Li4MnOF5 crystallizes in the monoclinic Cm space group. There are eight inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one F(1), one F(8), and two equivalent F(2) atoms. In the second Li site, Li(2) is bonded to one F(1), one F(4), one F(9), and two equivalent F(3) atoms to form LiF5 trigonal bipyramids that share corners with three equivalent Li(2)F5 trigonal bipyramids, corners with three equivalent Li(6)F5 trigonal bipyramids,  an edgeedge with one Li(8)F4 trigonal pyramid, edges with two equivalent Li(3)F4 trigonal pyramids, and edges with two equivalent Li(4)F4 trigonal pyramids. In the third Li site, Li(3) is bonded to one F(3), one F(6), and two equivalent F(1) atoms to form distorted LiF4 trigonal pyramids that share  a cornercorner with one Li(5)OF4 trigonal bipyramid,  a cornercorner with one Li(4)F4 trigonal pyramid, corners with three equivalent Li(3)F4 trigonal pyramids,  an edgeedge with one Li(6)F5 trigonal bipyramid, and edges with two equivalent Li(2)F5 trigonal bipyramids. In the fourth Li site, Li(4) is bonded to one F(3), one F(7), and two equivalent F(4) atoms to form LiF4 trigonal pyramids that share  a cornercorner with one Li(7)F4 tetrahedra,  a cornercorner with one Li(3)F4 trigonal pyramid, corners with three equivalent Li(4)F4 trigonal pyramids, corners with three equivalent Li(8)F4 trigonal pyramids,  an edgeedge with one Li(6)F5 trigonal bipyramid, and edges with two equivalent Li(2)F5 trigonal bipyramids. In the fifth Li site, Li(5) is bonded to one O(2), one F(6), one F(8), and two equivalent F(2) atoms to form distorted LiOF4 trigonal bipyramids that share  a cornercorner with one Li(6)F5 trigonal bipyramid, corners with two equivalent Li(3)F4 trigonal pyramids,  an edgeedge with one Mn(2)O3F2 trigonal bipyramid, and edges with two equivalent Mn(1)O3F2 trigonal bipyramids. In the sixth Li site, Li(6) is bonded to one F(6), one F(7), one F(9), and two equivalent F(3) atoms to form LiF5 trigonal bipyramids that share  a cornercorner with one Li(7)F4 tetrahedra,  a cornercorner with one Li(5)OF4 trigonal bipyramid, corners with six equivalent Li(2)F5 trigonal bipyramids,  an edgeedge with one Li(8)F4 trigonal pyramid, edges with two equivalent Li(3)F4 trigonal pyramids, and edges with two equivalent Li(4)F4 trigonal pyramids. In the seventh Li site, Li(7) is bonded to one F(10), one F(7), and two equivalent F(5) atoms to form LiF4 tetrahedra that share  a cornercorner with one Li(6)F5 trigonal bipyramid,  a cornercorner with one Mn(2)O3F2 trigonal bipyramid, corners with two equivalent Mn(1)O3F2 trigonal bipyramids,  a cornercorner with one Li(8)F4 trigonal pyramid, and corners with two equivalent Li(4)F4 trigonal pyramids. In the eighth Li site, Li(8) is bonded to one F(7), one F(9), and two equivalent F(4) atoms to form LiF4 trigonal pyramids that share  a cornercorner with one Li(7)F4 tetrahedra, corners with six equivalent Li(4)F4 trigonal pyramids,  an edgeedge with one Li(6)F5 trigonal bipyramid, and edges with two equivalent Li(2)F5 trigonal bipyramids. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), two equivalent O(1), one F(2), and one F(5) atom to form MnO3F2 trigonal bipyramids that share  a cornercorner with one Li(7)F4 tetrahedra, corners with three equivalent Mn(1)O3F2 trigonal bipyramids, corners with three equivalent Mn(2)O3F2 trigonal bipyramids, and  an edgeedge with one Li(5)OF4 trigonal bipyramid. In the second Mn site, Mn(2) is bonded to one O(2), two equivalent O(1), one F(10), and one F(8) atom to form MnO3F2 trigonal bipyramids that share  a cornercorner with one Li(7)F4 tetrahedra, corners with six equivalent Mn(1)O3F2 trigonal bipyramids, and  an edgeedge with one Li(5)OF4 trigonal bipyramid. