LiMn3OF5 crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(2), one F(3), one F(4), one F(5), and one F(9) atom. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(1), one F(1), one F(2), one F(6), and one F(8) atom. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one F(1), one F(10), one F(2), one F(3), and one F(5) atom to form a mixture of distorted edge and corner-sharing MnOF5 octahedra. The corner-sharing octahedral tilt angles range from 51-57°. In the second Mn site, Mn(2) is bonded to one O(1), one F(1), one F(10), one F(5), one F(8), and one F(9) atom to form a mixture of distorted edge and corner-sharing MnOF5 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 51-59°. In the third Mn site, Mn(3) is bonded in a 6-coordinate geometry to one O(2), one F(2), one F(3), one F(4), one F(6), and one F(7) atom. In the fourth Mn site, Mn(4) is bonded to one O(1), one F(1), one F(3), one F(5), one F(6), and one F(7) atom to form a mixture of distorted edge and corner-sharing MnOF5 octahedra. The corner-sharing octahedral tilt angles range from 53-57°. In the fifth Mn site, Mn(5) is bonded to one O(1), one F(4), one F(6), one F(7), one F(8), and one F(9) atom to form a mixture of distorted edge and corner-sharing MnOF5 octahedra. The corner-sharing octahedral tilt angles are 53°. In the sixth Mn site, Mn(6) is bonded to one O(2), one F(10), one F(2), one F(4), one F(8), and one F(9) atom to form a mixture of distorted edge and corner-sharing MnOF5 octahedra. The corner-sharing octahedral tilt angles range from 51-53°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Mn(2), one Mn(4), and one Mn(5) atom to form OLiMn3 tetrahedra that share  a cornercorner with one F(4)LiMn3 tetrahedra, corners with two equivalent F(5)LiMn3 tetrahedra,  a cornercorner with one F(1)LiMn3 trigonal pyramid,  a cornercorner with one F(2)LiMn3 trigonal pyramid,  a cornercorner with one F(3)LiMn3 trigonal pyramid,  a cornercorner with one F(6)LiMn3 trigonal pyramid,  an edgeedge with one F(1)LiMn3 trigonal pyramid,  an edgeedge with one F(6)LiMn3 trigonal pyramid, and  an edgeedge with one F(9)LiMn3 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one Mn(1), one Mn(3), and one Mn(6) atom to form OLiMn3 tetrahedra that share  a cornercorner with one F(4)LiMn3 tetrahedra, corners with two equivalent F(5)LiMn3 tetrahedra,  a cornercorner with one F(1)LiMn3 trigonal pyramid,  a cornercorner with one F(2)LiMn3 trigonal pyramid,  a cornercorner with one F(3)LiMn3 trigonal pyramid,  a cornercorner with one F(6)LiMn3 trigonal pyramid,  an edgeedge with one F(4)LiMn3 tetrahedra,  an edgeedge with one F(2)LiMn3 trigonal pyramid,  an edgeedge with one F(3)LiMn3 trigonal pyramid, and  an edgeedge with one F(9)LiMn3 trigonal pyramid. There are ten inequivalent F sites. In the first F site, F(1) 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 O(1)LiMn3 tetrahedra,  a cornercorner with one O(2)LiMn3 tetrahedra,  a cornercorner with one F(5)LiMn3 tetrahedra,  a cornercorner with one F(9)LiMn3 trigonal pyramid, corners with two equivalent F(2)LiMn3 trigonal pyramids, corners with two equivalent F(3)LiMn3 trigonal pyramids,  an edgeedge with one O(1)LiMn3 tetrahedra,  an edgeedge with one F(5)LiMn3 tetrahedra, and  an