Li2MnF5 crystallizes in the orthorhombic P2_12_12_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to one F(1), one F(5), and two equivalent F(2) atoms. In the second Li site, Li(2) is bonded to one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form distorted LiF5 square pyramids that share corners with three equivalent Mn(1)F5 square pyramids and  an edgeedge with one Mn(1)F5 square pyramid. Mn(1) is bonded to one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form MnF5 square pyramids that share corners with three equivalent Li(2)F5 square pyramids and  an edgeedge with one Li(2)F5 square pyramid. There are five inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one Mn(1) atom. In the second F site, F(2) is bonded to one Li(2), two equivalent Li(1), and one Mn(1) atom to form corner-sharing FLi3Mn tetrahedra. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(2) and one Mn(1) atom. In the fourth F site, F(4) is bonded in a distorted bent 150 degrees geometry to one Li(2) and one Mn(1) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Mn(1) atom.
Li2MnF5 crystallizes in the orthorhombic P2_12_12_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to one F(1), one F(5), and two equivalent F(2) atoms. The Li(1)-F(1) bond length is 1.90 Å. The Li(1)-F(5) bond length is 1.93 Å. There is one shorter (2.06 Å) and one longer (2.07 Å) Li(1)-F(2) bond length. In the second Li site, Li(2) is bonded to one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form distorted LiF5 square pyramids that share corners with three equivalent Mn(1)F5 square pyramids and  an edgeedge with one Mn(1)F5 square pyramid. The Li(2)-F(1) bond length is 2.18 Å. The Li(2)-F(2) bond length is 2.08 Å. The Li(2)-F(3) bond length is 1.95 Å. The Li(2)-F(4) bond length is 1.98 Å. The Li(2)-F(5) bond length is 2.07 Å. Mn(1) is bonded to one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form MnF5 square pyramids that share corners with three equivalent Li(2)F5 square pyramids and  an edgeedge with one Li(2)F5 square pyramid. The Mn(1)-F(1) bond length is 1.87 Å. The Mn(1)-F(2) bond length is 2.06 Å. The Mn(1)-F(3) bond length is 1.87 Å. The Mn(1)-F(4) bond length is 1.87 Å. The Mn(1)-F(5) bond length is 1.88 Å. There are five inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one Mn(1) atom. In the second F site, F(2) is bonded to one Li(2), two equivalent Li(1), and one Mn(1) atom to form corner-sharing FLi3Mn tetrahedra. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(2) and one Mn(1) atom. In the fourth F site, F(4) is bonded in a distorted bent 150 degrees geometry to one Li(2) and one Mn(1) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Mn(1) atom.