LiMn2F5 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(3), one F(5), and one F(8) atom to form LiF4 tetrahedra that share  a cornercorner with one Mn(4)F6 octahedra, corners with two equivalent Mn(1)F6 octahedra, corners with two equivalent Mn(2)F6 octahedra, and corners with three equivalent Mn(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 51-61°. In the second Li site, Li(2) is bonded to one F(1), one F(10), one F(7), and one F(9) atom to form LiF4 tetrahedra that share corners with two equivalent Mn(1)F6 octahedra, corners with two equivalent Mn(2)F6 octahedra, corners with two equivalent Mn(3)F6 octahedra, and corners with two equivalent Mn(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-58°. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(6), and one F(7) atom to form MnF6 octahedra that share corners with two equivalent Mn(4)F6 octahedra, corners with two equivalent Li(1)F4 tetrahedra, corners with two equivalent Li(2)F4 tetrahedra,  an edgeedge with one Mn(3)F6 octahedra,  an edgeedge with one Mn(4)F6 octahedra, and edges with two equivalent Mn(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 14-21°. In the second Mn site, Mn(2) is bonded to one F(1), one F(2), one F(4), one F(5), one F(6), and one F(9) atom to form distorted MnF6 octahedra that share corners with two equivalent Li(1)F4 tetrahedra, corners with two equivalent Li(2)F4 tetrahedra,  an edgeedge with one Mn(3)F6 octahedra, edges with two equivalent Mn(1)F6 octahedra, and edges with two equivalent Mn(4)F6 octahedra. In the third Mn site, Mn(3) is bonded to one F(3), one F(5), one F(6), one F(8), and two equivalent F(10) atoms to form MnF6 octahedra that share corners with two equivalent Li(2)F4 tetrahedra, corners with three equivalent Li(1)F4 tetrahedra,  an edgeedge with one Mn(1)F6 octahedra,  an edgeedge with one Mn(2)F6 octahedra,  an edgeedge with one Mn(3)F6 octahedra, and  an edgeedge with one Mn(4)F6 octahedra. In the fourth Mn site, Mn(4) is bonded to one F(6), one F(7), one F(8), one F(9), and two equivalent F(4) atoms to form distorted MnF6 octahedra that share corners with two equivalent Mn(1)F6 octahedra,  a cornercorner with one Li(1)F4 tetrahedra, corners with two equivalent Li(2)F4 tetrahedra,  an edgeedge with one Mn(1)F6 octahedra,  an edgeedge with one Mn(3)F6 octahedra,  an edgeedge with one Mn(4)F6 octahedra, and edges with two equivalent Mn(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 14-21°. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(2), one Mn(1), and one Mn(2) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Mn(1), and one Mn(2) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(1), one Mn(1), and one Mn(3) atom. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Mn(1), one Mn(2), and two equivalent Mn(4) atoms. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(1), one Mn(2), and one Mn(3) atom. In the sixth F site, F(6) is bonded in a rectangular see-saw-like geometry to one Mn(1), one Mn(2), one Mn(3), and one Mn(4) atom. In the seventh F site, F(7) is bonded in a trigonal planar geometry to one Li(2), one Mn(1), and one Mn(4) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(3), and one Mn(4) atom. In the ninth F site, F(9) is bonded in a trigonal planar geometry to one Li(2), one Mn(2), and one Mn(4) atom. In the tenth F site, F(10) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Mn(3) atoms.
