Li2MnF4 crystallizes in the orthorhombic Imm2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(2), two equivalent F(3), and two equivalent F(4) atoms to form edge-sharing LiF6 octahedra. In the second Li site, Li(2) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms to form edge-sharing LiF6 octahedra. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 6-coordinate geometry to two equivalent F(1), two equivalent F(2), and two equivalent F(4) atoms. In the second Mn site, Mn(2) is bonded in a 4-coordinate geometry to two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), two equivalent Li(2), and one Mn(1) atom to form distorted FLi3Mn trigonal pyramids that share corners with seven equivalent F(2)Li3Mn2 trigonal bipyramids,  a cornercorner with one F(1)Li3Mn trigonal pyramid, corners with two equivalent F(4)Li3Mn2 trigonal pyramids, corners with four equivalent F(3)Li3Mn trigonal pyramids,  an edgeedge with one F(1)Li3Mn trigonal pyramid, and edges with two equivalent F(4)Li3Mn2 trigonal pyramids. In the second F site, F(2) is bonded to one Li(1), two equivalent Li(2), one Mn(1), and one Mn(2) atom to form distorted FLi3Mn2 trigonal bipyramids that share  a cornercorner with one F(2)Li3Mn2 trigonal bipyramid, corners with two equivalent F(3)Li3Mn trigonal pyramids, corners with seven equivalent F(1)Li3Mn trigonal pyramids, edges with two equivalent F(3)Li3Mn trigonal pyramids, edges with four equivalent F(4)Li3Mn2 trigonal pyramids, and  a faceface with one F(2)Li3Mn2 trigonal bipyramid. In the third F site, F(3) is bonded to one Li(2), two equivalent Li(1), and one Mn(2) atom to form FLi3Mn trigonal pyramids that share corners with two equivalent F(2)Li3Mn2 trigonal bipyramids,  a cornercorner with one F(3)Li3Mn trigonal pyramid, corners with four equivalent F(1)Li3Mn trigonal pyramids, corners with seven equivalent F(4)Li3Mn2 trigonal pyramids, edges with two equivalent F(2)Li3Mn2 trigonal bipyramids, and  an edgeedge with one F(3)Li3Mn trigonal pyramid. In the fourth F site, F(4) is bonded to one Li(2), two equivalent Li(1), one Mn(1), and one Mn(2) atom to form distorted FLi3Mn2 trigonal pyramids that share  a cornercorner with one F(4)Li3Mn2 trigonal pyramid, corners with two equivalent F(1)Li3Mn trigonal pyramids, corners with seven equivalent F(3)Li3Mn trigonal pyramids, edges with four equivalent F(2)Li3Mn2 trigonal bipyramids, edges with two equivalent F(1)Li3Mn trigonal pyramids, and  a faceface with one F(4)Li3Mn2 trigonal pyramid.
Li2MnF4 crystallizes in the orthorhombic Imm2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(2), two equivalent F(3), and two equivalent F(4) atoms to form edge-sharing LiF6 octahedra. The Li(1)-F(1) bond length is 1.99 Å. The Li(1)-F(2) bond length is 2.03 Å. Both Li(1)-F(3) bond lengths are 2.08 Å. Both Li(1)-F(4) bond lengths are 2.16 Å. In the second Li site, Li(2) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms to form edge-sharing LiF6 octahedra. The Li(2)-F(3) bond length is 1.95 Å. The Li(2)-F(4) bond length is 2.00 Å. Both Li(2)-F(1) bond lengths are 2.07 Å. Both Li(2)-F(2) bond lengths are 2.20 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 6-coordinate geometry to two equivalent F(1), two equivalent F(2), and two equivalent F(4) atoms. Both Mn(1)-F(1) bond lengths are 2.10 Å. Both Mn(1)-F(2) bond lengths are 2.45 Å. Both Mn(1)-F(4) bond lengths are 2.07 Å. In the second Mn site, Mn(2) is bonded in a 4-coordinate geometry to two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. Both Mn(2)-F(2) bond lengths are 2.06 Å. Both Mn(2)-F(3) bond lengths are 2.08 Å. Both Mn(2)-F(4) bond lengths are 2.62 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), two equivalent Li(2), and one Mn(1) atom to form distorted FLi3Mn trigonal pyramids that share corners with seven equivalent F(2)Li3Mn2 trigonal bipyramids,  a cornercorner with one F(1)Li3Mn trigonal pyramid, corners with two equivalent F(4)Li3Mn2 trigonal pyramids, corners with four equivalent F(3)Li3Mn trigonal pyramids,  an edgeedge with one F(1)Li3Mn trigonal pyramid, and edges with two equivalent F(4)Li3Mn2 trigonal pyramids. In the second F site, F(2) is bonded to one Li(1), two equivalent Li(2), one Mn(1), and one Mn(2) atom to form distorted FLi3Mn2 trigonal bipyramids that share  a cornercorner with one F(2)Li3Mn2 trigonal bipyramid, corners with two equivalent F(3)Li3Mn trigonal pyramids, corners with seven equivalent F(1)Li3Mn trigonal pyramids, edges with two equivalent F(3)Li3Mn trigonal pyramids, edges with four equivalent F(4)Li3Mn2 trigonal pyramids, and  a faceface with one F(2)Li3Mn2 trigonal bipyramid. In the third F site, F(3) is bonded to one Li(2), two equivalent Li(1), and one Mn(2) atom to form FLi3Mn trigonal pyramids that share corners with two equivalent F(2)Li3Mn2 trigonal bipyramids,  a cornercorner with one F(3)Li3Mn trigonal pyramid, corners with four equivalent F(1)Li3Mn trigonal pyramids, corners with seven equivalent F(4)Li3Mn2 trigonal pyramids, edges with two equivalent F(2)Li3Mn2 trigonal bipyramids, and  an edgeedge with one F(3)Li3Mn trigonal pyramid. In the fourth F site, F(4) is bonded to one Li(2), two equivalent Li(1), one Mn(1), and one Mn(2) atom to form distorted FLi3Mn2 trigonal pyramids that share  a cornercorner with one F(4)Li3Mn2 trigonal pyramid, corners with two equivalent F(1)Li3Mn trigonal pyramids, corners with seven equivalent F(3)Li3Mn trigonal pyramids, edges with four equivalent F(2)Li3Mn2 trigonal bipyramids, edges with two equivalent F(1)Li3Mn trigonal pyramids, and  a faceface with one F(4)Li3Mn2 trigonal pyramid.