LiMn6(OF2)4 crystallizes in the triclinic P1 space group. Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one F(4), one F(5), 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 O(4), one F(2), one F(3), one F(5), and one F(8) atom to form MnO2F4 octahedra that share corners with two equivalent Mn(4)O2F4 octahedra, corners with two equivalent Mn(5)O2F4 octahedra, corners with four equivalent Mn(6)OF5 octahedra, and  an edgeedge with one Mn(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 40-67°. In the second Mn site, Mn(2) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), one F(4), and one F(5) atom. In the third Mn site, Mn(3) is bonded to one O(3), one O(4), one F(1), one F(3), one F(4), and one F(7) atom to form MnO2F4 octahedra that share corners with two equivalent Mn(4)O2F4 octahedra, corners with two equivalent Mn(6)OF5 octahedra, corners with four equivalent Mn(5)O2F4 octahedra, and  an edgeedge with one Mn(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 42-55°. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(2), one F(1), one F(4), one F(6), and one F(8) atom to form MnO2F4 octahedra that share corners with two equivalent Mn(1)O2F4 octahedra, corners with two equivalent Mn(3)O2F4 octahedra,  an edgeedge with one Mn(5)O2F4 octahedra, and  an edgeedge with one Mn(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 40-55°. In the fifth Mn site, Mn(5) is bonded to one O(3), one O(4), one F(1), one F(2), one F(6), and one F(7) atom to form MnO2F4 octahedra that share corners with two equivalent Mn(1)O2F4 octahedra, corners with four equivalent Mn(3)O2F4 octahedra,  an edgeedge with one Mn(4)O2F4 octahedra, and  an edgeedge with one Mn(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 42-57°. In the sixth Mn site, Mn(6) is bonded to one O(1), one F(2), one F(3), one F(5), one F(7), and one F(8) atom to form a mixture of corner and edge-sharing MnOF5 octahedra. The corner-sharing octahedral tilt angles range from 46-67°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Mn(2), one Mn(4), and one Mn(6) atom to form OLiMn3 trigonal pyramids that share  a cornercorner with one O(2)LiMn3 trigonal pyramid,  a cornercorner with one F(8)LiMn3 trigonal pyramid,  an edgeedge with one O(2)LiMn3 trigonal pyramid, and  an edgeedge with one F(8)LiMn3 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one Mn(1), one Mn(2), and one Mn(4) atom to form distorted OLiMn3 trigonal pyramids that share  a cornercorner with one O(1)LiMn3 trigonal pyramid,  a cornercorner with one F(8)LiMn3 trigonal pyramid,  an edgeedge with one O(1)LiMn3 trigonal pyramid, and  an edgeedge with one F(8)LiMn3 trigonal pyramid. In the third O site, O(3) is bonded in a trigonal planar geometry to one Mn(2), one Mn(3), and one Mn(5) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Mn(1), one Mn(3), and one Mn(5) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Mn(3), one Mn(4), and one Mn(5) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Mn(1), one Mn(5), and one Mn(6) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(3), and one Mn(6) atom. In the fourth F site, F(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(2), one Mn(3), and one Mn(4) atom. In the fifth F site, F(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(2), and one Mn(6) atom. In the sixth F site, F(6) is bonded in a water-like geometry to one Mn(4) and one Mn(5) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Mn(3), one Mn(5), and one Mn(6) atom. In the eighth F site, F(8) is bonded to one Li(1), one Mn(1), one Mn(4), and one Mn(6) atom to form distorted FLiMn3 trigonal pyramids that share  a cornercorner with one O(1)LiMn3 trigonal pyramid,  a cornercorner with one O(2)LiMn3 trigonal pyramid,  an edgeedge with one O(1)LiMn3 trigonal pyramid, and  an edgeedge with one O(2)LiMn3 trigonal pyramid.
