners with two equivalent F(5)Li3Mn tetrahedra,  a cornercorner with one F(2)Li2Mn2 trigonal pyramid, corners with two equivalent F(9)Li2Mn2 trigonal pyramids,  an edgeedge with one F(2)Li2Mn2 trigonal pyramid, and  an edgeedge with one F(7)Li3Mn trigonal pyramid. There are eleven inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(4), and one Mn(2) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Mn(1), and one Mn(3) atom to form distorted FLi2Mn2 trigonal pyramids that share  a cornercorner with one F(4)Li3Mn tetrahedra,  a cornercorner with one F(5)Li3Mn tetrahedra, corners with two equivalent F(6)Li3Mn tetrahedra,  a cornercorner with one O(1)LiMn3 trigonal pyramid, corners with two equivalent F(7)Li3Mn trigonal pyramids,  an edgeedge with one F(4)Li3Mn tetrahedra,  an edgeedge with one F(5)Li3Mn tetrahedra,  an edgeedge with one O(1)LiMn3 trigonal pyramid, and  an edgeedge with one F(9)Li2Mn2 trigonal pyramid. In the third F site, F(3) is bonded in a distorted bent 150 degrees geometry to one Li(2), one Mn(1), and one Mn(2) atom. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), one Li(4), and one Mn(3) atom to form FLi3Mn tetrahedra that share  a cornercorner with one F(6)Li3Mn tetrahedra, corners with two equivalent F(5)Li3Mn tetrahedra,  a cornercorner with one F(2)Li2Mn2 trigonal pyramid, corners with two equivalent O(1)LiMn3 trigonal pyramids, corners with two equivalent F(9)Li2Mn2 trigonal pyramids,  an edgeedge with one F(6)Li3Mn tetrahedra,  an edgeedge with one F(2)Li2Mn2 trigonal pyramid, and  an edgeedge with one F(7)Li3Mn trigonal pyramid. In the fifth F site, F(5) is bonded to one Li(1), one Li(2), one Li(3), and one Mn(1) atom to form distorted FLi3Mn tetrahedra that share corners with two equivalent F(4)Li3Mn tetrahedra,  a cornercorner with one F(2)Li2Mn2 trigonal pyramid,  a cornercorner with one F(7)Li3Mn trigonal pyramid, corners with two equivalent O(1)LiMn3 trigonal pyramids, corners with two equivalent F(9)Li2Mn2 trigonal pyramids,  an edgeedge with one F(6)Li3Mn tetrahedra,  an edgeedge with one F(2)Li2Mn2 trigonal pyramid, and  an edgeedge with one F(7)Li3Mn trigonal pyramid. In the sixth F site, F(6) is bonded to one Li(2), one Li(3), one Li(4), and one Mn(3) atom to form FLi3Mn tetrahedra that share  a cornercorner with one F(4)Li3Mn tetrahedra,  a cornercorner with one O(1)LiMn3 trigonal pyramid,  a cornercorner with one F(9)Li2Mn2 trigonal pyramid, corners with two equivalent F(2)Li2Mn2 trigonal pyramids, corners with two equivalent F(7)Li3Mn trigonal pyramids,  an edgeedge with one F(4)Li3Mn tetrahedra,  an edgeedge with one F(5)Li3Mn tetrahedra, and  an edgeedge with one F(9)Li2Mn2 trigonal pyramid. In the seventh F site, F(7) is bonded to one Li(1), one Li(3), one Li(4), and one Mn(1) atom to form distorted FLi3Mn trigonal pyramids that share  a cornercorner with one F(5)Li3Mn tetrahedra, corners with two equivalent F(6)Li3Mn tetrahedra,  a cornercorner with one F(9)Li2Mn2 trigonal pyramid, corners with two equivalent F(2)Li2Mn2 trigonal pyramids,  an edgeedge with one F(4)Li3Mn tetrahedra,  an edgeedge with one F(5)Li3Mn tetrahedra,  an edgeedge with one O(1)LiMn3 trigonal pyramid, and  an edgeedge with one F(9)Li2Mn2 trigonal pyramid. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one Li(3), one Mn(2), and one Mn(3) atom. In the ninth F site, F(9) is bonded to one Li(3), one Li(4), one Mn(1), and one Mn(3) atom to form distorted FLi2Mn2 trigonal pyramids that share  a cornercorner with one F(6)Li3Mn tetrahedra, corners with two equivalent F(4)Li3Mn tetrahedra, corners with two equivalent F(5)Li3Mn tetrahedra,  a cornercorner with one F(7)Li3Mn trigonal pyramid, corners with two equivalent O(1)LiMn3 trigonal pyramids,  an edgeedge with one F(6)Li3Mn tetrahedra,  an edgeedge with one F(2)Li2Mn2 trigonal pyramid, and  an edgeedge with one F(7)Li3Mn trigonal pyramid. In the tenth F site, F(10) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one Mn(2) atom. In the eleventh F site, F(11) is bonded in a rectangular see-saw-like geometry to one Li(4), one Mn(1), one Mn(2), and one Mn(3) atom.
