Li4Mn3OF11 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(10), one F(3), one F(4), one F(5), and one F(8) atom to form distorted LiF6 pentagonal pyramids that share  a cornercorner with one Li(2)F6 octahedra, corners with two equivalent Mn(3)OF5 octahedra,  a cornercorner with one Li(3)F6 pentagonal pyramid,  an edgeedge with one Li(2)F6 octahedra,  an edgeedge with one Li(3)F6 pentagonal pyramid, and  an edgeedge with one Li(4)F6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 40-72°. In the second Li site, Li(2) is bonded to one F(1), one F(3), 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(3)OF5 octahedra,  a cornercorner with one Li(1)F6 pentagonal pyramid,  a cornercorner with one Li(3)F6 pentagonal pyramid,  a cornercorner with one Li(4)F6 pentagonal pyramid,  an edgeedge with one Li(1)F6 pentagonal pyramid,  an edgeedge with one Li(3)F6 pentagonal pyramid, and  an edgeedge with one Li(4)F6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 46-60°. In the third Li site, Li(3) is bonded to one F(10), one F(5), one F(6), one F(7), one F(8), and one F(9) atom to form distorted LiF6 pentagonal pyramids that share  a cornercorner with one Li(2)F6 octahedra, corners with two equivalent Mn(3)OF5 octahedra,  a cornercorner with one Li(1)F6 pentagonal pyramid,  a cornercorner with one Li(4)F6 pentagonal pyramid,  an edgeedge with one Li(2)F6 octahedra,  an edgeedge with one Li(1)F6 pentagonal pyramid, and  an edgeedge with one Li(4)F6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 42-65°. In the fourth Li site, Li(4) is bonded to one F(11), one F(2), one F(4), one F(6), one F(8), and one F(9) atom to form distorted LiF6 pentagonal pyramids that share  a cornercorner with one Li(2)F6 octahedra, corners with two equivalent Mn(3)OF5 octahedra,  a cornercorner with one Li(3)F6 pentagonal pyramid,  an edgeedge with one Li(2)F6 octahedra,  an edgeedge with one Li(1)F6 pentagonal pyramid, and  an edgeedge with one Li(3)F6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 39-68°. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 6-coordinate geometry to one O(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom. In the second Mn site, Mn(2) is bonded in a 7-coordinate geometry to one O(1), one F(1), one F(11), one F(3), one F(5), one F(8), and one F(9) atom. In the third Mn site, Mn(3) is bonded to one O(1), one F(1), one F(10), one F(11), one F(2), and one F(7) atom to form MnOF5 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Li(1)F6 pentagonal pyramids, corners with two equivalent Li(3)F6 pentagonal pyramids, and corners with two equivalent Li(4)F6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 46-60°. O(1) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(3) atom. There are eleven inequivalent F sites. In the first F site, F(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Mn(2), and one Mn(3) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Li(4), one Mn(1), and one Mn(3) atom. In the third F site, F(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), 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(1) atom to form a mixture of corner and edge-sharing FLi3Mn tetrahedra. In the fifth F site, F(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), one Mn(1), and one Mn(2) atom. In the sixth F site, F(6) is bonded to one Li(2), one Li(3), one Li(4), and one Mn(1) atom to form a mixture of corner and edge-sharing FLi3Mn tetrahedra. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), and one Mn(3) atom. In the eighth F site, F(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), one Li(4), and one Mn(2) atom. In the ninth F site, F(9) is bonded to one Li(2), one Li(3), one Li(4), and one Mn(2) atom to form a mixture of distorted corner and edge-sharing FLi3Mn tetrahedra. 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(3) atom. In the eleventh F site, F(11) is bonded in a distorted trigonal non-coplanar geometry to one Li(4), 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 to one F(1), one F(10), one F(3), one F(4), one F(5), and one F(8) atom to form distorted LiF6 pentagonal pyramids that share  a cornercorner with one Li(2)F6 octahedra, corners with two equivalent Mn(3)OF5 octahedra,  a cornercorner with one Li(3)F6 pentagonal pyramid,  an edgeedge with one Li(2)F6 octahedra,  an edgeedge with one Li(3)F6 pentagonal pyramid, and  an edgeedge with one Li(4)F6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 40-72°. The Li(1)-F(1) bond length is 2.24 Å. The Li(1)-F(10) bond length is 2.02 Å. The Li(1)-F(3) bond length is 2.28 Å. The Li(1)-F(4) bond length is 2.26 Å. The Li(1)-F(5) bond length is 2.01 Å. The Li(1)-F(8) bond length is 2.10 Å. In the second Li site, Li(2) is bonded to one F(1), one F(3), 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(3)OF5 