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Mn(2), and two equivalent Mn(1) atoms to form OLiMn3 trigonal pyramids that share corners with three equivalent O(1)LiMn3 trigonal pyramids, corners with three equivalent O(2)LiMn3 trigonal pyramids,  an edgeedge with one F(8)Li3Mn tetrahedra, and edges with two equivalent F(2)Li3Mn tetrahedra. In the second O site, O(2) is bonded to one Li(5), one Mn(2), and two equivalent Mn(1) atoms to form distorted OLiMn3 trigonal pyramids that share corners with six equivalent O(1)LiMn3 trigonal pyramids,  an edgeedge with one F(8)Li3Mn tetrahedra, and edges with two equivalent F(2)Li3Mn tetrahedra. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), and two equivalent Li(3) atoms. In the second F site, F(2) is bonded to one Li(5), two equivalent Li(1), and one Mn(1) atom to form FLi3Mn tetrahedra that share corners with three equivalent F(2)Li3Mn tetrahedra, corners with three equivalent F(8)Li3Mn tetrahedra,  an edgeedge with one O(2)LiMn3 trigonal pyramid, and edges with two equivalent O(1)LiMn3 trigonal pyramids. In the third F site, F(3) is bonded to one Li(3), one Li(4), one Li(6), and two equivalent Li(2) atoms to form FLi5 trigonal bipyramids that share corners with three equivalent F(3)Li5 trigonal bipyramids, corners with three equivalent F(9)Li4 trigonal pyramids,  an edgeedge with one F(7)Li5 trigonal bipyramid, and edges with two equivalent F(4)Li4 trigonal pyramids. In the fourth F site, F(4) is bonded to one Li(2), one Li(8), and two equivalent Li(4) atoms to form FLi4 trigonal pyramids that share corners with three equivalent F(7)Li5 trigonal bipyramids, corners with three equivalent F(4)Li4 trigonal pyramids, edges with two equivalent F(3)Li5 trigonal bipyramids, and  an edgeedge with one F(9)Li4 trigonal pyramid. In the fifth F site, F(5) is bonded in a bent 120 degrees geometry to one Li(7) and one Mn(1) atom. In the sixth F site, F(6) is bonded in a distorted see-saw-like geometry to one Li(5), one Li(6), and two equivalent Li(3) atoms. In the seventh F site, F(7) is bonded to one Li(6), one Li(7), one Li(8), and two equivalent Li(4) atoms to form FLi5 trigonal bipyramids that share corners with six equivalent F(4)Li4 trigonal pyramids, edges with two equivalent F(3)Li5 trigonal bipyramids, and  an edgeedge with one F(9)Li4 trigonal pyramid. In the eighth F site, F(8) is bonded to one Li(5), two equivalent Li(1), and one Mn(2) atom to form FLi3Mn tetrahedra that share corners with six equivalent F(2)Li3Mn tetrahedra,  an edgeedge with one O(2)LiMn3 trigonal pyramid, and edges with two equivalent O(1)LiMn3 trigonal pyramids. In the ninth F site, F(9) is bonded to one Li(6), one Li(8), and two equivalent Li(2) atoms to form FLi4 trigonal pyramids that share corners with six equivalent F(3)Li5 trigonal bipyramids,  an edgeedge with one F(7)Li5 trigonal bipyramid, and edges with two equivalent F(4)Li4 trigonal pyramids. In the tenth F site, F(10) is bonded in a bent 120 degrees geometry to one Li(7) and one Mn(2) atom.
Li4MnOF5 crystallizes in the monoclinic Cm space group. There are eight inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one F(1), one F(8), and two equivalent F(2) atoms. The Li(1)-O(1) bond length is 2.35 Å. The Li(1)-F(1) bond length is 1.83 Å. The Li(1)-F(8) bond length is 1.98 Å. There is one shorter (2.02 Å) and one longer (2.03 Å) Li(1)-F(2) bond length. In the second Li site, Li(2) is bonded to one F(1), one F(4), one F(9), and two equivalent F(3) atoms to form LiF5 trigonal bipyramids that share corners with three equivalent Li(2)F5 trigonal bipyramids, corners with three equivalent Li(6)F5 trigonal bipyramids,  an edgeedge with one Li(8)F4 trigonal pyramid, edges with two equivalent Li(3)F4 trigonal pyramids, and edges with two