LiMn2F5 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(3), one F(5), and one F(8) atom to form LiF4 tetrahedra that share  a cornercorner with one Mn(4)F6 octahedra, corners with two equivalent Mn(1)F6 octahedra, corners with two equivalent Mn(2)F6 octahedra, and corners with three equivalent Mn(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 51-61°. The Li(1)-F(2) bond length is 1.92 Å. The Li(1)-F(3) bond length is 1.91 Å. The Li(1)-F(5) bond length is 1.91 Å. The Li(1)-F(8) bond length is 1.91 Å. In the second Li site, Li(2) is bonded to one F(1), one F(10), one F(7), and one F(9) atom to form LiF4 tetrahedra that share corners with two equivalent Mn(1)F6 octahedra, corners with two equivalent Mn(2)F6 octahedra, corners with two equivalent Mn(3)F6 octahedra, and corners with two equivalent Mn(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-58°. The Li(2)-F(1) bond length is 1.94 Å. The Li(2)-F(10) bond length is 1.90 Å. The Li(2)-F(7) bond length is 1.92 Å. The Li(2)-F(9) bond length is 1.93 Å. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(6), and one F(7) atom to form MnF6 octahedra that share corners with two equivalent Mn(4)F6 octahedra, corners with two equivalent Li(1)F4 tetrahedra, corners with two equivalent Li(2)F4 tetrahedra,  an edgeedge with one Mn(3)F6 octahedra,  an edgeedge with one Mn(4)F6 octahedra, and edges with two equivalent Mn(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 14-21°. The Mn(1)-F(1) bond length is 2.13 Å. The Mn(1)-F(2) bond length is 2.11 Å. The Mn(1)-F(3) bond length is 2.08 Å. The Mn(1)-F(4) bond length is 2.32 Å. The Mn(1)-F(6) bond length is 2.32 Å. The Mn(1)-F(7) bond length is 2.09 Å. In the second Mn site, Mn(2) is bonded to one F(1), one F(2), one F(4), one F(5), one F(6), and one F(9) atom to form distorted MnF6 octahedra that share corners with two equivalent Li(1)F4 tetrahedra, corners with two equivalent Li(2)F4 tetrahedra,  an edgeedge with one Mn(3)F6 octahedra, edges with two equivalent Mn(1)F6 octahedra, and edges with two equivalent Mn(4)F6 octahedra. The Mn(2)-F(1) bond length is 2.08 Å. The Mn(2)-F(2) bond length is 2.08 Å. The Mn(2)-F(4) bond length is 2.26 Å. The Mn(2)-F(5) bond length is 2.16 Å. The Mn(2)-F(6) bond length is 2.23 Å. The Mn(2)-F(9) bond length is 2.18 Å. In the third Mn site, Mn(3) is bonded to one F(3), one F(5), one F(6), one F(8), and two equivalent F(10) atoms to form MnF6 octahedra that share corners with two equivalent Li(2)F4 tetrahedra, corners with three equivalent Li(1)F4 tetrahedra,  an edgeedge with one Mn(1)F6 octahedra,  an edgeedge with one Mn(2)F6 octahedra,  an edgeedge with one Mn(3)F6 octahedra, and  an edgeedge with one Mn(4)F6 octahedra. The Mn(3)-F(3) bond length is 2.15 Å. The Mn(3)-F(5) bond length is 2.13 Å. The Mn(3)-F(6) bond length is 2.24 Å. The Mn(3)-F(8) bond length is 2.16 Å. There is one shorter (2.06 Å) and one longer (2.23 Å) Mn(3)-F(10) bond length. In the fourth Mn site, Mn(4) is bonded to one F(6), one F(7), one F(8), one F(9), and two equivalent F(4) atoms to form distorted MnF6 octahedra that share corners with two equivalent Mn(1)F6 octahedra,  a cornercorner with one Li(1)F4 tetrahedra, corners with two equivalent Li(2)F4 tetrahedra,  an edgeedge with one Mn(1)F6 octahedra,  an edgeedge with one Mn(3)F6 octahedra,  an edgeedge with one Mn(4)F6 octahedra, and edges with two equivalent Mn(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 14-21°. The Mn(4)-F(6) bond length is 2.32 Å. The Mn(4)-F(7) bond length is 2.12 Å. The Mn(4)-F(8) bond length is 2.06 Å. The Mn(4)-F(9) bond length is 2.10 Å. There is one shorter (2.23 Å) and one longer (2.29 Å) Mn(4)-F(4) bond length. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(2), one Mn(1), and one Mn(2) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Mn(1), and one Mn(2) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(1), one Mn(1), and one Mn(3) atom. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Mn(1), one Mn(2), and two equivalent Mn(4) atoms. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(1), one Mn(2), and one Mn(3) atom. In the sixth F site, F(6) is bonded in a rectangular see-saw-like geometry to one Mn(1), one Mn(2), one Mn(3), and one Mn(4) atom. In the seventh F site, F(7) is bonded in a trigonal planar geometry to one Li(2), one Mn(1), and one Mn(4) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(3), and one Mn(4) atom. In the ninth F site, F(9) is bonded in a trigonal planar geometry to one Li(2), one Mn(2), and one Mn(4) atom. In the tenth F site, F(10) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Mn(3) atoms.