Li2MnF4 is Aluminum carbonitride-like structured and crystallizes in the monoclinic C2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(3), one F(4), and two equivalent F(1) atoms to form LiF5 trigonal bipyramids that share corners with two equivalent Li(3)F6 octahedra, corners with three equivalent Li(2)F6 octahedra, corners with two equivalent Li(1)F5 trigonal bipyramids, corners with two equivalent Mn(1)F5 trigonal bipyramids,  an edgeedge with one Li(3)F6 octahedra, and edges with two equivalent Mn(1)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 38-71°. In the second Li site, Li(2) is bonded to two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form LiF6 octahedra that share corners with four equivalent Mn(1)F5 trigonal bipyramids, corners with six equivalent Li(1)F5 trigonal bipyramids, edges with two equivalent Li(3)F6 octahedra, and edges with two equivalent Mn(1)F5 trigonal bipyramids. In the third Li site, Li(3) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form distorted LiF6 octahedra that share corners with four equivalent Li(1)F5 trigonal bipyramids, corners with six equivalent Mn(1)F5 trigonal bipyramids, edges with two equivalent Li(2)F6 octahedra, and edges with two equivalent Li(1)F5 trigonal bipyramids. Mn(1) is bonded to one F(1), one F(3), one F(4), and two equivalent F(2) atoms to form distorted MnF5 trigonal bipyramids that share corners with two equivalent Li(2)F6 octahedra, corners with three equivalent Li(3)F6 octahedra, corners with two equivalent Li(1)F5 trigonal bipyramids, corners with two equivalent Mn(1)F5 trigonal bipyramids,  an edgeedge with one Li(2)F6 octahedra, and edges with two equivalent Li(1)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 48-72°. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted see-saw-like geometry to one Li(3), two equivalent Li(1), and one Mn(1) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), and two equivalent Mn(1) atoms to form distorted FLi2Mn2 trigonal pyramids that share corners with three equivalent F(4)Li3Mn tetrahedra, corners with three equivalent F(2)Li2Mn2 trigonal pyramids, corners with five equivalent F(3)Li3Mn trigonal pyramids, and  an edgeedge with one F(4)Li3Mn tetrahedra. In the third F site, F(3) is bonded to one Li(1), one Li(2), one Li(3), and one Mn(1) atom to form distorted FLi3Mn trigonal pyramids that share corners with two equivalent F(4)Li3Mn tetrahedra, corners with two equivalent F(3)Li3Mn trigonal pyramids, corners with five equivalent F(2)Li2Mn2 trigonal pyramids, and edges with two equivalent F(4)Li3Mn tetrahedra. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), one Li(3), and one Mn(1) atom to form FLi3Mn tetrahedra that share corners with two equivalent F(4)Li3Mn tetrahedra, corners with two equivalent F(3)Li3Mn trigonal pyramids, corners with three equivalent F(2)Li2Mn2 trigonal pyramids,  an edgeedge with one F(2)Li2Mn2 trigonal pyramid, and edges with two equivalent F(3)Li3Mn trigonal pyramids.
Li2MnF4 is Aluminum carbonitride-like structured and crystallizes in the monoclinic C2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(3), one F(4), and two equivalent F(1) atoms to form LiF5 trigonal bipyramids that share corners with two equivalent Li(3)F6 octahedra, corners with three equivalent Li(2)F6 octahedra, corners with two equivalent Li(1)F5 trigonal bipyramids, corners with two equivalent Mn(1)F5 trigonal bipyramids,  an edgeedge with one Li(3)F6 octahedra, and edges with two equivalent Mn(1)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 38-71°. The Li(1)-F(2) bond length is 1.93 Å. The Li(1)-F(3) bond length is 2.00 Å. The Li(1)-F(4) bond length is 2.15 Å. There is one shorter (1.91 Å) and one longer (2.09 Å) Li(1)-F(1) bond length. In the second Li site, Li(2) is bonded to two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form LiF6 octahedra that share corners with four equivalent Mn(1)F5 trigonal bipyramids, corners with six equivalent Li(1)F5 trigonal bipyramids, edges with two equivalent Li(3)F6 octahedra, and edges with two equivalent Mn(1)F5 trigonal bipyramids. Both Li(2)-F(2) bond lengths are 2.26 Å. Both Li(2)-F(3) bond lengths are 2.03 Å. Both Li(2)-F(4) bond lengths are 2.09 Å. In the third Li site, Li(3) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form distorted LiF6 octahedra that share corners with four equivalent Li(1)F5 trigonal bipyramids, corners with six equivalent Mn(1)F5 trigonal bipyramids, edges with two equivalent Li(2)F6 octahedra, and edges with two equivalent Li(1)F5 trigonal bipyramids. Both Li(3)-F(1) bond lengths are 2.26 Å. Both Li(3)-F(3) bond lengths are 2.12 Å. Both Li(3)-F(4) bond lengths are 2.11 Å. Mn(1) is bonded to one F(1), one F(3), one F(4), and two equivalent F(2) atoms to form distorted MnF5 trigonal bipyramids that share corners with two equivalent Li(2)F6 octahedra, corners with three equivalent Li(3)F6 octahedra, corners with two equivalent Li(1)F5 trigonal bipyramids, corners with two equivalent Mn(1)F5 trigonal bipyramids,  an edgeedge with one Li(2)F6 octahedra, and edges with two equivalent Li(1)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 48-72°. The Mn(1)-F(1) bond length is 2.06 Å. The Mn(1)-F(3) bond length is 2.10 Å. The Mn(1)-F(4) bond length is 2.10 Å. There is one shorter (2.06 Å) and one longer (2.20 Å) Mn(1)-F(2) bond length. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted see-saw-like geometry to one Li(3), two equivalent Li(1), and one Mn(1) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), and two equivalent Mn(1) atoms to form distorted FLi2Mn2 trigonal pyramids that share corners with three equivalent F(4)Li3Mn tetrahedra, corners with three equivalent F(2)Li2Mn2 trigonal pyramids, corners with five equivalent F(3)Li3Mn trigonal pyramids, and  an edgeedge with one F(4)Li3Mn tetrahedra. In the third F site, F(3) is bonded to one Li(1), one Li(2), one Li(3), and one Mn(1) atom to form distorted FLi3Mn trigonal pyramids that share corners with two equivalent F(4)Li3Mn tetrahedra, corners with two equivalent F(3)Li3Mn trigonal pyramids, corners with five equivalent F(2)Li2Mn2 trigonal pyramids, and edges with two equivalent F(4)Li3Mn tetrahedra. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), one Li(3), and one Mn(1) atom to form FLi3Mn tetrahedra that share corners with two equivalent F(4)Li3Mn tetrahedra, corners with two equivalent F(3)Li3Mn trigonal pyramids, corners with three equivalent F(2)Li2Mn2 trigonal pyramids,  an edgeedge with one F(2)Li2Mn2 trigonal pyramid, and edges with two equivalent F(3)Li3Mn trigonal pyramids.