edgeedge with one F(6)LiMn3 trigonal pyramid. In the second F site, F(2) is bonded to one Li(2), one Mn(1), one Mn(3), and one Mn(6) atom to form distorted FLiMn3 trigonal pyramids that share  a cornercorner with one O(1)LiMn3 tetrahedra,  a cornercorner with one O(2)LiMn3 tetrahedra,  a cornercorner with one F(5)LiMn3 tetrahedra, corners with two equivalent F(4)LiMn3 tetrahedra,  a cornercorner with one F(9)LiMn3 trigonal pyramid, corners with two equivalent F(1)LiMn3 trigonal pyramids, corners with two equivalent F(6)LiMn3 trigonal pyramids,  an edgeedge with one O(2)LiMn3 tetrahedra, and  an edgeedge with one F(3)LiMn3 trigonal pyramid. In the third F site, F(3) is bonded to one Li(1), one Mn(1), one Mn(3), and one Mn(4) atom to form FLiMn3 trigonal pyramids that share  a cornercorner with one O(1)LiMn3 tetrahedra,  a cornercorner with one O(2)LiMn3 tetrahedra,  a cornercorner with one F(5)LiMn3 tetrahedra, corners with two equivalent F(4)LiMn3 tetrahedra,  a cornercorner with one F(9)LiMn3 trigonal pyramid, corners with two equivalent F(1)LiMn3 trigonal pyramids, corners with two equivalent F(6)LiMn3 trigonal pyramids,  an edgeedge with one O(2)LiMn3 tetrahedra,  an edgeedge with one F(5)LiMn3 tetrahedra, and  an edgeedge with one F(2)LiMn3 trigonal pyramid. In the fourth F site, F(4) is bonded to one Li(1), one Mn(3), one Mn(5), and one Mn(6) atom to form distorted FLiMn3 tetrahedra that share  a cornercorner with one O(1)LiMn3 tetrahedra,  a cornercorner with one O(2)LiMn3 tetrahedra,  a cornercorner with one F(5)LiMn3 tetrahedra,  a cornercorner with one F(9)LiMn3 trigonal pyramid, corners with two equivalent F(2)LiMn3 trigonal pyramids, corners with two equivalent F(3)LiMn3 trigonal pyramids,  an edgeedge with one O(2)LiMn3 tetrahedra,  an edgeedge with one F(6)LiMn3 trigonal pyramid, and  an edgeedge with one F(9)LiMn3 trigonal pyramid. In the fifth F site, F(5) is bonded to one Li(1), one Mn(1), one Mn(2), and one Mn(4) atom to form FLiMn3 tetrahedra that share  a cornercorner with one F(4)LiMn3 tetrahedra, corners with two equivalent O(1)LiMn3 tetrahedra, corners with two equivalent O(2)LiMn3 tetrahedra,  a cornercorner with one F(1)LiMn3 trigonal pyramid,  a cornercorner with one F(2)LiMn3 trigonal pyramid,  a cornercorner with one F(3)LiMn3 trigonal pyramid,  a cornercorner with one F(6)LiMn3 trigonal pyramid, corners with two equivalent F(9)LiMn3 trigonal pyramids,  an edgeedge with one F(1)LiMn3 trigonal pyramid, and  an edgeedge with one F(3)LiMn3 trigonal pyramid. In the sixth F site, F(6) is bonded to one Li(2), one Mn(3), one Mn(4), and one Mn(5) atom to form FLiMn3 trigonal pyramids that share  a cornercorner with one O(1)LiMn3 tetrahedra,  a cornercorner with one O(2)LiMn3 tetrahedra,  a cornercorner with one F(5)LiMn3 tetrahedra,  a cornercorner with one F(9)LiMn3 trigonal pyramid, corners with two equivalent F(2)LiMn3 trigonal pyramids, corners with two equivalent F(3)LiMn3 trigonal pyramids,  an edgeedge with one O(1)LiMn3 tetrahedra,  an edgeedge with one F(4)LiMn3 tetrahedra, and  an edgeedge with one F(1)LiMn3 trigonal pyramid. In the seventh F site, F(7) is bonded in a 3-coordinate geometry to one Mn(3), one Mn(4), and one Mn(5) atom. In the eighth F