Li2MnF5 crystallizes in the orthorhombic Pna2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(2), one F(4), and one F(5) atom to form LiF4 tetrahedra that share  a cornercorner with one Li(2)F4 tetrahedra, corners with four equivalent Mn(1)F5 trigonal bipyramids, and  an edgeedge with one 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(5) atom to form LiF4 tetrahedra that share  a cornercorner with one Li(1)F4 tetrahedra, corners with four equivalent Mn(1)F5 trigonal bipyramids, and  an edgeedge with one Li(1)F4 tetrahedra. 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 trigonal bipyramids that share corners with four equivalent Li(1)F4 tetrahedra and corners with four equivalent Li(2)F4 tetrahedra. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one Mn(1) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one Mn(1) atom. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one Li(2) and one Mn(1) atom. In the fourth F site, F(4) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one Mn(1) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Mn(1) atom.
Li2MnF5 crystallizes in the orthorhombic Pna2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(2), one F(4), and one F(5) atom to form LiF4 tetrahedra that share  a cornercorner with one Li(2)F4 tetrahedra, corners with four equivalent Mn(1)F5 trigonal bipyramids, and  an edgeedge with one Li(2)F4 tetrahedra. The Li(1)-F(1) bond length is 1.93 Å. The Li(1)-F(2) bond length is 1.94 Å. The Li(1)-F(4) bond length is 1.82 Å. The Li(1)-F(5) bond length is 1.89 Å. In the second Li site, Li(2) is bonded to one F(1), one F(2), one F(3), and one F(5) atom to form LiF4 tetrahedra that share  a cornercorner with one Li(1)F4 tetrahedra, corners with four equivalent Mn(1)F5 trigonal bipyramids, and  an edgeedge with one Li(1)F4 tetrahedra. The Li(2)-F(1) bond length is 1.95 Å. The Li(2)-F(2) bond length is 1.98 Å. The Li(2)-F(3) bond length is 1.85 Å. The Li(2)-F(5) bond length is 1.86 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 trigonal bipyramids that share corners with four equivalent Li(1)F4 tetrahedra and corners with four equivalent Li(2)F4 tetrahedra. The Mn(1)-F(1) bond length is 1.88 Å. The Mn(1)-F(2) bond length is 1.88 Å. The Mn(1)-F(3) bond length is 2.01 Å. The Mn(1)-F(4) bond length is 1.87 Å. The Mn(1)-F(5) bond length is 1.97 Å. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one Mn(1) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one Mn(1) atom. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one Li(2) and one Mn(1) atom. In the fourth F site, F(4) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one Mn(1) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Mn(1) atom.