LiMn6(OF2)4 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(3), one F(2), one F(3), and one F(7) atom to form distorted LiOF3 trigonal pyramids that share  a cornercorner with one Mn(3)O2F4 octahedra, corners with two equivalent Mn(1)O2F4 octahedra,  an edgeedge with one Mn(3)O2F4 octahedra, and  an edgeedge with one Mn(6)OF4 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 2-63°. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(4), one F(2), one F(3), one F(5), and one F(8) atom to form MnO2F4 octahedra that share corners with two equivalent Mn(4)O2F4 octahedra, corners with three equivalent Mn(6)OF4 trigonal bipyramids, corners with two equivalent Li(1)OF3 trigonal pyramids, and  an edgeedge with one Mn(3)O2F4 octahedra. The corner-sharing octahedral tilt angles are 47°. In the second Mn site, Mn(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one F(5), and one F(6) atom. In the third Mn site, Mn(3) is bonded to one O(3), one O(4), one F(1), one F(3), one F(4), and one F(7) atom to form distorted MnO2F4 octahedra that share corners with two equivalent Mn(4)O2F4 octahedra,  a cornercorner with one Mn(6)OF4 trigonal bipyramid,  a cornercorner with one Li(1)OF3 trigonal pyramid,  an edgeedge with one Mn(1)O2F4 octahedra, and  an edgeedge with one Li(1)OF3 trigonal pyramid. The corner-sharing octahedral tilt angles range from 17-70°. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(2), one F(1), one F(4), one F(6), and one F(8) atom to form distorted MnO2F4 octahedra that share corners with two equivalent Mn(1)O2F4 octahedra, corners with two equivalent Mn(3)O2F4 octahedra, and  an edgeedge with one Mn(6)OF4 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 17-70°. In the fifth Mn site, Mn(5) is bonded in a 6-coordinate geometry to one O(3), one O(4), one F(1), one F(4), one F(6), and one F(7) atom. In the sixth Mn site, Mn(6) is bonded to one O(1), one F(2), one F(5), one F(7), and one F(8) atom to form distorted MnOF4 trigonal bipyramids that share  a cornercorner with one Mn(3)O2F4 octahedra, corners with three equivalent Mn(1)O2F4 octahedra,  an edgeedge with one Mn(4)O2F4 octahedra, and  an edgeedge with one Li(1)OF3 trigonal pyramid. The corner-sharing octahedral tilt angles range from 42-58°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Mn(2), one Mn(4), and one Mn(6) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(4) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(2), one Mn(3), and one Mn(5) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(3), and one Mn(5) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Mn(3), one Mn(4), and one Mn(5) atom. 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(6) atom. In the third F site, F(3) is bonded in a T-shaped geometry to one Li(1), one Mn(1), and one Mn(3) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Mn(3), one Mn(4), and one Mn(5) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(2), and one Mn(6) atom. In the sixth F site, F(6) is bonded in a T-shaped geometry to one Mn(2), one Mn(4), and one Mn(5) atom. In the seventh F site, F(7) is bonded in a distorted see-saw-like geometry to one Li(1), one Mn(3), one Mn(5), and one Mn(6) atom. In the eighth F site, F(8) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(4), and one Mn(6) atom.