site, F(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Mn(2), one Mn(5), and one Mn(6) atom. In the ninth F site, F(9) is bonded to one Li(1), one Mn(2), one Mn(5), and one Mn(6) atom to form FLiMn3 trigonal pyramids that share  a cornercorner with one F(4)LiMn3 tetrahedra, corners with two equivalent F(5)LiMn3 tetrahedra,  a cornercorner with one F(1)LiMn3 trigonal pyramid,  a cornercorner with one F(2)LiMn3 trigonal pyramid,  a cornercorner with one F(3)LiMn3 trigonal pyramid,  a cornercorner with one F(6)LiMn3 trigonal pyramid,  an edgeedge with one O(1)LiMn3 tetrahedra,  an edgeedge with one O(2)LiMn3 tetrahedra, and  an edgeedge with one F(4)LiMn3 tetrahedra. In the tenth F site, F(10) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(2), and one Mn(6) atom.
LiMn3OF5 crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(2), one F(3), one F(4), one F(5), and one F(9) atom. The Li(1)-O(2) bond length is 1.99 Å. The Li(1)-F(3) bond length is 2.17 Å. The Li(1)-F(4) bond length is 2.09 Å. The Li(1)-F(5) bond length is 2.38 Å. The Li(1)-F(9) bond length is 2.13 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(1), one F(1), one F(2), one F(6), and one F(8) atom. The Li(2)-O(1) bond length is 1.98 Å. The Li(2)-F(1) bond length is 2.01 Å. The Li(2)-F(2) bond length is 2.04 Å. The Li(2)-F(6) bond length is 2.26 Å. The Li(2)-F(8) bond length is 2.28 Å. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one F(1), one F(10), one F(2), one F(3), and one F(5) atom to form a mixture of distorted edge and corner-sharing MnOF5 octahedra. The corner-sharing octahedral tilt angles range from 51-57°. The Mn(1)-O(2) bond length is 2.02 Å. The Mn(1)-F(1) bond length is 2.18 Å. The Mn(1)-F(10) bond length is 2.22 Å. The Mn(1)-F(2) bond length is 2.32 Å. The Mn(1)-F(3) bond length is 2.19 Å. The Mn(1)-F(5) bond length is 2.23 Å. In the second Mn site, Mn(2) is bonded to one O(1), one F(1), one F(10), one F(5), one F(8), and one F(9) atom to form a mixture of distorted edge and corner-sharing MnOF5 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 51-59°. The Mn(2)-O(1) bond length is 2.06 Å. The Mn(2)-F(1) bond length is 2.26 Å. The Mn(2)-F(10) bond length is 2.20 Å. The Mn(2)-F(5) bond length is 2.19 Å. The Mn(2)-F(8) bond length is 2.25 Å. The Mn(2)-F(9) bond length is 2.17 Å. In the third Mn site, Mn(3) is bonded in a 6-coordinate geometry to one O(2), one F(2), one F(3), one F(4), one F(6), and one F(7) atom. The Mn(3)-O(2) bond length is 2.04 Å. The Mn(3)-F(2) bond length is 2.17 Å. The Mn(3)-F(3) bond length is 2.26 Å. The Mn(3)-F(4) bond length is 2.31 Å. The Mn(3)-F(6) bond length is 2.15 Å. The Mn(3)-F(7) bond length is 2.20 Å. In the fourth Mn site, Mn(4) is bonded to one O(1), one F(1), one F(3), one F(5), one F(6), and one F(7) atom to form a mixture of distorted edge and corner-sharing MnOF5 octahedra. The corner-sharing octahedral tilt angles range from 53-57°. The Mn(4)-O(1) bond length is 2.03 Å. The Mn(4)-F(1) bond length is 2.28 Å. The Mn(4)-F(3) bond length is 2.17 Å. The Mn(4)-F(5) bond length is 2.25 Å. The Mn(4)-F(6) bond length is 2.24 Å. The Mn(4)-F(7) bond length is 2.23 Å. In the fifth Mn site, Mn(5) is bonded to one O(1), one F(4), one F(6), one F(7), one F(8), and one F(9) atom to form a mixture of