Li6Mn(OF2)2 crystallizes in the triclinic P-1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(4), and two equivalent F(3) atoms to form distorted LiOF3 trigonal pyramids that share corners with two equivalent Mn(1)O2F4 octahedra, corners with two equivalent Li(4)O2F2 tetrahedra,  a cornercorner with one Li(3)O2F2 trigonal pyramid,  a cornercorner with one Li(5)OF3 trigonal pyramid,  an edgeedge with one Mn(2)O2F4 octahedra,  an edgeedge with one Li(3)O2F2 trigonal pyramid,  an edgeedge with one Li(1)OF3 trigonal pyramid, and  an edgeedge with one Li(5)OF3 trigonal pyramid. The corner-sharing octahedral tilt angles range from 52-70°. In the second Li site, Li(2) is bonded in a distorted see-saw-like geometry to one O(1), one F(1), one F(2), and one F(4) atom. In the third Li site, Li(3) is bonded to one O(1), one O(2), one F(1), and one F(3) atom to form distorted LiO2F2 trigonal pyramids that share  a cornercorner with one Mn(1)O2F4 octahedra,  a cornercorner with one Mn(2)O2F4 octahedra, corners with two equivalent Li(4)O2F2 tetrahedra,  a cornercorner with one Li(1)OF3 trigonal pyramid,  a cornercorner with one Li(5)OF3 trigonal pyramid,  an edgeedge with one Mn(1)O2F4 octahedra,  an edgeedge with one Li(1)OF3 trigonal pyramid, and  an edgeedge with one Li(5)OF3 trigonal pyramid. The corner-sharing octahedral tilt angles range from 48-61°. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one F(2), and one F(4) atom to form distorted LiO2F2 tetrahedra that share  a cornercorner with one Mn(1)O2F4 octahedra,  a cornercorner with one Mn(2)O2F4 octahedra, corners with two equivalent Li(3)O2F2 trigonal pyramids, corners with two equivalent Li(1)OF3 trigonal pyramids,  an edgeedge with one Mn(2)O2F4 octahedra, and  an edgeedge with one Li(5)OF3 trigonal pyramid. The corner-sharing octahedral tilt angles range from 44-62°. In the fifth Li site, Li(5) is bonded to one O(2), one F(1), one F(3), and one F(4) atom to form distorted LiOF3 trigonal pyramids that share  a cornercorner with one Mn(1)O2F4 octahedra,  a cornercorner with one Mn(2)O2F4 octahedra,  a cornercorner with one Li(3)O2F2 trigonal pyramid,  a cornercorner with one Li(1)OF3 trigonal pyramid,  an edgeedge with one Mn(1)O2F4 octahedra,  an edgeedge with one Li(4)O2F2 tetrahedra,  an edgeedge with one Li(3)O2F2 trigonal pyramid, and  an edgeedge with one Li(1)OF3 trigonal pyramid. The corner-sharing octahedral tilt angles range from 48-65°. In the sixth Li site, Li(6) is bonded in a distorted see-saw-like geometry to one O(2), one F(1), and two equivalent F(2) atoms. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(2), two equivalent F(1), and two equivalent F(3) atoms to form distorted MnO2F4 octahedra that share corners with two equivalent Li(4)O2F2 tetrahedra, corners with two equivalent Li(3)O2F2 trigonal pyramids, corners with two equivalent Li(5)OF3 trigonal pyramids, corners with four equivalent Li(1)OF3 trigonal pyramids, edges with two equivalent Li(3)O2F2 trigonal pyramids, and edges with two equivalent Li(5)OF3 trigonal pyramids. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent F(2), and two equivalent F(4) atoms to form distorted MnO2F4 octahedra that share corners with two equivalent Li(4)O2F2 tetrahedra, corners with two equivalent Li(3)O2F2 trigonal pyramids, corners with two equivalent Li(5)OF3 trigonal pyramids, edges with two equivalent Li(4)O2F2 tetrahedra, and edges with two equivalent Li(1)OF3 trigonal pyramids. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one Mn(2) atom to form distorted OLi4Mn trigonal bipyramids that share  a cornercorner with one O(1)Li4Mn trigonal bipyramid,  a cornercorner with one F(3)Li4Mn trigonal bipyramid, corners with two equivalent O(2)Li4Mn trigonal bipyramids, and  an edgeedge with one F(3)Li4Mn trigonal bipyramid. In the second O site, O(2) is bonded to one Li(3), one Li(4), one Li(5), one Li(6), and one Mn(1) atom to form distorted OLi4Mn trigonal bipyramids that share  a cornercorner with one O(2)Li4Mn trigonal bipyramid, corners with two equivalent O(1)Li4Mn trigonal bipyramids, corners with two equivalent F(3)Li4Mn trigonal bipyramids, and  an edgeedge with one F(3)Li4Mn trigonal bipyramid. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Li(5), one Li(6), and one Mn(1) atom. In the second F site, F(2) is bonded in a 5-coordinate geometry to one Li(2), one Li(4), two equivalent Li(6), and one Mn(2) atom. In the third F site, F(3) is bonded to one Li(3), one Li(5), two equivalent Li(1), and one Mn(1) atom to form distorted FLi4Mn trigonal bipyramids that share  a cornercorner with one O(1)Li4Mn trigonal bipyramid,  a cornercorner with one F(3)Li4Mn trigonal bipyramid, corners with two equivalent O(2)Li4Mn trigonal bipyramids,  an edgeedge with one O(1)Li4Mn trigonal bipyramid,  an edgeedge with one O(2)Li4Mn trigonal bipyramid, and  an edgeedge with one F(3)Li4Mn trigonal bipyramid. In the fourth F site, F(4) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(4), one Li(5), and one Mn(2) atom.
Li6Mn(OF2)2 crystallizes in the triclinic P-1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(4), and two equivalent F(3) atoms to form distorted LiOF3 trigonal pyramids that share corners with two equivalent Mn(1)O2F4 octahedra, corners with two equivalent Li(4)O2F2 tetrahedra,  a cornercorner with one Li(3)O2F2 trigonal pyramid,  a cornercorner with one Li(5)OF3 trigonal pyramid,  an edgeedge with one Mn(2)O2F4 octahedra,  an edgeedge with one Li(3)O2F2 trigonal pyramid,  an edgeedge with one Li(1)OF3 trigonal pyramid, and  an edgeedge with one Li(5)OF3 trigonal pyramid. The corner-sharing octahedral tilt angles range from 52-70°. The Li(1)-O(1) bond length is 1.89 Å. The Li(1)-F(4) bond length is 1.94 Å. There is one shorter (1.90 Å) and one longer (1.97 Å) Li(1)-F(3) bond length. In the second Li site, Li(2) is bonded in a distorted see-saw-like geometry to one O(1), one F(1), one F(2), and one F(4) atom. The Li(2)-O(1) bond length is 1.92 Å. The Li(2)-F(1) bond length is 1.98 Å. The Li(2)-F(2) bond length is 1.96 Å. The Li(2)-F(4) bond length is 2.00 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one F(1), and one F(3) atom to form distorted LiO2F2 trigonal pyramids that share  a cornercorner with one Mn(1)O2F4 octahedra,  a cornercorner with one Mn(2)O2F4 octahedra, corners with two equivalent Li(4)O2F2 tetrahedra,  a cornercorner with one Li(1)OF3 trigonal pyramid,  a cornercorner with one Li(5)OF3 trigonal pyramid,  an edgeedge with one Mn(1)O2F4 octahedra,  an edgeedge with one Li(1)OF3 trigonal pyramid, and  an edgeedge with one Li(5)OF3 trigonal pyramid. The corner-sharing octahedral tilt angles range from 48-61°. The Li(3)-O(1) bond length is 1.93 Å. The Li(3)-O(2) bond length is 1.94 Å. The Li(3)-F(1) bond length is 1.96 Å. The Li(3)-F(3) bond length is 2.01 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one F(2), and one F(4) atom to form distorted LiO2F2 tetrahedra that share  a cornercorner with one Mn(1)O2F4 octahedra,  a cornercorner with one Mn(2)O2F4 octahedra, corners with two equivalent Li(3)O2F2 trigonal pyramids, corners with two equivalent Li(1)OF3 trigonal pyramids,  an edgeedge with one Mn(2)O2F4 octahedra, and  an edgeedge with one Li(5)OF3 trigonal pyramid. The corner-sharing octahedral tilt angles range from 44-62°. The Li(4)-O(1) bond length is 1.94 Å. The Li(4)-O(2) bond length is 1.95 Å. The Li(4)-F(2) bond length is 2.03 Å. The Li(4)-F(4) bond length