equivalent Li(4)F4 trigonal pyramids. The Li(2)-F(1) bond length is 2.15 Å. The Li(2)-F(4) bond length is 2.04 Å. The Li(2)-F(9) bond length is 1.92 Å. There is one shorter (2.02 Å) and one longer (2.03 Å) Li(2)-F(3) bond length. In the third Li site, Li(3) is bonded to one F(3), one F(6), and two equivalent F(1) atoms to form distorted LiF4 trigonal pyramids that share  a cornercorner with one Li(5)OF4 trigonal bipyramid,  a cornercorner with one Li(4)F4 trigonal pyramid, corners with three equivalent Li(3)F4 trigonal pyramids,  an edgeedge with one Li(6)F5 trigonal bipyramid, and edges with two equivalent Li(2)F5 trigonal bipyramids. The Li(3)-F(3) bond length is 1.87 Å. The Li(3)-F(6) bond length is 1.87 Å. Both Li(3)-F(1) bond lengths are 1.87 Å. In the fourth Li site, Li(4) is bonded to one F(3), one F(7), and two equivalent F(4) atoms to form LiF4 trigonal pyramids that share  a cornercorner with one Li(7)F4 tetrahedra,  a cornercorner with one Li(3)F4 trigonal pyramid, corners with three equivalent Li(4)F4 trigonal pyramids, corners with three equivalent Li(8)F4 trigonal pyramids,  an edgeedge with one Li(6)F5 trigonal bipyramid, and edges with two equivalent Li(2)F5 trigonal bipyramids. The Li(4)-F(3) bond length is 1.99 Å. The Li(4)-F(7) bond length is 2.07 Å. Both Li(4)-F(4) bond lengths are 1.92 Å. In the fifth Li site, Li(5) is bonded to one O(2), one F(6), one F(8), and two equivalent F(2) atoms to form distorted LiOF4 trigonal bipyramids that share  a cornercorner with one Li(6)F5 trigonal bipyramid, corners with two equivalent Li(3)F4 trigonal pyramids,  an edgeedge with one Mn(2)O3F2 trigonal bipyramid, and edges with two equivalent Mn(1)O3F2 trigonal bipyramids. The Li(5)-O(2) bond length is 2.20 Å. The Li(5)-F(6) bond length is 1.83 Å. The Li(5)-F(8) bond length is 2.03 Å. Both Li(5)-F(2) bond lengths are 2.09 Å. In the sixth Li site, Li(6) is bonded to one F(6), one F(7), one F(9), and two equivalent F(3) atoms to form LiF5 trigonal bipyramids that share  a cornercorner with one Li(7)F4 tetrahedra,  a cornercorner with one Li(5)OF4 trigonal bipyramid, corners with six equivalent Li(2)F5 trigonal bipyramids,  an edgeedge with one Li(8)F4 trigonal pyramid, edges with two equivalent Li(3)F4 trigonal pyramids, and edges with two equivalent Li(4)F4 trigonal pyramids. The Li(6)-F(6) bond length is 2.17 Å. The Li(6)-F(7) bond length is 2.24 Å. The Li(6)-F(9) bond length is 1.88 Å. Both Li(6)-F(3) bond lengths are 1.97 Å. In the seventh Li site, Li(7) is bonded to one F(10), one F(7), and two equivalent F(5) atoms to form LiF4 tetrahedra that share  a cornercorner with one Li(6)F5 trigonal bipyramid,  a cornercorner with one Mn(2)O3F2 trigonal bipyramid, corners with two equivalent Mn(1)O3F2 trigonal bipyramids,  a cornercorner with one Li(8)F4 trigonal pyramid, and corners with two equivalent Li(4)F4 trigonal pyramids. The Li(7)-F(10) bond length is 1.90 Å. The Li(7)-F(7) bond length is 1.84 Å. Both Li(7)-F(5) bond lengths are 1.90 Å. In the eighth Li site, Li(8) is bonded to one F(7), one F(9), and two equivalent F(4) atoms to form LiF4 trigonal pyramids that share  a cornercorner with one Li(7)F4 tetrahedra, corners with six equivalent Li(4)F4 trigonal pyramids,  an edgeedge with one Li(6)F5 trigonal bipyramid, and edges with two equivalent Li(2)F5 trigonal bipyramids. The Li(8)-F(7) bond length is 2.08 Å. The Li(8)-F(9) bond length is 1.96 Å. Both Li(8)-F(4) bond lengths are 1.93 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), two equivalent O(1), one F(2), and one F(5) atom to form MnO3F2 trigonal bipyramids that share  a cornercorner with one Li(7)F4 tetrahedra, corners with three equivalent Mn(1)O3F2 trigonal bipyramids, corners with three equivalent Mn(2)O3F2 