distorted edge and corner-sharing MnOF5 octahedra. The corner-sharing octahedral tilt angles are 53°. The Mn(5)-O(1) bond length is 2.04 Å. The Mn(5)-F(4) bond length is 2.22 Å. The Mn(5)-F(6) bond length is 2.25 Å. The Mn(5)-F(7) bond length is 2.19 Å. The Mn(5)-F(8) bond length is 2.15 Å. The Mn(5)-F(9) bond length is 2.32 Å. In the sixth Mn site, Mn(6) is bonded to one O(2), one F(10), one F(2), one F(4), one F(8), and one F(9) atom to form a mixture of distorted edge and corner-sharing MnOF5 octahedra. The corner-sharing octahedral tilt angles range from 51-53°. The Mn(6)-O(2) bond length is 2.05 Å. The Mn(6)-F(10) bond length is 2.14 Å. The Mn(6)-F(2) bond length is 2.24 Å. The Mn(6)-F(4) bond length is 2.23 Å. The Mn(6)-F(8) bond length is 2.24 Å. The Mn(6)-F(9) bond length is 2.22 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Mn(2), one Mn(4), and one Mn(5) atom to form OLiMn3 tetrahedra that share  a cornercorner with one F(4)LiMn3 tetrahedra, corners with two equivalent F(5)LiMn3 tetrahedra,  a cornercorner with one F(1)LiMn3 trigonal pyramid,  a cornercorner with one F(2)LiMn3 trigonal pyramid,  a cornercorner with one F(3)LiMn3 trigonal pyramid,  a cornercorner with one F(6)LiMn3 trigonal pyramid,  an edgeedge with one F(1)LiMn3 trigonal pyramid,  an edgeedge with one F(6)LiMn3 trigonal pyramid, and  an edgeedge with one F(9)LiMn3 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one Mn(1), one Mn(3), and one Mn(6) atom to form OLiMn3 tetrahedra that share  a cornercorner with one F(4)LiMn3 tetrahedra, corners with two equivalent F(5)LiMn3 tetrahedra,  a cornercorner with one F(1)LiMn3 trigonal pyramid,  a cornercorner with one F(2)LiMn3 trigonal pyramid,  a cornercorner with one F(3)LiMn3 trigonal pyramid,  a cornercorner with one F(6)LiMn3 trigonal pyramid,  an edgeedge with one F(4)LiMn3 tetrahedra,  an edgeedge with one F(2)LiMn3 trigonal pyramid,  an edgeedge with one F(3)LiMn3 trigonal pyramid, and  an edgeedge with one F(9)LiMn3 trigonal pyramid. There are ten inequivalent F sites. In the first F site, F(1) 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 O(1)LiMn3 tetrahedra,  a cornercorner with one O(2)LiMn3 tetrahedra,  a cornercorner with one F(5)LiMn3 tetrahedra,  a cornercorner with one F(9)LiMn3 trigonal pyramid, corners with two equivalent F(2)LiMn3 trigonal pyramids, corners with two equivalent F(3)LiMn3 trigonal pyramids,  an edgeedge with one O(1)LiMn3 tetrahedra,  an edgeedge with one F(5)LiMn3 tetrahedra, and  an edgeedge with one F(6)LiMn3 trigonal pyramid. In the second F site, F(2) is bonded to one Li(2), one Mn(1), one Mn(3), and one Mn(6) atom to form distorted FLiMn3 trigonal pyramids that share  a cornercorner with one O(1)LiMn3 tetrahedra,  a cornercorner with one O(2)LiMn3 tetrahedra,  a cornercorner with one F(5)LiMn3 tetrahedra, corners with two equivalent F(4)LiMn3 tetrahedra,  a cornercorner with one F(9)LiMn3 trigonal pyramid, corners with two equivalent F(1)LiMn3 trigonal pyramids, corners with two equivalent F(6)LiMn3 trigonal pyramids,  an edgeedge with one O(2)LiMn3 tetrahedra, and  an edgeedge with one F(3)LiMn3 trigonal pyramid. In the third F site, F(3) is bonded to one Li(1), one Mn(1), one Mn(3), and one Mn(4) atom to form FLiMn3 