LiMnOF2 crystallizes in the monoclinic Pc space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(2), one F(3), and one F(4) atom to form LiF4 tetrahedra that share  a cornercorner with one Li(4)O2F4 octahedra,  a cornercorner with one Mn(4)O2F4 octahedra, corners with two equivalent Mn(1)O3F3 octahedra, corners with two equivalent Mn(3)OF5 octahedra, and corners with two equivalent Li(3)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 49-63°. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(2), one O(4), one F(2), one F(4), one F(5), and one F(7) atom. In the third Li site, Li(3) is bonded to one O(1), one F(1), one F(3), and one F(7) atom to form LiOF3 tetrahedra that share corners with two equivalent Li(4)O2F4 octahedra, corners with two equivalent Mn(1)O3F3 octahedra, corners with two equivalent Mn(3)OF5 octahedra, and corners with two equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-72°. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one F(2), one F(5), one F(7), and one F(8) atom to form distorted LiO2F4 octahedra that share  a cornercorner with one Mn(4)O2F4 octahedra,  a cornercorner with one Li(1)F4 tetrahedra, corners with two equivalent Li(3)OF3 tetrahedra,  an edgeedge with one Mn(4)O2F4 octahedra,  an edgeedge with one Mn(3)OF5 octahedra, and edges with two equivalent Mn(1)O3F3 octahedra. The corner-sharing octahedral tilt angles are 59°. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(3), one F(1), one F(2), and one F(8) atom to form MnO3F3 octahedra that share corners with three equivalent Mn(4)O2F4 octahedra, corners with two equivalent Li(1)F4 tetrahedra, corners with two equivalent Li(3)OF3 tetrahedra, and edges with two equivalent Li(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 10-47°. In the second Mn site, Mn(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one F(5), and one F(6) atom. In the third Mn site, Mn(3) is bonded to one O(4), one F(3), one F(4), one F(5), one F(6), and one F(7) atom to form distorted MnOF5 octahedra that share  a cornercorner with one Mn(4)O2F4 octahedra, corners with two equivalent Li(1)F4 tetrahedra, corners with two equivalent Li(3)OF3 tetrahedra,  an edgeedge with one Li(4)O2F4 octahedra, and  an edgeedge with one Mn(4)O2F4 octahedra. The corner-sharing octahedral tilt angles are 63°. In the fourth Mn site, Mn(4) is bonded to one O(2), one O(3), one F(4), one F(5), one F(6), and one F(8) atom to form MnO2F4 octahedra that share  a cornercorner with one Li(4)O2F4 octahedra,  a cornercorner with one Mn(3)OF5 octahedra, corners with three equivalent Mn(1)O3F3 octahedra,  a cornercorner with one Li(1)F4 tetrahedra,  an edgeedge with one Li(4)O2F4 octahedra, and  an edgeedge with one Mn(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 10-63°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), one Li(4), one Mn(1), and one Mn(2) atom to form distorted OLi2Mn2 tetrahedra that share corners with two equivalent F(7)Li3Mn tetrahedra,  a cornercorner with one O(2)Li2Mn3 trigonal bipyramid,  an edgeedge with one F(2)Li3Mn tetrahedra, and  an edgeedge with one O(2)Li2Mn3 trigonal bipyramid. In the second O site, O(2) is bonded to one Li(2), one Li(4), one Mn(1), one Mn(2), and one Mn(4) atom to form OLi2Mn3 trigonal bipyramids that share  a cornercorner with one O(1)Li2Mn2 tetrahedra,  a cornercorner with one F(2)Li3Mn tetrahedra,  an edgeedge with one O(1)Li2Mn2 tetrahedra,  an edgeedge with one F(2)Li3Mn tetrahedra,  an edgeedge with one F(7)Li3Mn tetrahedra, and  an edgeedge with one F(4)Li2Mn2 trigonal pyramid. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(4) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(2), one Mn(2), and one Mn(3) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(1), one Li(3), and one Mn(1) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(4), and one Mn(1) atom to form FLi3Mn tetrahedra that share corners with two equivalent F(7)Li3Mn tetrahedra,  a cornercorner with one O(2)Li2Mn3 trigonal bipyramid, corners with two equivalent F(4)Li2Mn2 trigonal pyramids,  an edgeedge with one O(1)Li2Mn2 tetrahedra, and  an edgeedge with one O(2)Li2Mn3 trigonal bipyramid. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(1), one Li(3), and one Mn(3) atom. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), one Mn(3), and one Mn(4) atom to form distorted FLi2Mn2 trigonal pyramids that share corners with two equivalent F(2)Li3Mn tetrahedra,  an edgeedge with one F(7)Li3Mn tetrahedra, and  an edgeedge with one O(2)Li2Mn3 trigonal bipyramid. In the fifth F site, F(5) is bonded in a 5-coordinate geometry to one Li(2), one Li(4), one Mn(2), one Mn(3), and one Mn(4) atom. In the sixth F site, F(6) is bonded in a trigonal planar geometry to one Mn(2), one Mn(3), and one Mn(4) atom. In the seventh F site, F(7) is bonded to one Li(2), one Li(3), one Li(4), and one Mn(3) atom to form FLi3Mn tetrahedra that share corners with two equivalent O(1)Li2Mn2 tetrahedra, corners with two equivalent F(2)Li3Mn tetrahedra,  an edgeedge with one O(2)Li2Mn3 trigonal bipyramid, and  an edgeedge with one F(4)Li2Mn2 trigonal pyramid. In the eighth F site, F(8) is bonded in a trigonal planar geometry to one Li(4), one Mn(1), and one Mn(4) atom.
LiMnOF2 crystallizes in the monoclinic Pc space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(2), one F(3), and one F(4) atom to form LiF4 tetrahedra that share  a cornercorner with one Li(4)O2F4 octahedra,  a cornercorner with one Mn(4)O2F4 octahedra, corners with two equivalent Mn(1)O3F3 octahedra, corners with two equivalent Mn(3)OF5 octahedra, and corners with two equivalent Li(3)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 49-63°. The Li(1)-F(1) bond length is 1.91 Å. The Li(1)-F(2) bond length is 1.95 Å. The Li(1)-F(3) bond length is 1.88 Å. The Li(1)-F(4) bond length is 1.92 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(2), one O(4), one F(2), one F(4), one F(5), and one F(7) atom. The Li(2)-O(2) bond length is 2.20 Å. The Li(2)-O(4) bond length is 1.98 Å. The Li(2)-F(2) bond length is 2.01 Å. The Li(2)-F(4) bond length is 2.19 Å. The Li(2)-F(5) bond length is 2.53 Å. The Li(2)-F(7) bond length is 1.99 Å. In the third Li site, Li(3) is bonded to one O(1), one F(1), one F(3), and one F(7) atom to form LiOF3 tetrahedra that share corners with two equivalent Li(4)O2F4 octahedra, corners with two equivalent Mn(1)O3F3 octahedra, corners with two equivalent Mn(3)OF5 octahedra, and corners with two equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-72°. The Li(3)-O(1) bond length is 1.97 Å. The Li(3)-F(1) bond length is 1.88 Å. The Li(3)-F(3) bond length is 1.89 Å. The Li(3)-F(7) bond length is 1.94 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one F(2), one F(5), one F(7), and one F(8) atom to form distorted LiO2F4 octahedra that share  a cornercorner with one Mn(4)O2F4 octahedra,  a cornercorner with one Li(1)F4 tetrahedra, corners with two equivalent Li(3)OF3 tetrahedra,  an edgeedge with one Mn(4)O2F4 octahedra,  an edgeedge with one Mn(3)OF5 octahedra, and edges with two equivalent Mn(1)O3F3 octahedra. The corner-sharing octahedral tilt angles are 59°. The Li(4)-O(1) bond length is 2.23 Å. The Li(4)-O(2) bond length is 2.32 Å. The Li(4)-F(2) bond length is 2.02 Å. The Li(4)-F(5) bond length is 2.02 Å. The Li(4)-F(7) bond length is 2.14 Å. The Li(4)-F(8) bond length is 1.99 Å. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(3), one F(1), one F(2), and one F(8) atom to form MnO3F3 octahedra that share corners with three equivalent Mn(4)O2F4 octahedra, corners with two equivalent Li(1)F4 tetrahedra, corners with two equivalent Li(3)OF3 tetrahedra, and edges with two equivalent Li(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 10-47°. The Mn(1)-O(1) bond length is 1.85 Å. The Mn(1)-O(2) bond length is 2.24 Å. The Mn(1)-O(3) bond length is 2.05 Å. The Mn(1)-F(1) bond length is 1.96 Å. The Mn(1)-F(2) bond length is 2.05 Å. The Mn(1)-F(8) bond length is 2.03 Å. In the second Mn site, Mn(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one F(5), and one