LiMn6(OF2)4 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(3), one F(2), one F(3), and one F(7) atom to form distorted LiOF3 trigonal pyramids that share  a cornercorner with one Mn(3)O2F4 octahedra, corners with two equivalent Mn(1)O2F4 octahedra,  an edgeedge with one Mn(3)O2F4 octahedra, and  an edgeedge with one Mn(6)OF4 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 2-63°. The Li(1)-O(3) bond length is 1.94 Å. The Li(1)-F(2) bond length is 1.93 Å. The Li(1)-F(3) bond length is 2.02 Å. The Li(1)-F(7) bond length is 1.96 Å. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(4), one F(2), one F(3), one F(5), and one F(8) atom to form MnO2F4 octahedra that share corners with two equivalent Mn(4)O2F4 octahedra, corners with three equivalent Mn(6)OF4 trigonal bipyramids, corners with two equivalent Li(1)OF3 trigonal pyramids, and  an edgeedge with one Mn(3)O2F4 octahedra. The corner-sharing octahedral tilt angles are 47°. The Mn(1)-O(2) bond length is 1.91 Å. The Mn(1)-O(4) bond length is 1.92 Å. The Mn(1)-F(2) bond length is 1.98 Å. The Mn(1)-F(3) bond length is 2.35 Å. The Mn(1)-F(5) bond length is 2.14 Å. The Mn(1)-F(8) bond length is 2.00 Å. In the second Mn site, Mn(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one F(5), and one F(6) atom. The Mn(2)-O(1) bond length is 1.86 Å. The Mn(2)-O(2) bond length is 1.95 Å. The Mn(2)-O(3) bond length is 1.96 Å. The Mn(2)-F(5) bond length is 2.33 Å. The Mn(2)-F(6) bond length is 2.04 Å. In the third Mn site, Mn(3) is bonded to one O(3), one O(4), one F(1), one F(3), one F(4), and one F(7) atom to form distorted MnO2F4 octahedra that share corners with two equivalent Mn(4)O2F4 octahedra,  a cornercorner with one Mn(6)OF4 trigonal bipyramid,  a cornercorner with one Li(1)OF3 trigonal pyramid,  an edgeedge with one Mn(1)O2F4 octahedra, and  an edgeedge with one Li(1)OF3 trigonal pyramid. The corner-sharing octahedral tilt angles range from 17-70°. The Mn(3)-O(3) bond length is 1.91 Å. The Mn(3)-O(4) bond length is 1.90 Å. The Mn(3)-F(1) bond length is 2.52 Å. The Mn(3)-F(3) bond length is 1.96 Å. The Mn(3)-F(4) bond length is 1.92 Å. The Mn(3)-F(7) bond length is 2.30 Å. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(2), one F(1), one F(4), one F(6), and one F(8) atom to form distorted MnO2F4 octahedra that share corners with two equivalent Mn(1)O2F4 octahedra, corners with two equivalent Mn(3)O2F4 octahedra, and  an edgeedge with one Mn(6)OF4 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 17-70°. The Mn(4)-O(1) bond length is 2.00 Å. The Mn(4)-O(2) bond length is 2.08 Å. The Mn(4)-F(1) bond length is 2.17 Å. The Mn(4)-F(4) bond length is 2.39 Å. The Mn(4)-F(6) bond length is 2.14 Å. The Mn(4)-F(8) bond length is 2.34 Å. In the fifth Mn site, Mn(5) is bonded in a 6-coordinate geometry to one O(3), one O(4), one F(1), one F(4), one F(6), and one F(7) atom. The Mn(5)-O(3) bond length is 2.26 Å. The Mn(5)-O(4) bond length is 2.02 Å. The Mn(5)-F(1) bond length is 2.18 Å. The Mn(5)-F(4) bond length is 2.47 Å. The Mn(5)-F(6) bond length is 2.16 Å. The Mn(5)-F(7) bond length is 2.16 Å. In the sixth Mn site, Mn(6) is bonded to one O(1), one F(2), one F(5), one F(7), and one F(8) atom to form distorted MnOF4 trigonal bipyramids that share  a cornercorner with one Mn(3)O2F4 octahedra, corners with three equivalent Mn(1)O2F4 octahedra,  an edgeedge with one Mn(4)O2F4 octahedra, and  an edgeedge with one Li(1)OF3 trigonal pyramid. The corner-sharing octahedral tilt angles range from 42-58°. The Mn(6)-O(1) bond length is 2.05 Å. The Mn(6)-F(2) bond length is 2.11 Å. The Mn(6)-F(5) bond length is 2.06 Å. The Mn(6)-F(7) bond length is 2.34 Å. The Mn(6)-F(8) bond length is 2.13 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Mn(2), one Mn(4), and one Mn(6) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(4) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(2), one Mn(3), and one Mn(5) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(3), and one Mn(5) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Mn(3), one Mn(4), and one Mn(5) atom. 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(6) atom. In the third F site, F(3) is bonded in a T-shaped geometry to one Li(1), one Mn(1), and one Mn(3) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Mn(3), one Mn(4), and one Mn(5) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(2), and one Mn(6) atom. In the sixth F site, F(6) is bonded in a T-shaped geometry to one Mn(2), one Mn(4), and one Mn(5) atom. In the seventh F site, F(7) is bonded in a distorted see-saw-like geometry to one Li(1), one Mn(3), one Mn(5), and one Mn(6) atom. In the eighth F site, F(8) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(4), and one Mn(6) atom.