Li2Mn3F8 crystallizes in the monoclinic P2_1/c 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 two equivalent F(3) atoms to form distorted LiF5 trigonal bipyramids that share corners with three equivalent Mn(1)F6 pentagonal pyramids,  a cornercorner with one Mn(2)F5 trigonal bipyramid,  an edgeedge with one Mn(1)F6 pentagonal pyramid,  an edgeedge with one Li(1)F5 trigonal bipyramid, and  an edgeedge with one Mn(2)F5 trigonal bipyramid. In the second Li site, Li(2) is bonded to one F(5), one F(6), one F(7), and one F(8) atom to form LiF4 tetrahedra that share corners with three equivalent Mn(2)F5 trigonal bipyramids and  an edgeedge with one Mn(1)F6 pentagonal pyramid. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one F(2), one F(3), one F(5), one F(6), and two equivalent F(1) atoms to form distorted MnF6 pentagonal pyramids that share corners with three equivalent Li(1)F5 trigonal bipyramids, corners with four equivalent Mn(2)F5 trigonal bipyramids,  an edgeedge with one Mn(1)F6 pentagonal pyramid,  an edgeedge with one Li(2)F4 tetrahedra, and  an edgeedge with one Li(1)F5 trigonal bipyramid. In the second Mn site, Mn(2) is bonded to one F(2), one F(3), one F(5), one F(6), and one F(8) atom to form MnF5 trigonal bipyramids that share corners with four equivalent Mn(1)F6 pentagonal pyramids, corners with three equivalent Li(2)F4 tetrahedra,  a cornercorner with one Li(1)F5 trigonal bipyramid, and  an edgeedge with one Li(1)F5 trigonal bipyramid. In the third Mn site, Mn(3) is bonded in a 6-coordinate geometry to one F(1), one F(8), two equivalent F(4), and two equivalent F(7) atoms. There are eight inequivalent F sites. In the first F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Mn(3) atoms. In the second F site, F(8) is bonded in a trigonal planar geometry to one Li(2), one Mn(2), and one Mn(3) atom. In the third F site, F(1) is bonded in a 4-coordinate geometry to one Li(1), one Mn(3), and two equivalent Mn(1) atoms. In the fourth 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 fifth F site, F(3) is bonded to two equivalent Li(1), one Mn(1), and one Mn(2) atom to form distorted edge-sharing FLi2Mn2 trigonal pyramids. In the sixth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Mn(3) atoms. In the seventh F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(1), and one Mn(2) atom. In the eighth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(1), and one Mn(2) atom.
Li2Mn3F8 crystallizes in the monoclinic P2_1/c 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 two equivalent F(3) atoms to form distorted LiF5 trigonal bipyramids that share corners with three equivalent Mn(1)F6 pentagonal pyramids,  a cornercorner with one Mn(2)F5 trigonal bipyramid,  an edgeedge with one Mn(1)F6 pentagonal pyramid,  an edgeedge with one Li(1)F5 trigonal bipyramid, and  an edgeedge with one Mn(2)F5 trigonal bipyramid. The Li(1)-F(1) bond length is 1.97 Å. The Li(1)-F(2) bond length is 1.90 Å. The Li(1)-F(4) bond length is 1.84 Å. There is one shorter (1.95 Å) and one longer (2.37 Å) Li(1)-F(3) bond length. In the second Li site, Li(2) is bonded to one F(5), one F(6), one F(7), and one F(8) atom to form LiF4 tetrahedra that share corners with three equivalent Mn(2)F5 trigonal bipyramids and  an edgeedge with one Mn(1)F6 pentagonal pyramid. The Li(2)-F(5) bond length is 1.87 Å. The Li(2)-F(6) bond length is 1.89 Å. The Li(2)-F(7) bond length is 1.82 Å. The Li(2)-F(8) bond length is 1.90 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one F(2), one F(3), one F(5), one F(6), and two equivalent F(1) atoms to form distorted MnF6 pentagonal pyramids that share corners with three equivalent Li(1)F5 trigonal bipyramids, corners with four equivalent Mn(2)F5 trigonal bipyramids,  an edgeedge with one Mn(1)F6 pentagonal pyramid,  an edgeedge with one Li(2)F4 tetrahedra, and  an edgeedge with one Li(1)F5 trigonal bipyramid. The Mn(1)-F(2) bond length is 2.10 Å. The Mn(1)-F(3) bond length is 2.17 Å. The Mn(1)-F(5) bond length is 2.14 Å. The Mn(1)-F(6) bond length is 2.20 Å. There is one shorter (2.14 Å) and one longer (2.30 Å) Mn(1)-F(1) bond length. In the second Mn site, Mn(2) is bonded to one F(2), one F(3), one F(5), one F(6), and one F(8) atom to form MnF5 trigonal bipyramids that share corners with four equivalent Mn(1)F6 pentagonal pyramids, corners with three equivalent Li(2)F4 tetrahedra,  a cornercorner with one Li(1)F5 trigonal bipyramid, and  an edgeedge with one Li(1)F5 trigonal bipyramid. The Mn(2)-F(2) bond length is 2.12 Å. The Mn(2)-F(3) bond length is 2.21 Å. The Mn(2)-F(5) bond length is 2.02 Å. The Mn(2)-F(6) bond length is 2.04 Å. The Mn(2)-F(8) bond length is 2.15 Å. In the third Mn site, Mn(3) is bonded in a 6-coordinate geometry to one F(1), one F(8), two equivalent F(4), and two equivalent F(7) atoms. The Mn(3)-F(1) bond length is 2.54 Å. The Mn(3)-F(8) bond length is 2.11 Å. There is one shorter (2.05 Å) and one longer (2.19 Å) Mn(3)-F(4) bond length. There is one shorter (2.10 Å) and one longer (2.42 Å) Mn(3)-F(7) bond length. There are eight inequivalent F sites. In the first F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Mn(3) atoms. In the second F site, F(8) is bonded in a trigonal planar geometry to one Li(2), one Mn(2), and one Mn(3) atom. In the third F site, F(1) is bonded in a 4-coordinate geometry to one Li(1), one Mn(3), and two equivalent Mn(1) atoms. In the fourth 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 fifth F site, F(3) is bonded to two equivalent Li(1), one Mn(1), and one Mn(2) atom to form distorted edge-sharing FLi2Mn2 trigonal pyramids. In the sixth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Mn(3) atoms. In the seventh F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(1), and one Mn(2) atom. In the eighth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(1), and one Mn(2) atom.