is 1.96 Å. In the fifth Li site, Li(5) is bonded to one O(2), one F(1), one F(3), and one F(4) atom to form distorted LiOF3 trigonal pyramids that share  a cornercorner with one Mn(1)O2F4 octahedra,  a cornercorner with one Mn(2)O2F4 octahedra,  a cornercorner with one Li(3)O2F2 trigonal pyramid,  a cornercorner with one Li(1)OF3 trigonal pyramid,  an edgeedge with one Mn(1)O2F4 octahedra,  an edgeedge with one Li(4)O2F2 tetrahedra,  an edgeedge with one Li(3)O2F2 trigonal pyramid, and  an edgeedge with one Li(1)OF3 trigonal pyramid. The corner-sharing octahedral tilt angles range from 48-65°. The Li(5)-O(2) bond length is 1.90 Å. The Li(5)-F(1) bond length is 1.97 Å. The Li(5)-F(3) bond length is 1.96 Å. The Li(5)-F(4) bond length is 1.99 Å. In the sixth Li site, Li(6) is bonded in a distorted see-saw-like geometry to one O(2), one F(1), and two equivalent F(2) atoms. The Li(6)-O(2) bond length is 1.90 Å. The Li(6)-F(1) bond length is 1.97 Å. There is one shorter (1.92 Å) and one longer (1.95 Å) Li(6)-F(2) bond length. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(2), two equivalent F(1), and two equivalent F(3) atoms to form distorted MnO2F4 octahedra that share corners with two equivalent Li(4)O2F2 tetrahedra, corners with two equivalent Li(3)O2F2 trigonal pyramids, corners with two equivalent Li(5)OF3 trigonal pyramids, corners with four equivalent Li(1)OF3 trigonal pyramids, edges with two equivalent Li(3)O2F2 trigonal pyramids, and edges with two equivalent Li(5)OF3 trigonal pyramids. Both Mn(1)-O(2) bond lengths are 1.99 Å. Both Mn(1)-F(1) bond lengths are 2.49 Å. Both Mn(1)-F(3) bond lengths are 2.40 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent F(2), and two equivalent F(4) atoms to form distorted MnO2F4 octahedra that share corners with two equivalent Li(4)O2F2 tetrahedra, corners with two equivalent Li(3)O2F2 trigonal pyramids, corners with two equivalent Li(5)OF3 trigonal pyramids, edges with two equivalent Li(4)O2F2 tetrahedra, and edges with two equivalent Li(1)OF3 trigonal pyramids. Both Mn(2)-O(1) bond lengths are 2.00 Å. Both Mn(2)-F(2) bond lengths are 2.40 Å. Both Mn(2)-F(4) bond lengths are 2.49 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and one Mn(2) atom to form distorted OLi4Mn trigonal bipyramids that share  a cornercorner with one O(1)Li4Mn trigonal bipyramid,  a cornercorner with one F(3)Li4Mn trigonal bipyramid, corners with two equivalent O(2)Li4Mn trigonal bipyramids, and  an edgeedge with one F(3)Li4Mn trigonal bipyramid. In the second O site, O(2) is bonded to one Li(3), one Li(4), one Li(5), one Li(6), and one Mn(1) atom to form distorted OLi4Mn trigonal bipyramids that share  a cornercorner with one O(2)Li4Mn trigonal bipyramid, corners with two equivalent O(1)Li4Mn trigonal bipyramids, corners with two equivalent F(3)Li4Mn trigonal bipyramids, and  an edgeedge with one F(3)Li4Mn trigonal bipyramid. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Li(5), one Li(6), and one Mn(1) atom. In the second F site, F(2) is bonded in a 5-coordinate geometry to one Li(2), one Li(4), two equivalent Li(6), and one Mn(2) atom. In the third F site, F(3) is bonded to one Li(3), one Li(5), two equivalent Li(1), and one Mn(1) atom to form distorted FLi4Mn trigonal bipyramids that share  a cornercorner with one O(1)Li4Mn trigonal bipyramid,  a cornercorner with one F(3)Li4Mn trigonal bipyramid, corners with two equivalent O(2)Li4Mn trigonal bipyramids,  an edgeedge with one O(1)Li4Mn trigonal bipyramid,  an edgeedge with one O(2)Li4Mn trigonal bipyramid, and  an edgeedge with one F(3)Li4Mn trigonal bipyramid. In the fourth F site, F(4) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(4), one Li(5), and one Mn(2) atom.