Li3MnF5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one F(1), one F(3), and two equivalent F(4) atoms. In the second Li site, Li(2) is bonded to one F(1), one F(2), one F(3), and two equivalent F(4) atoms to form LiF5 trigonal bipyramids that share corners with four equivalent Mn(1)F6 octahedra and  an edgeedge with one Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 39-59°. Mn(1) is bonded to one F(1), one F(3), two equivalent F(2), and two equivalent F(4) atoms to form MnF6 octahedra that share corners with two equivalent Mn(1)F6 octahedra, corners with four equivalent Li(2)F5 trigonal bipyramids, and  an edgeedge with one Li(2)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 39°. There are four inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one Mn(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Mn(1) atoms. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one Mn(1) atom. In the fourth F site, F(4) is bonded in a distorted see-saw-like geometry to one Li(2), two equivalent Li(1), and one Mn(1) atom.
Li3MnF5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one F(1), one F(3), and two equivalent F(4) atoms. The Li(1)-F(1) bond length is 2.02 Å. The Li(1)-F(3) bond length is 1.89 Å. There is one shorter (1.91 Å) and one longer (1.93 Å) Li(1)-F(4) bond length. In the second Li site, Li(2) is bonded to one F(1), one F(2), one F(3), and two equivalent F(4) atoms to form LiF5 trigonal bipyramids that share corners with four equivalent Mn(1)F6 octahedra and  an edgeedge with one Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 39-59°. The Li(2)-F(1) bond length is 1.98 Å. The Li(2)-F(2) bond length is 1.94 Å. The Li(2)-F(3) bond length is 1.99 Å. Both Li(2)-F(4) bond lengths are 2.13 Å. Mn(1) is bonded to one F(1), one F(3), two equivalent F(2), and two equivalent F(4) atoms to form MnF6 octahedra that share corners with two equivalent Mn(1)F6 octahedra, corners with four equivalent Li(2)F5 trigonal bipyramids, and  an edgeedge with one Li(2)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 39°. The Mn(1)-F(1) bond length is 2.15 Å. The Mn(1)-F(3) bond length is 2.11 Å. There is one shorter (2.15 Å) and one longer (2.20 Å) Mn(1)-F(2) bond length. Both Mn(1)-F(4) bond lengths are 2.15 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one Mn(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Mn(1) atoms. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one Mn(1) atom. In the fourth F site, F(4) is bonded in a distorted see-saw-like geometry to one Li(2), two equivalent Li(1), and one Mn(1) atom.