Li2Mn4OF8 is Ilmenite-derived structured and crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(3), one F(5), one F(6), one F(7), and one F(8) atom to form LiF6 octahedra that share corners with three equivalent Mn(1)OF5 octahedra, corners with three equivalent Mn(2)OF5 octahedra, corners with three equivalent Mn(4)OF5 pentagonal pyramids, and edges with three equivalent Mn(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-63°. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(7) atom. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one F(2), one F(4), one F(5), one F(6), and one F(8) atom to form distorted MnOF5 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Mn(3)F6 octahedra, edges with three equivalent Mn(4)OF5 pentagonal pyramids, and  a faceface with one Mn(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 46-63°. In the second Mn site, Mn(2) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(7) atom to form MnOF5 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Mn(3)F6 octahedra, corners with three equivalent Mn(4)OF5 pentagonal pyramids, and  a faceface with one Mn(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-63°. In the third Mn site, Mn(3) is bonded to one F(1), one F(3), one F(5), one F(6), one F(7), and one F(8) atom to form MnF6 octahedra that share corners with three equivalent Mn(1)OF5 octahedra, corners with three equivalent Mn(2)OF5 octahedra, edges with three equivalent Li(1)F6 octahedra, and  a faceface with one Mn(4)OF5 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 46-63°. In the fourth Mn site, Mn(4) is bonded to one O(1), one F(2), one F(4), one F(5), one F(6), and one F(8) atom to form distorted MnOF5 pentagonal pyramids that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Mn(2)OF5 octahedra, edges with three equivalent Mn(1)OF5 octahedra, and  a faceface with one Mn(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-55°. O(1) is bonded to one Li(2), one Mn(1), one Mn(2), and one Mn(4) atom to form distorted OLiMn3 trigonal pyramids that share corners with two equivalent F(2)LiMn3 trigonal pyramids, corners with two equivalent F(5)LiMn3 trigonal pyramids,  an edgeedge with one F(1)Li2Mn2 trigonal pyramid, and  an edgeedge with one F(2)LiMn3 trigonal pyramid. There are eight inequivalent F sites. In the first F site, F(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(2), and one Mn(3) atom. In the second F site, F(4) is bonded in a 4-coordinate geometry to one Li(2), one Mn(1), one Mn(2), and one Mn(4) atom. In the third F site, F(5) is bonded to one Li(1), one Mn(1), one Mn(3), and one Mn(4) atom to form distorted FLiMn3 trigonal pyramids that share corners with two equivalent O(1)LiMn3 trigonal pyramids, corners with two equivalent F(1)Li2Mn2 trigonal pyramids, and corners with two equivalent F(2)LiMn3 trigonal pyramids. In the fourth F site, F(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(3), and one Mn(4) atom. In the fifth F site, F(7) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(2), and one Mn(3) atom. In the sixth F site, F(8) is bonded in a distorted see-saw-like geometry to one Li(1), one Mn(1), one Mn(3), and one Mn(4) atom. In the seventh F site, F(1) is bonded to one Li(1), one Li(2), one Mn(2), and one Mn(3) atom to form distorted FLi2Mn2 trigonal pyramids that share corners with two equivalent F(2)LiMn3 trigonal pyramids, corners with two equivalent F(5)LiMn3 trigonal pyramids, and  an edgeedge with one O(1)LiMn3 trigonal pyramid. In the eighth F site, F(2) 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 corners with two equivalent O(1)LiMn3 trigonal pyramids, corners with two equivalent F(1)Li2Mn2 trigonal pyramids, corners with two equivalent F(5)LiMn3 trigonal pyramids, and  an edgeedge with one O(1)LiMn3 trigonal pyramid.
