LiMnOF2 is Ilmenite-derived structured and crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent F(2), and two equivalent F(3) atoms. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent F(1), and two equivalent F(4) atoms. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one F(1), one F(2), one F(3), and one F(4) atom to form edge-sharing MnO2F4 octahedra. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), one F(1), one F(2), one F(3), and one F(4) atom to form edge-sharing MnO2F4 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Mn(1), and one Mn(2) atom to form distorted OLi2Mn2 trigonal pyramids that share corners with four equivalent F(2)Li2Mn2 trigonal pyramids,  an edgeedge with one O(1)Li2Mn2 trigonal pyramid,  an edgeedge with one F(1)Li2Mn2 trigonal pyramid, and  an edgeedge with one F(2)Li2Mn2 trigonal pyramid. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to two equivalent Li(2), one Mn(1), and one Mn(2) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(2), one Mn(1), and one Mn(2) atom to form distorted FLi2Mn2 trigonal pyramids that share corners with two equivalent F(2)Li2Mn2 trigonal pyramids,  an edgeedge with one O(1)Li2Mn2 trigonal pyramid, and  an edgeedge with one F(1)Li2Mn2 trigonal pyramid. In the second F site, F(2) is bonded to two equivalent Li(1), one Mn(1), and one Mn(2) atom to form distorted FLi2Mn2 trigonal pyramids that share corners with two equivalent F(1)Li2Mn2 trigonal pyramids, corners with four equivalent O(1)Li2Mn2 trigonal pyramids,  an edgeedge with one O(1)Li2Mn2 trigonal pyramid, and  an edgeedge with one F(2)Li2Mn2 trigonal pyramid. In the third F site, F(3) is bonded in a 4-coordinate geometry to two equivalent Li(1), one Mn(1), and one Mn(2) atom. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to two equivalent Li(2), one Mn(1), and one Mn(2) atom.
LiMnOF2 is Ilmenite-derived structured and crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent F(2), and two equivalent F(3) atoms. There is one shorter (2.03 Å) and one longer (2.34 Å) Li(1)-O(1) bond length. There is one shorter (1.93 Å) and one longer (2.27 Å) Li(1)-F(2) bond length. There is one shorter (2.07 Å) and one longer (2.45 Å) Li(1)-F(3) bond length. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent F(1), and two equivalent F(4) atoms. There is one shorter (2.03 Å) and one longer (2.36 Å) Li(2)-O(2) bond length. There is one shorter (1.94 Å) and one longer (2.31 Å) Li(2)-F(1) bond length. There is one shorter (2.05 Å) and one longer (2.41 Å) Li(2)-F(4) bond length. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one F(1), one F(2), one F(3), and one F(4) atom to form edge-sharing MnO2F4 octahedra. The Mn(1)-O(1) bond length is 1.88 Å. The Mn(1)-O(2) bond length is 1.89 Å. The Mn(1)-F(1) bond length is 2.21 Å. The Mn(1)-F(2) bond length is 2.13 Å. The Mn(1)-F(3) bond length is 2.04 Å. The Mn(1)-F(4) bond length is 2.05 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), one F(1), one F(2), one F(3), and one F(4) atom to form edge-sharing MnO2F4 octahedra. The Mn(2)-O(1) bond length is 1.89 Å. The Mn(2)-O(2) bond length is 1.90 Å. The Mn(2)-F(1) bond length is 2.04 Å. The Mn(2)-F(2) bond length is 2.07 Å. The Mn(2)-F(3) bond length is 2.14 Å. The Mn(2)-F(4) bond length is 2.07 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Mn(1), and one Mn(2) atom to form distorted OLi2Mn2 trigonal pyramids that share corners with four equivalent F(2)Li2Mn2 trigonal pyramids,  an edgeedge with one O(1)Li2Mn2 trigonal pyramid,  an edgeedge with one F(1)Li2Mn2 trigonal pyramid, and  an edgeedge with one F(2)Li2Mn2 trigonal pyramid. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to two equivalent Li(2), one Mn(1), and one Mn(2) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(2), one Mn(1), and one Mn(2) atom to form distorted FLi2Mn2 trigonal pyramids that share corners with two equivalent F(2)Li2Mn2 trigonal pyramids,  an edgeedge with one O(1)Li2Mn2 trigonal pyramid, and  an edgeedge with one F(1)Li2Mn2 trigonal pyramid. In the second F site, F(2) is bonded to two equivalent Li(1), one Mn(1), and one Mn(2) atom to form distorted FLi2Mn2 trigonal pyramids that share corners with two equivalent F(1)Li2Mn2 trigonal pyramids, corners with four equivalent O(1)Li2Mn2 trigonal pyramids,  an edgeedge with one O(1)Li2Mn2 trigonal pyramid, and  an edgeedge with one F(2)Li2Mn2 trigonal pyramid. In the third F site, F(3) is bonded in a 4-coordinate geometry to two equivalent Li(1), one Mn(1), and one Mn(2) atom. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to two equivalent Li(2), one Mn(1), and one Mn(2) atom.