Li3MnF5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(4), and two equivalent F(2) atoms to form distorted LiF4 tetrahedra that share corners with two equivalent Li(2)F4 tetrahedra, corners with four equivalent Mn(1)F5 trigonal bipyramids, and edges with two equivalent Li(2)F4 tetrahedra. In the second Li site, Li(2) 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(1)F4 tetrahedra,  a cornercorner with one Li(2)F4 tetrahedra, corners with four equivalent Mn(1)F5 trigonal bipyramids,  an edgeedge with one Li(1)F4 tetrahedra, and  an edgeedge with one Li(2)F4 tetrahedra. Mn(1) is bonded to one F(1), one F(3), one F(4), and two equivalent F(2) atoms to form MnF5 trigonal bipyramids that share corners with four equivalent Li(1)F4 tetrahedra and corners with eight equivalent Li(2)F4 tetrahedra. 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(1), two equivalent Li(2), and one Mn(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Mn(1) atom. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Li(2) and one Mn(1) atom. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), 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 to one F(1), one F(4), and two equivalent F(2) atoms to form distorted LiF4 tetrahedra that share corners with two equivalent Li(2)F4 tetrahedra, corners with four equivalent Mn(1)F5 trigonal bipyramids, and edges with two equivalent Li(2)F4 tetrahedra. The Li(1)-F(1) bond length is 1.95 Å. The Li(1)-F(4) bond length is 1.96 Å. Both Li(1)-F(2) bond lengths are 1.83 Å. In the second Li site, Li(2) 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(1)F4 tetrahedra,  a cornercorner with one Li(2)F4 tetrahedra, corners with four equivalent Mn(1)F5 trigonal bipyramids,  an edgeedge with one Li(1)F4 tetrahedra, and  an edgeedge with one Li(2)F4 tetrahedra. The Li(2)-F(1) bond length is 2.02 Å. The Li(2)-F(2) bond length is 1.85 Å. The Li(2)-F(3) bond length is 2.00 Å. The Li(2)-F(4) bond length is 2.05 Å. Mn(1) is bonded to one F(1), one F(3), one F(4), and two equivalent F(2) atoms to form MnF5 trigonal bipyramids that share corners with four equivalent Li(1)F4 tetrahedra and corners with eight equivalent Li(2)F4 tetrahedra. The Mn(1)-F(1) bond length is 2.13 Å. The Mn(1)-F(3) bond length is 2.10 Å. The Mn(1)-F(4) bond length is 2.12 Å. Both Mn(1)-F(2) bond lengths are 2.04 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(1), two equivalent Li(2), and one Mn(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Mn(1) atom. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Li(2) and one Mn(1) atom. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one Mn(1) atom.