trigonal pyramids that share  a cornercorner with one O(1)LiMn3 tetrahedra,  a cornercorner with one O(2)LiMn3 tetrahedra,  a cornercorner with one F(5)LiMn3 tetrahedra, corners with two equivalent F(4)LiMn3 tetrahedra,  a cornercorner with one F(9)LiMn3 trigonal pyramid, corners with two equivalent F(1)LiMn3 trigonal pyramids, corners with two equivalent F(6)LiMn3 trigonal pyramids,  an edgeedge with one O(2)LiMn3 tetrahedra,  an edgeedge with one F(5)LiMn3 tetrahedra, and  an edgeedge with one F(2)LiMn3 trigonal pyramid. In the fourth F site, F(4) is bonded to one Li(1), one Mn(3), one Mn(5), and one Mn(6) atom to form distorted FLiMn3 tetrahedra that share  a cornercorner with one O(1)LiMn3 tetrahedra,  a cornercorner with one O(2)LiMn3 tetrahedra,  a cornercorner with one F(5)LiMn3 tetrahedra,  a cornercorner with one F(9)LiMn3 trigonal pyramid, corners with two equivalent F(2)LiMn3 trigonal pyramids, corners with two equivalent F(3)LiMn3 trigonal pyramids,  an edgeedge with one O(2)LiMn3 tetrahedra,  an edgeedge with one F(6)LiMn3 trigonal pyramid, and  an edgeedge with one F(9)LiMn3 trigonal pyramid. In the fifth F site, F(5) is bonded to one Li(1), one Mn(1), one Mn(2), and one Mn(4) atom to form FLiMn3 tetrahedra that share  a cornercorner with one F(4)LiMn3 tetrahedra, corners with two equivalent O(1)LiMn3 tetrahedra, corners with two equivalent O(2)LiMn3 tetrahedra,  a cornercorner with one F(1)LiMn3 trigonal pyramid,  a cornercorner with one F(2)LiMn3 trigonal pyramid,  a cornercorner with one F(3)LiMn3 trigonal pyramid,  a cornercorner with one F(6)LiMn3 trigonal pyramid, corners with two equivalent F(9)LiMn3 trigonal pyramids,  an edgeedge with one F(1)LiMn3 trigonal pyramid, and  an edgeedge with one F(3)LiMn3 trigonal pyramid. In the sixth F site, F(6) is bonded to one Li(2), one Mn(3), one Mn(4), and one Mn(5) atom to form FLiMn3 trigonal pyramids that share  a cornercorner with one O(1)LiMn3 tetrahedra,  a cornercorner with one O(2)LiMn3 tetrahedra,  a cornercorner with one F(5)LiMn3 tetrahedra,  a cornercorner with one F(9)LiMn3 trigonal pyramid, corners with two equivalent F(2)LiMn3 trigonal pyramids, corners with two equivalent F(3)LiMn3 trigonal pyramids,  an edgeedge with one O(1)LiMn3 tetrahedra,  an edgeedge with one F(4)LiMn3 tetrahedra, and  an edgeedge with one F(1)LiMn3 trigonal pyramid. In the seventh F site, F(7) is bonded in a 3-coordinate geometry to one Mn(3), one Mn(4), and one Mn(5) atom. In the eighth F site, F(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Mn(2), one Mn(5), and one Mn(6) atom. In the ninth F site, F(9) is bonded to one Li(1), one Mn(2), one Mn(5), and one Mn(6) atom to form FLiMn3 trigonal pyramids that share  a cornercorner with one F(4)LiMn3 tetrahedra, corners with two equivalent F(5)LiMn3 tetrahedra,  a cornercorner with one F(1)LiMn3 trigonal pyramid,  a cornercorner with one F(2)LiMn3 trigonal pyramid,  a cornercorner with one F(3)LiMn3 trigonal pyramid,  a cornercorner with one F(6)LiMn3 trigonal pyramid,  an edgeedge with one O(1)LiMn3 tetrahedra,  an edgeedge with one O(2)LiMn3 tetrahedra, and  an edgeedge with one F(4)LiMn3 tetrahedra. In the tenth F site, F(10) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(2), and one Mn(6) atom.