Li4Mn3OF11 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(1), one F(10), one F(2), one F(4), one F(5), and one F(7) atom. The Li(1)-O(1) bond length is 2.47 Å. The Li(1)-F(10) bond length is 1.99 Å. The Li(1)-F(2) bond length is 2.17 Å. The Li(1)-F(4) bond length is 2.12 Å. The Li(1)-F(5) bond length is 1.95 Å. The Li(1)-F(7) bond length is 2.07 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom. The Li(2)-F(1) bond length is 2.05 Å. The Li(2)-F(2) bond length is 2.28 Å. The Li(2)-F(3) bond length is 1.93 Å. The Li(2)-F(4) bond length is 2.08 Å. The Li(2)-F(5) bond length is 2.25 Å. The Li(2)-F(6) bond length is 2.25 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one F(10), one F(5), one F(6), one F(7), one F(8), and one F(9) atom. The Li(3)-F(10) bond length is 2.04 Å. The Li(3)-F(5) bond length is 2.15 Å. The Li(3)-F(6) bond length is 2.24 Å. The Li(3)-F(7) bond length is 2.19 Å. The Li(3)-F(8) bond length is 1.92 Å. The Li(3)-F(9) bond length is 2.16 Å. In the fourth Li site, Li(4) is bonded to one F(1), one F(11), one F(4), one F(6), one F(7), and one F(9) atom to form distorted LiF6 octahedra that share corners with two equivalent Mn(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-62°. The Li(4)-F(1) bond length is 2.01 Å. The Li(4)-F(11) bond length is 2.22 Å. The Li(4)-F(4) bond length is 2.05 Å. The Li(4)-F(6) bond length is 1.97 Å. The Li(4)-F(7) bond length is 2.19 Å. The Li(4)-F(9) bond length is 2.28 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 7-coordinate geometry to one O(1), one F(11), one F(2), one F(3), one F(5), one F(7), and one F(9) atom. The Mn(1)-O(1) bond length is 1.97 Å. The Mn(1)-F(11) bond length is 2.18 Å. The Mn(1)-F(2) bond length is 2.47 Å. The Mn(1)-F(3) bond length is 2.36 Å. The Mn(1)-F(5) bond length is 2.02 Å. The Mn(1)-F(7) bond length is 1.89 Å. The Mn(1)-F(9) bond length is 1.96 Å. In the second Mn site, Mn(2) is bonded to one O(1), one F(1), one F(10), one F(11), one F(3), and one F(8) atom to form MnOF5 octahedra that share corners with two equivalent Li(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-62°. The Mn(2)-O(1) bond length is 2.11 Å. The Mn(2)-F(1) bond length is 1.90 Å. The Mn(2)-F(10) bond length is 1.90 Å. The Mn(2)-F(11) bond length is 2.10 Å. The Mn(2)-F(3) bond length is 1.87 Å. The Mn(2)-F(8) bond length is 1.85 Å. In the third Mn site, Mn(3) is bonded in a 7-coordinate geometry to one O(1), one F(11), one F(2), one F(4), one F(6), one F(8), and one F(9) atom. The Mn(3)-O(1) bond length is 1.90 Å. The Mn(3)-F(11) bond length is 2.40 Å. The Mn(3)-F(2) bond length is 1.93 Å. The Mn(3)-F(4) bond length is 1.92 Å. The Mn(3)-F(6) bond length is 1.97 Å. The Mn(3)-F(8) bond length is 2.66 Å. The Mn(3)-F(9) bond length is 2.34 Å. O(1) is bonded to one Li(1), one Mn(1), one Mn(2), and one Mn(3) atom to form distorted OLiMn3 trigonal pyramids that share  a cornercorner with one F(6)Li3Mn tetrahedra, corners with two equivalent F(4)Li3Mn tetrahedra, corners with two equivalent F(5)Li3Mn tetrahedra,  a cornercorner with one F(2)Li2Mn2 trigonal pyramid, corners with two equivalent F(9)Li2Mn2 trigonal pyramids,  an edgeedge with one F(2)Li2Mn2 trigonal pyramid, and  an edgeedge with one F(7)Li3Mn trigonal pyramid. There are eleven inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(4), and one