trigonal bipyramids, and  an edgeedge with one Li(5)OF4 trigonal bipyramid. The Mn(1)-O(2) bond length is 1.97 Å. There is one shorter (1.96 Å) and one longer (2.00 Å) Mn(1)-O(1) bond length. The Mn(1)-F(2) bond length is 1.98 Å. The Mn(1)-F(5) bond length is 1.85 Å. In the second Mn site, Mn(2) is bonded to one O(2), two equivalent O(1), one F(10), and one F(8) atom to form MnO3F2 trigonal bipyramids that share  a cornercorner with one Li(7)F4 tetrahedra, corners with six equivalent Mn(1)O3F2 trigonal bipyramids, and  an edgeedge with one Li(5)OF4 trigonal bipyramid. The Mn(2)-O(2) bond length is 2.03 Å. Both Mn(2)-O(1) bond lengths are 1.95 Å. The Mn(2)-F(10) bond length is 1.86 Å. The Mn(2)-F(8) bond length is 1.99 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Mn(2), and two equivalent Mn(1) atoms to form OLiMn3 trigonal pyramids that share corners with three equivalent O(1)LiMn3 trigonal pyramids, corners with three equivalent O(2)LiMn3 trigonal pyramids,  an edgeedge with one F(8)Li3Mn tetrahedra, and edges with two equivalent F(2)Li3Mn tetrahedra. In the second O site, O(2) is bonded to one Li(5), one Mn(2), and two equivalent Mn(1) atoms to form distorted OLiMn3 trigonal pyramids that share corners with six equivalent O(1)LiMn3 trigonal pyramids,  an edgeedge with one F(8)Li3Mn tetrahedra, and edges with two equivalent F(2)Li3Mn tetrahedra. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), and two equivalent Li(3) atoms. In the second F site, F(2) is bonded to one Li(5), two equivalent Li(1), and one Mn(1) atom to form FLi3Mn tetrahedra that share corners with three equivalent F(2)Li3Mn tetrahedra, corners with three equivalent F(8)Li3Mn tetrahedra,  an edgeedge with one O(2)LiMn3 trigonal pyramid, and edges with two equivalent O(1)LiMn3 trigonal pyramids. In the third F site, F(3) is bonded to one Li(3), one Li(4), one Li(6), and two equivalent Li(2) atoms to form FLi5 trigonal bipyramids that share corners with three equivalent F(3)Li5 trigonal bipyramids, corners with three equivalent F(9)Li4 trigonal pyramids,  an edgeedge with one F(7)Li5 trigonal bipyramid, and edges with two equivalent F(4)Li4 trigonal pyramids. In the fourth F site, F(4) is bonded to one Li(2), one Li(8), and two equivalent Li(4) atoms to form FLi4 trigonal pyramids that share corners with three equivalent F(7)Li5 trigonal bipyramids, corners with three equivalent F(4)Li4 trigonal pyramids, edges with two equivalent F(3)Li5 trigonal bipyramids, and  an edgeedge with one F(9)Li4 trigonal pyramid. In the fifth F site, F(5) is bonded in a bent 120 degrees geometry to one Li(7) and one Mn(1) atom. In the sixth F site, F(6) is bonded in a distorted see-saw-like geometry to one Li(5), one Li(6), and two equivalent Li(3) atoms. In the seventh F site, F(7) is bonded to one Li(6), one Li(7), one Li(8), and two equivalent Li(4) atoms to form FLi5 trigonal bipyramids that share corners with six equivalent F(4)Li4 trigonal pyramids, edges with two equivalent F(3)Li5 trigonal bipyramids, and  an edgeedge with one F(9)Li4 trigonal pyramid. In the eighth F site, F(8) is bonded to one Li(5), two equivalent Li(1), and one Mn(2) atom to form FLi3Mn tetrahedra that share corners with six equivalent F(2)Li3Mn tetrahedra,  an edgeedge with one O(2)LiMn3 trigonal pyramid, and edges with two equivalent O(1)LiMn3 trigonal pyramids. In the ninth F site, F(9) is bonded to one Li(6), one Li(8), and two equivalent Li(2) atoms to form FLi4 trigonal pyramids that share corners with six equivalent F(3)Li5 trigonal bipyramids,  an edgeedge with one F(7)Li5 trigonal bipyramid, and edges with two equivalent F(4)Li4 trigonal pyramids. In the tenth F site, F(10) is bonded in a bent 120 degrees geometry to one Li(7) and one Mn(2) atom.