LiMn6(OF2)4 crystallizes in the triclinic P1 space group. Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one F(4), one F(5), and one F(8) atom. The Li(1)-O(1) bond length is 1.90 Å. The Li(1)-O(2) bond length is 1.98 Å. The Li(1)-F(4) bond length is 1.99 Å. The Li(1)-F(5) bond length is 2.19 Å. The Li(1)-F(8) bond length is 1.85 Å. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(4), one F(2), one F(3), one F(5), and one F(8) atom to form MnO2F4 octahedra that share corners with two equivalent Mn(4)O2F4 octahedra, corners with two equivalent Mn(5)O2F4 octahedra, corners with four equivalent Mn(6)OF5 octahedra, and  an edgeedge with one Mn(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 40-67°. The Mn(1)-O(2) bond length is 2.15 Å. The Mn(1)-O(4) bond length is 2.05 Å. The Mn(1)-F(2) bond length is 2.14 Å. The Mn(1)-F(3) bond length is 2.16 Å. The Mn(1)-F(5) bond length is 2.14 Å. The Mn(1)-F(8) bond length is 2.22 Å. In the second Mn site, Mn(2) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), one F(4), and one F(5) atom. The Mn(2)-O(1) bond length is 2.03 Å. The Mn(2)-O(2) bond length is 2.00 Å. The Mn(2)-O(3) bond length is 1.96 Å. The Mn(2)-F(4) bond length is 2.54 Å. The Mn(2)-F(5) bond length is 2.28 Å. In the third Mn site, Mn(3) is bonded to one O(3), one O(4), one F(1), one F(3), one F(4), and one F(7) atom to form MnO2F4 octahedra that share corners with two equivalent Mn(4)O2F4 octahedra, corners with two equivalent Mn(6)OF5 octahedra, corners with four equivalent Mn(5)O2F4 octahedra, and  an edgeedge with one Mn(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 42-55°. The Mn(3)-O(3) bond length is 2.03 Å. The Mn(3)-O(4) bond length is 2.03 Å. The Mn(3)-F(1) bond length is 2.15 Å. The Mn(3)-F(3) bond length is 2.10 Å. The Mn(3)-F(4) bond length is 2.17 Å. The Mn(3)-F(7) bond length is 2.17 Å. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(2), one F(1), one F(4), one F(6), and one F(8) atom to form MnO2F4 octahedra that share corners with two equivalent Mn(1)O2F4 octahedra, corners with two equivalent Mn(3)O2F4 octahedra,  an edgeedge with one Mn(5)O2F4 octahedra, and  an edgeedge with one Mn(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 40-55°. The Mn(4)-O(1) bond length is 1.91 Å. The Mn(4)-O(2) bond length is 1.91 Å. The Mn(4)-F(1) bond length is 2.18 Å. The Mn(4)-F(4) bond length is 2.05 Å. The Mn(4)-F(6) bond length is 2.03 Å. The Mn(4)-F(8) bond length is 2.26 Å. In the fifth Mn site, Mn(5) is bonded to one O(3), one O(4), one F(1), one F(2), one F(6), and one F(7) atom to form MnO2F4 octahedra that share corners with two equivalent Mn(1)O2F4 octahedra, corners with four equivalent Mn(3)O2F4 octahedra,  an edgeedge with one Mn(4)O2F4 octahedra, and  an edgeedge with one Mn(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 42-57°. The Mn(5)-O(3) bond length is 2.00 Å. The Mn(5)-O(4) bond length is 1.95 Å. The Mn(5)-F(1) bond length is 2.13 Å. The Mn(5)-F(2) bond length is 2.10 Å. The Mn(5)-F(6) bond length is 2.11 Å. The Mn(5)-F(7) bond length is 2.12 Å. In the sixth Mn site, Mn(6) is bonded to one O(1), one F(2), one F(3), one F(5), one F(7), and one F(8) atom to form a mixture of corner and edge-sharing MnOF5 octahedra. The corner-sharing octahedral tilt angles range from 46-67°. The Mn(6)-O(1) bond length is 2.08 Å. The Mn(6)-F(2) bond length is 2.13 Å. The Mn(6)-F(3) bond length is 2.09 Å. The Mn(6)-F(5) bond length is 2.13 Å. The Mn(6)-F(7) bond length is 2.18 Å. The Mn(6)-F(8) bond length is 2.17 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Mn(2), one Mn(4), and one Mn(6) atom to form OLiMn3 trigonal pyramids that share  a cornercorner with one O(2)LiMn3 trigonal pyramid,  a cornercorner with one F(8)LiMn3 trigonal pyramid,  an edgeedge with one O(2)LiMn3 trigonal pyramid, and  an edgeedge with one F(8)LiMn3 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one Mn(1), one Mn(2), and one Mn(4) atom to form distorted OLiMn3 trigonal pyramids that share  a cornercorner with one O(1)LiMn3 trigonal pyramid,  a cornercorner with one F(8)LiMn3 trigonal pyramid,  an edgeedge with one O(1)LiMn3 trigonal pyramid, and  an edgeedge with one F(8)LiMn3 trigonal pyramid. In the third O site, O(3) is bonded in a trigonal planar geometry to one Mn(2), one Mn(3), and one Mn(5) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Mn(1), one Mn(3), and one Mn(5) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Mn(3), one Mn(4), and one Mn(5) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Mn(1), one Mn(5), and one Mn(6) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(3), and one Mn(6) atom. In the fourth F site, F(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(2), one Mn(3), and one Mn(4) atom. In the fifth F site, F(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(2), and one Mn(6) atom. In the sixth F site, F(6) is bonded in a water-like geometry to one Mn(4) and one Mn(5) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Mn(3), one Mn(5), and one Mn(6) atom. In the eighth F site, F(8) is bonded to one Li(1), one Mn(1), one Mn(4), and one Mn(6) atom to form distorted FLiMn3 trigonal pyramids that share  a cornercorner with one O(1)LiMn3 trigonal pyramid,  a cornercorner with one O(2)LiMn3 trigonal pyramid,  an edgeedge with one O(1)LiMn3 trigonal pyramid, and  an edgeedge with one O(2)LiMn3 trigonal pyramid.