F(6) atom. The Mn(2)-O(1) bond length is 1.92 Å. The Mn(2)-O(2) bond length is 1.98 Å. The Mn(2)-O(3) bond length is 1.93 Å. The Mn(2)-O(4) bond length is 2.01 Å. The Mn(2)-F(5) bond length is 2.56 Å. The Mn(2)-F(6) bond length is 2.04 Å. In the third Mn site, Mn(3) is bonded to one O(4), one F(3), one F(4), one F(5), one F(6), and one F(7) atom to form distorted MnOF5 octahedra that share  a cornercorner with one Mn(4)O2F4 octahedra, corners with two equivalent Li(1)F4 tetrahedra, corners with two equivalent Li(3)OF3 tetrahedra,  an edgeedge with one Li(4)O2F4 octahedra, and  an edgeedge with one Mn(4)O2F4 octahedra. The corner-sharing octahedral tilt angles are 63°. The Mn(3)-O(4) bond length is 1.80 Å. The Mn(3)-F(3) bond length is 1.94 Å. The Mn(3)-F(4) bond length is 2.03 Å. The Mn(3)-F(5) bond length is 2.26 Å. The Mn(3)-F(6) bond length is 2.17 Å. The Mn(3)-F(7) bond length is 2.01 Å. In the fourth Mn site, Mn(4) is bonded to one O(2), one O(3), one F(4), one F(5), one F(6), and one F(8) atom to form MnO2F4 octahedra that share  a cornercorner with one Li(4)O2F4 octahedra,  a cornercorner with one Mn(3)OF5 octahedra, corners with three equivalent Mn(1)O3F3 octahedra,  a cornercorner with one Li(1)F4 tetrahedra,  an edgeedge with one Li(4)O2F4 octahedra, and  an edgeedge with one Mn(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 10-63°. The Mn(4)-O(2) bond length is 1.94 Å. The Mn(4)-O(3) bond length is 1.89 Å. The Mn(4)-F(4) bond length is 2.21 Å. The Mn(4)-F(5) bond length is 2.00 Å. The Mn(4)-F(6) bond length is 2.20 Å. The Mn(4)-F(8) bond length is 2.05 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), one Li(4), one Mn(1), and one Mn(2) atom to form distorted OLi2Mn2 tetrahedra that share corners with two equivalent F(7)Li3Mn tetrahedra,  a cornercorner with one O(2)Li2Mn3 trigonal bipyramid,  an edgeedge with one F(2)Li3Mn tetrahedra, and  an edgeedge with one O(2)Li2Mn3 trigonal bipyramid. In the second O site, O(2) is bonded to one Li(2), one Li(4), one Mn(1), one Mn(2), and one Mn(4) atom to form OLi2Mn3 trigonal bipyramids that share  a cornercorner with one O(1)Li2Mn2 tetrahedra,  a cornercorner with one F(2)Li3Mn tetrahedra,  an edgeedge with one O(1)Li2Mn2 tetrahedra,  an edgeedge with one F(2)Li3Mn tetrahedra,  an edgeedge with one F(7)Li3Mn tetrahedra, and  an edgeedge with one F(4)Li2Mn2 trigonal pyramid. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(4) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(2), one Mn(2), and one Mn(3) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(1), one Li(3), and one Mn(1) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(4), and one Mn(1) atom to form FLi3Mn tetrahedra that share corners with two equivalent F(7)Li3Mn tetrahedra,  a cornercorner with one O(2)Li2Mn3 trigonal bipyramid, corners with two equivalent F(4)Li2Mn2 trigonal pyramids,  an edgeedge with one O(1)Li2Mn2 tetrahedra, and  an edgeedge with one O(2)Li2Mn3 trigonal bipyramid. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(1), one Li(3), and one Mn(3) atom. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), one Mn(3), and one Mn(4) atom to form distorted FLi2Mn2 trigonal pyramids that share corners with two equivalent F(2)Li3Mn tetrahedra,  an edgeedge with one F(7)Li3Mn tetrahedra, and  an edgeedge with one O(2)Li2Mn3 trigonal bipyramid. In the fifth F site, F(5) is bonded in a 5-coordinate geometry to one Li(2), one Li(4), one Mn(2), one Mn(3), and one Mn(4) atom. In the sixth F site, F(6) is bonded in a trigonal planar geometry to one Mn(2), one Mn(3), and one Mn(4) atom. In the seventh F site, F(7) is bonded to one Li(2), one Li(3), one Li(4), and one Mn(3) atom to form FLi3Mn tetrahedra that share corners with two equivalent O(1)Li2Mn2 tetrahedra, corners with two equivalent F(2)Li3Mn tetrahedra,  an edgeedge with one O(2)Li2Mn3 trigonal bipyramid, and  an edgeedge with one F(4)Li2Mn2 trigonal pyramid. In the eighth F site, F(8) is bonded in a trigonal planar geometry to one Li(4), one Mn(1), and one Mn(4) atom.