Mn(2) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Mn(1), and one Mn(3) atom to form distorted FLi2Mn2 trigonal pyramids that share  a cornercorner with one F(4)Li3Mn tetrahedra,  a cornercorner with one F(5)Li3Mn tetrahedra, corners with two equivalent F(6)Li3Mn tetrahedra,  a cornercorner with one O(1)LiMn3 trigonal pyramid, corners with two equivalent F(7)Li3Mn trigonal pyramids,  an edgeedge with one F(4)Li3Mn tetrahedra,  an edgeedge with one F(5)Li3Mn tetrahedra,  an edgeedge with one O(1)LiMn3 trigonal pyramid, and  an edgeedge with one F(9)Li2Mn2 trigonal pyramid. In the third F site, F(3) is bonded in a distorted bent 150 degrees geometry to one Li(2), one Mn(1), and one Mn(2) atom. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), one Li(4), and one Mn(3) atom to form FLi3Mn tetrahedra that share  a cornercorner with one F(6)Li3Mn tetrahedra, corners with two equivalent F(5)Li3Mn tetrahedra,  a cornercorner with one F(2)Li2Mn2 trigonal pyramid, corners with two equivalent O(1)LiMn3 trigonal pyramids, corners with two equivalent F(9)Li2Mn2 trigonal pyramids,  an edgeedge with one F(6)Li3Mn tetrahedra,  an edgeedge with one F(2)Li2Mn2 trigonal pyramid, and  an edgeedge with one F(7)Li3Mn trigonal pyramid. In the fifth F site, F(5) is bonded to one Li(1), one Li(2), one Li(3), and one Mn(1) atom to form distorted FLi3Mn tetrahedra that share corners with two equivalent F(4)Li3Mn tetrahedra,  a cornercorner with one F(2)Li2Mn2 trigonal pyramid,  a cornercorner with one F(7)Li3Mn trigonal pyramid, corners with two equivalent O(1)LiMn3 trigonal pyramids, corners with two equivalent F(9)Li2Mn2 trigonal pyramids,  an edgeedge with one F(6)Li3Mn tetrahedra,  an edgeedge with one F(2)Li2Mn2 trigonal pyramid, and  an edgeedge with one F(7)Li3Mn trigonal pyramid. In the sixth F site, F(6) is bonded to one Li(2), one Li(3), one Li(4), and one Mn(3) atom to form FLi3Mn tetrahedra that share  a cornercorner with one F(4)Li3Mn tetrahedra,  a cornercorner with one O(1)LiMn3 trigonal pyramid,  a cornercorner with one F(9)Li2Mn2 trigonal pyramid, corners with two equivalent F(2)Li2Mn2 trigonal pyramids, corners with two equivalent F(7)Li3Mn trigonal pyramids,  an edgeedge with one F(4)Li3Mn tetrahedra,  an edgeedge with one F(5)Li3Mn tetrahedra, and  an edgeedge with one F(9)Li2Mn2 trigonal pyramid. In the seventh F site, F(7) is bonded to one Li(1), one Li(3), one Li(4), and one Mn(1) atom to form distorted FLi3Mn trigonal pyramids that share  a cornercorner with one F(5)Li3Mn tetrahedra, corners with two equivalent F(6)Li3Mn tetrahedra,  a cornercorner with one F(9)Li2Mn2 trigonal pyramid, corners with two equivalent F(2)Li2Mn2 trigonal pyramids,  an edgeedge with one F(4)Li3Mn tetrahedra,  an edgeedge with one F(5)Li3Mn tetrahedra,  an edgeedge with one O(1)LiMn3 trigonal pyramid, and  an edgeedge with one F(9)Li2Mn2 trigonal pyramid. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one Li(3), one Mn(2), and one Mn(3) atom. In the ninth F site, F(9) is bonded to one Li(3), one Li(4), one Mn(1), and one Mn(3) atom to form distorted FLi2Mn2 trigonal pyramids that share  a cornercorner with one F(6)Li3Mn tetrahedra, corners with two equivalent F(4)Li3Mn tetrahedra, corners with two equivalent F(5)Li3Mn tetrahedra,  a cornercorner with one F(7)Li3Mn trigonal pyramid, corners with two equivalent O(1)LiMn3 trigonal pyramids,  an edgeedge with one F(6)Li3Mn tetrahedra,  an edgeedge with one F(2)Li2Mn2 trigonal pyramid, and  an edgeedge with one F(7)Li3Mn trigonal pyramid. In the tenth F site, F(10) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one Mn(2) atom. In the eleventh F site, F(11) is bonded in a rectangular see-saw-like geometry to one Li(4), one Mn(1), one Mn(2), and one Mn(3) atom.