Li2Mn2F7 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(3), one F(4), one F(5), and two equivalent F(6) atoms to form LiF5 trigonal bipyramids that share corners with three equivalent Mn(2)F6 octahedra,  a cornercorner with one Li(2)F5 trigonal bipyramid,  an edgeedge with one Li(1)F5 trigonal bipyramid, and  an edgeedge with one Li(2)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 46-58°. In the second Li site, Li(2) is bonded to one F(1), one F(3), one F(4), one F(5), and one F(7) atom to form LiF5 trigonal bipyramids that share corners with four equivalent Mn(2)F6 octahedra,  a cornercorner with one Li(1)F5 trigonal bipyramid, and  an edgeedge with one Li(1)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 22-68°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 6-coordinate geometry to one F(2), one F(3), one F(6), one F(7), and two equivalent F(4) atoms. In the second Mn site, Mn(2) is bonded to one F(2), one F(5), one F(6), one F(7), and two equivalent F(1) atoms to form MnF6 octahedra that share corners with three equivalent Li(1)F5 trigonal bipyramids, corners with four equivalent Li(2)F5 trigonal bipyramids, and  an edgeedge with one Mn(2)F6 octahedra. There are seven inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(2) and two equivalent Mn(2) atoms. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Mn(1) and one Mn(2) atom. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one Mn(1) atom. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing FLi2Mn2 tetrahedra. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one Mn(2) atom. In the sixth F site, F(6) is bonded to two equivalent Li(1), one Mn(1), and one Mn(2) atom to form a mixture of distorted corner and edge-sharing FLi2Mn2 trigonal pyramids. In the seventh F site, F(7) is bonded in a distorted T-shaped geometry to one Li(2), one Mn(1), and one Mn(2) atom.
Li2Mn2F7 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(3), one F(4), one F(5), and two equivalent F(6) atoms to form LiF5 trigonal bipyramids that share corners with three equivalent Mn(2)F6 octahedra,  a cornercorner with one Li(2)F5 trigonal bipyramid,  an edgeedge with one Li(1)F5 trigonal bipyramid, and  an edgeedge with one Li(2)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 46-58°. The Li(1)-F(3) bond length is 1.89 Å. The Li(1)-F(4) bond length is 1.89 Å. The Li(1)-F(5) bond length is 2.04 Å. There is one shorter (2.22 Å) and one longer (2.25 Å) Li(1)-F(6) bond length. In the second Li site, Li(2) is bonded to one F(1), one F(3), one F(4), one F(5), and one F(7) atom to form LiF5 trigonal bipyramids that share corners with four equivalent Mn(2)F6 octahedra,  a cornercorner with one Li(1)F5 trigonal bipyramid, and  an edgeedge with one Li(1)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 22-68°. The Li(2)-F(1) bond length is 2.17 Å. The Li(2)-F(3) bond length is 2.01 Å. The Li(2)-F(4) bond length is 2.08 Å. The Li(2)-F(5) bond length is 1.98 Å. The Li(2)-F(7) bond length is 1.99 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 6-coordinate geometry to one F(2), one F(3), one F(6), one F(7), and two equivalent F(4) atoms. The Mn(1)-F(2) bond length is 2.09 Å. The Mn(1)-F(3) bond length is 2.03 Å. The Mn(1)-F(6) bond length is 2.37 Å. The Mn(1)-F(7) bond length is 2.12 Å. There is one shorter (2.13 Å) and one longer (2.20 Å) Mn(1)-F(4) bond length. In the second Mn site, Mn(2) is bonded to one F(2), one F(5), one F(6), one F(7), and two equivalent F(1) atoms to form MnF6 octahedra that share corners with three equivalent Li(1)F5 trigonal bipyramids, corners with four equivalent Li(2)F5 trigonal bipyramids, and  an edgeedge with one Mn(2)F6 octahedra. The Mn(2)-F(2) bond length is 1.88 Å. The Mn(2)-F(5) bond length is 1.87 Å. The Mn(2)-F(6) bond length is 1.97 Å. The Mn(2)-F(7) bond length is 2.11 Å. There is one shorter (1.95 Å) and one longer (2.23 Å) Mn(2)-F(1) bond length. There are seven inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(2) and two equivalent Mn(2) atoms. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Mn(1) and one Mn(2) atom. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one Mn(1) atom. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing FLi2Mn2 tetrahedra. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one Mn(2) atom. In the sixth F site, F(6) is bonded to two equivalent Li(1), one Mn(1), and one Mn(2) atom to form a mixture of distorted corner and edge-sharing FLi2Mn2 trigonal pyramids. In the seventh F site, F(7) is bonded in a distorted T-shaped geometry to one Li(2), one Mn(1), and one Mn(2) atom.