octahedra,  a cornercorner with one Li(1)F6 pentagonal pyramid,  a cornercorner with one Li(3)F6 pentagonal pyramid,  a cornercorner with one Li(4)F6 pentagonal pyramid,  an edgeedge with one Li(1)F6 pentagonal pyramid,  an edgeedge with one Li(3)F6 pentagonal pyramid, and  an edgeedge with one Li(4)F6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 46-60°. The Li(2)-F(1) bond length is 1.99 Å. The Li(2)-F(3) bond length is 2.27 Å. The Li(2)-F(4) bond length is 2.09 Å. The Li(2)-F(6) bond length is 2.04 Å. The Li(2)-F(7) bond length is 2.17 Å. The Li(2)-F(9) bond length is 2.32 Å. In the third Li site, Li(3) is bonded to one F(10), one F(5), one F(6), one F(7), one F(8), and one F(9) atom to form distorted LiF6 pentagonal pyramids that share  a cornercorner with one Li(2)F6 octahedra, corners with two equivalent Mn(3)OF5 octahedra,  a cornercorner with one Li(1)F6 pentagonal pyramid,  a cornercorner with one Li(4)F6 pentagonal pyramid,  an edgeedge with one Li(2)F6 octahedra,  an edgeedge with one Li(1)F6 pentagonal pyramid, and  an edgeedge with one Li(4)F6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 42-65°. The Li(3)-F(10) bond length is 2.16 Å. The Li(3)-F(5) bond length is 2.33 Å. The Li(3)-F(6) bond length is 2.03 Å. The Li(3)-F(7) bond length is 2.03 Å. The Li(3)-F(8) bond length is 2.17 Å. The Li(3)-F(9) bond length is 2.03 Å. In the fourth Li site, Li(4) is bonded to one F(11), one F(2), one F(4), one F(6), one F(8), and one F(9) atom to form distorted LiF6 pentagonal pyramids that share  a cornercorner with one Li(2)F6 octahedra, corners with two equivalent Mn(3)OF5 octahedra,  a cornercorner with one Li(3)F6 pentagonal pyramid,  an edgeedge with one Li(2)F6 octahedra,  an edgeedge with one Li(1)F6 pentagonal pyramid, and  an edgeedge with one Li(3)F6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 39-68°. The Li(4)-F(11) bond length is 2.25 Å. The Li(4)-F(2) bond length is 2.03 Å. The Li(4)-F(4) bond length is 2.03 Å. The Li(4)-F(6) bond length is 1.92 Å. The Li(4)-F(8) bond length is 2.36 Å. The Li(4)-F(9) bond length is 2.21 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 6-coordinate geometry to one O(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom. The Mn(1)-O(1) bond length is 1.90 Å. The Mn(1)-F(2) bond length is 2.44 Å. The Mn(1)-F(3) bond length is 1.94 Å. The Mn(1)-F(4) bond length is 1.96 Å. The Mn(1)-F(5) bond length is 1.97 Å. The Mn(1)-F(6) bond length is 2.08 Å. In the second Mn site, Mn(2) is bonded in a 7-coordinate geometry to one O(1), one F(1), one F(11), one F(3), one F(5), one F(8), and one F(9) atom. The Mn(2)-O(1) bond length is 1.94 Å. The Mn(2)-F(1) bond length is 2.34 Å. The Mn(2)-F(11) bond length is 1.93 Å. The Mn(2)-F(3) bond length is 2.36 Å. The Mn(2)-F(5) bond length is 2.44 Å. The Mn(2)-F(8) bond length is 1.91 Å. The Mn(2)-F(9) bond length is 1.90 Å. In the third Mn site, Mn(3) is bonded to one O(1), one F(1), one F(10), one F(11), one F(2), and one F(7) atom to form MnOF5 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Li(1)F6 pentagonal pyramids, corners with two equivalent Li(3)F6 pentagonal pyramids, and corners with two equivalent Li(4)F6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 46-60°. The Mn(3)-O(1) bond length is 1.97 Å. The Mn(3)-F(1) bond length is 2.09 Å. The Mn(3)-F(10) bond length is 1.88 Å. The Mn(3)-F(11) bond length is 2.08 Å. The Mn(3)-F(2) bond length is 1.88 Å. The Mn(3)-F(7) bond length is 1.92 Å. O(1) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(3) atom. There are eleven inequivalent F sites. In the first F site, F(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Mn(2), and one Mn(3) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Li(4), one Mn(1), and one Mn(3) atom. In the third F site, F(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), 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(1) atom to form a mixture of corner and edge-sharing FLi3Mn tetrahedra. In the fifth F site, F(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), one Mn(1), and one Mn(2) atom. In the sixth F site, F(6) is bonded to one Li(2), one Li(3), one Li(4), and one Mn(1) atom to form a mixture of corner and edge-sharing FLi3Mn tetrahedra. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), and one Mn(3) atom. In the eighth F site, F(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), one Li(4), and one Mn(2) atom. In the ninth F site, F(9) is bonded to one Li(2), one Li(3), one Li(4), and one Mn(2) atom to form a mixture of distorted corner and edge-sharing FLi3Mn tetrahedra. 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(3) atom. In the eleventh F site, F(11) is bonded in a distorted trigonal non-coplanar geometry to one Li(4), one Mn(2), and one Mn(3) atom.