Li2Mn4OF8 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(1), one F(2), one F(5), and one F(7) atom to form LiF4 tetrahedra that share corners with two equivalent Mn(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 59-61°. In the second Li site, Li(2) is bonded to one F(3), one F(4), one F(6), and one F(8) atom to form LiF4 trigonal pyramids that share corners with three equivalent Mn(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 50-63°. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 6-coordinate geometry to one O(1), one F(2), one F(3), one F(4), one F(5), and one F(8) atom. In the second Mn site, Mn(2) is bonded in a 5-coordinate geometry to one O(1), one F(2), one F(6), and two equivalent F(7) atoms. In the third Mn site, Mn(3) is bonded to one O(1), one F(3), one F(6), one F(8), and two equivalent F(1) atoms to form distorted MnOF5 octahedra that share corners with two equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(2)F4 trigonal pyramids, and  an edgeedge with one Mn(3)OF5 octahedra. In the fourth Mn site, Mn(4) is bonded in a 6-coordinate geometry to one O(1), one F(3), one F(4), one F(5), one F(7), and one F(8) atom. O(1) is bonded in a tetrahedral geometry to one Mn(1), one Mn(2), one Mn(3), and one Mn(4) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Mn(3) atoms. In the second F site, F(2) is bonded in a distorted 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 4-coordinate geometry to one Li(2), one Mn(1), one Mn(3), and one Mn(4) atom. In the fourth F site, F(4) is bonded in a trigonal non-coplanar geometry to one Li(2), one Mn(1), and one Mn(4) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one Mn(4) atom. In the sixth F site, F(6) is bonded in a trigonal planar geometry to one Li(2), one Mn(2), and one Mn(3) atom. In the seventh F site, F(7) is bonded in a 4-coordinate geometry to one Li(1), one Mn(4), and two equivalent Mn(2) atoms. In the eighth F site, F(8) is bonded in a 4-coordinate geometry to one Li(2), one Mn(1), one Mn(3), and one Mn(4) atom.
Li2Mn4OF8 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(1), one F(2), one F(5), and one F(7) atom to form LiF4 tetrahedra that share corners with two equivalent Mn(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 59-61°. The Li(1)-F(1) bond length is 1.87 Å. The Li(1)-F(2) bond length is 1.85 Å. The Li(1)-F(5) bond length is 1.88 Å. The Li(1)-F(7) bond length is 1.95 Å. In the second Li site, Li(2) is bonded to one F(3), one F(4), one F(6), and one F(8) atom to form LiF4 trigonal pyramids that share corners with three equivalent Mn(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 50-63°. The Li(2)-F(3) bond length is 1.94 Å. The Li(2)-F(4) bond length is 1.96 Å. The Li(2)-F(6) bond length is 1.92 Å. The Li(2)-F(8) bond length is 1.92 Å. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 6-coordinate geometry to one O(1), one F(2), one F(3), one F(4), one F(5), and one F(8) atom. The Mn(1)-O(1) bond length is 2.10 Å. The Mn(1)-F(2) bond length is 2.19 Å. The Mn(1)-F(3) bond length is 2.19 Å. The Mn(1)-F(4) bond length is 2.11 Å. The Mn(1)-F(5) bond length is 2.17 Å. The Mn(1)-F(8) bond length is 2.61 Å. In the second Mn site, Mn(2) is bonded in a 5-coordinate geometry to one O(1), one F(2), one F(6), and two equivalent F(7) atoms. The Mn(2)-O(1) bond length is 2.05 Å. The Mn(2)-F(2) bond length is 2.07 Å. The Mn(2)-F(6) bond length is 2.07 Å. There is one shorter (2.16 Å) and one longer (2.49 Å) Mn(2)-F(7) bond length. In the third Mn site, Mn(3) is bonded to one O(1), one F(3), one F(6), one F(8), and two equivalent F(1) atoms to form distorted MnOF5 octahedra that share corners with two equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(2)F4 trigonal pyramids, and  an edgeedge with one Mn(3)OF5 octahedra. The Mn(3)-O(1) bond length is 2.03 Å. The Mn(3)-F(3) bond length is 2.60 Å. The Mn(3)-F(6) bond length is 2.24 Å. The Mn(3)-F(8) bond length is 2.24 Å. There is one shorter (2.07 Å) and one longer (2.16 Å) Mn(3)-F(1) bond length. In the fourth Mn site, Mn(4) is bonded in a 6-coordinate geometry to one O(1), one F(3), one F(4), one F(5), one F(7), and one F(8) atom. The Mn(4)-O(1) bond length is 2.09 Å. The Mn(4)-F(3) bond length is 2.30 Å. The Mn(4)-F(4) bond length is 2.10 Å. The Mn(4)-F(5) bond length is 2.16 Å. The Mn(4)-F(7) bond length is 2.37 Å. The Mn(4)-F(8) bond length is 2.21 Å. O(1) is bonded in a tetrahedral geometry to one Mn(1), one Mn(2), one Mn(3), and one Mn(4) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Mn(3) atoms. In the second F site, F(2) is bonded in a distorted 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 4-coordinate geometry to one Li(2), one Mn(1), one Mn(3), and one Mn(4) atom. In the fourth F site, F(4) is bonded in a trigonal non-coplanar geometry to one Li(2), one Mn(1), and one Mn(4) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one Mn(4) atom. In the sixth F site, F(6) is bonded in a trigonal planar geometry to one Li(2), one Mn(2), and one Mn(3) atom. In the seventh F site, F(7) is bonded in a 4-coordinate geometry to one Li(1), one Mn(4), and two equivalent Mn(2) atoms. In the eighth F site, F(8) is bonded in a 4-coordinate geometry to one Li(2), one Mn(1), one Mn(3), and one Mn(4) atom.