Li2Mn4OF8 is Ilmenite-derived structured and crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(3), one F(5), one F(6), one F(7), and one F(8) atom to form LiF6 octahedra that share corners with three equivalent Mn(1)OF5 octahedra, corners with three equivalent Mn(2)OF5 octahedra, corners with three equivalent Mn(4)OF5 pentagonal pyramids, and edges with three equivalent Mn(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-63°. The Li(1)-F(1) bond length is 2.13 Å. The Li(1)-F(3) bond length is 2.17 Å. The Li(1)-F(5) bond length is 2.24 Å. The Li(1)-F(6) bond length is 2.07 Å. The Li(1)-F(7) bond length is 2.09 Å. The Li(1)-F(8) bond length is 2.12 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(7) atom. The Li(2)-O(1) bond length is 1.96 Å. The Li(2)-F(1) bond length is 2.29 Å. The Li(2)-F(2) bond length is 1.99 Å. The Li(2)-F(3) bond length is 2.48 Å. The Li(2)-F(4) bond length is 2.02 Å. The Li(2)-F(7) bond length is 2.50 Å. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one F(2), one F(4), one F(5), one F(6), and one F(8) atom to form distorted MnOF5 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Mn(3)F6 octahedra, edges with three equivalent Mn(4)OF5 pentagonal pyramids, and  a faceface with one Mn(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 46-63°. The Mn(1)-O(1) bond length is 2.06 Å. The Mn(1)-F(2) bond length is 2.27 Å. The Mn(1)-F(4) bond length is 2.41 Å. The Mn(1)-F(5) bond length is 2.14 Å. The Mn(1)-F(6) bond length is 2.18 Å. The Mn(1)-F(8) bond length is 2.15 Å. In the second Mn site, Mn(2) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(7) atom to form MnOF5 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Mn(3)F6 octahedra, corners with three equivalent Mn(4)OF5 pentagonal pyramids, and  a faceface with one Mn(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-63°. The Mn(2)-O(1) bond length is 2.06 Å. The Mn(2)-F(1) bond length is 2.12 Å. The Mn(2)-F(2) bond length is 2.33 Å. The Mn(2)-F(3) bond length is 2.15 Å. The Mn(2)-F(4) bond length is 2.28 Å. The Mn(2)-F(7) bond length is 2.14 Å. In the third Mn site, Mn(3) is bonded to one F(1), one F(3), one F(5), one F(6), one F(7), and one F(8) atom to form MnF6 octahedra that share corners with three equivalent Mn(1)OF5 octahedra, corners with three equivalent Mn(2)OF5 octahedra, edges with three equivalent Li(1)F6 octahedra, and  a faceface with one Mn(4)OF5 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 46-63°. The Mn(3)-F(1) bond length is 2.15 Å. The Mn(3)-F(3) bond length is 2.08 Å. The Mn(3)-F(5) bond length is 2.20 Å. The Mn(3)-F(6) bond length is 2.18 Å. The Mn(3)-F(7) bond length is 2.09 Å. The Mn(3)-F(8) bond length is 2.21 Å. In the fourth Mn site, Mn(4) is bonded to one O(1), one F(2), one F(4), one F(5), one F(6), and one F(8) atom to form distorted MnOF5 pentagonal pyramids that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Mn(2)OF5 octahedra, edges with three equivalent Mn(1)OF5 octahedra, and  a faceface with one Mn(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-55°. The Mn(4)-O(1) bond length is 2.00 Å. The Mn(4)-F(2) bond length is 2.14 Å. The Mn(4)-F(4) bond length is 2.06 Å. The Mn(4)-F(5) bond length is 2.42 Å. The Mn(4)-F(6) bond length is 2.35 Å. The Mn(4)-F(8) bond length is 2.39 Å. O(1) is bonded to one Li(2), one Mn(1), one Mn(2), and one Mn(4) atom to form distorted OLiMn3 trigonal pyramids that share corners with two equivalent F(2)LiMn3 trigonal pyramids, corners with two equivalent F(5)LiMn3 trigonal pyramids,  an edgeedge with one F(1)Li2Mn2 trigonal pyramid, and  an edgeedge with one F(2)LiMn3 trigonal pyramid. There are eight inequivalent F sites. In the first F site, F(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(2), and one Mn(3) atom. In the second F site, F(4) is bonded in a 4-coordinate geometry to one Li(2), one Mn(1), one Mn(2), and one Mn(4) atom. In the third F site, F(5) is bonded to one Li(1), one Mn(1), one Mn(3), and one Mn(4) atom to form distorted FLiMn3 trigonal pyramids that share corners with two equivalent O(1)LiMn3 trigonal pyramids, corners with two equivalent F(1)Li2Mn2 trigonal pyramids, and corners with two equivalent F(2)LiMn3 trigonal pyramids. In the fourth F site, F(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(3), and one Mn(4) atom. In the fifth F site, F(7) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(2), and one Mn(3) atom. In the sixth F site, F(8) is bonded in a distorted see-saw-like geometry to one Li(1), one Mn(1), one Mn(3), and one Mn(4) atom. In the seventh F site, F(1) is bonded to one Li(1), one Li(2), one Mn(2), and one Mn(3) atom to form distorted FLi2Mn2 trigonal pyramids that share corners with two equivalent F(2)LiMn3 trigonal pyramids, corners with two equivalent F(5)LiMn3 trigonal pyramids, and  an edgeedge with one O(1)LiMn3 trigonal pyramid. In the eighth F site, F(2) 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 corners with two equivalent O(1)LiMn3 trigonal pyramids, corners with two equivalent F(1)Li2Mn2 trigonal pyramids, corners with two equivalent F(5)LiMn3 trigonal pyramids, and  an edgeedge with one O(1)LiMn3 trigonal pyramid.