LiMn3OF8 crystallizes in the monoclinic Pc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(11), one F(3), one F(5), and one F(6) atom to form LiF4 tetrahedra that share  a cornercorner with one Mn(2)OF5 octahedra,  a cornercorner with one Mn(3)OF5 octahedra, corners with two equivalent Mn(6)F6 octahedra, and  an edgeedge with one Mn(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 33-69°. In the second Li site, Li(2) is bonded to one F(10), one F(15), one F(16), and one F(4) atom to form LiF4 tetrahedra that share  a cornercorner with one Mn(5)F6 octahedra,  a cornercorner with one Mn(6)F6 octahedra, corners with two equivalent Mn(3)OF5 octahedra, and  an edgeedge with one Mn(5)F6 octahedra. The corner-sharing octahedral tilt angles range from 38-69°. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one F(14), one F(7), and one F(8) atom. In the second Mn site, Mn(2) is bonded to one O(1), one F(1), one F(11), one F(3), one F(6), and one F(8) atom to form MnOF5 octahedra that share corners with four equivalent Mn(6)F6 octahedra,  a cornercorner with one Li(1)F4 tetrahedra, and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 39-46°. In the third Mn site, Mn(3) is bonded to one O(2), one F(10), one F(2), one F(4), one F(5), and one F(9) atom to form MnOF5 octahedra that share corners with four equivalent Mn(5)F6 octahedra,  a cornercorner with one Li(1)F4 tetrahedra, and corners with two equivalent Li(2)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-44°. In the fourth Mn site, Mn(4) is bonded in a 5-coordinate geometry to one O(1), one O(2), one F(12), one F(13), and one F(7) atom. In the fifth Mn site, Mn(5) is bonded to one F(10), one F(13), one F(16), one F(2), one F(4), and one F(9) atom to form MnF6 octahedra that share corners with four equivalent Mn(3)OF5 octahedra,  a cornercorner with one Li(2)F4 tetrahedra, and  an edgeedge with one Li(2)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-44°. In the sixth Mn site, Mn(6) is bonded to one F(1), one F(11), one F(12), one F(15), one F(3), and one F(8) atom to form MnF6 octahedra that share corners with four equivalent Mn(2)OF5 octahedra,  a cornercorner with one Li(2)F4 tetrahedra, and corners with two equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 39-46°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(2), and one Mn(4) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(3), and one Mn(4) atom. There are sixteen inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Mn(2) and one Mn(6) atom. In the second F site, F(2) is bonded in a 2-coordinate geometry to one Mn(3) and one Mn(5) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(2), and one Mn(6) atom. In the fourth F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Mn(3), and one Mn(5) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one Li(1) and one Mn(3) atom. In the sixth F site, F(6) is bonded in a bent 120 degrees geometry to one Li(1) and one Mn(2) atom. In the seventh F site, F(7) is bonded in a linear geometry to one Mn(1) and one Mn(4) atom. In the eighth F site, F(8) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(2), and one Mn(6) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one Mn(3) and one Mn(5) atom. In the tenth F site, F(10) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(3), and one Mn(5) atom. In the eleventh F site, F(11) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Mn(2), and one Mn(6) atom. In the twelfth F site, F(12) is bonded in a bent 120 degrees geometry to one Mn(4) and one Mn(6) atom. In the thirteenth F site, F(13) is bonded in a bent 120 degrees geometry to one Mn(4) and one Mn(5) atom. In the fourteenth F site, F(14) is bonded in a single-bond geometry to one Mn(1) atom. In the fifteenth F site, F(15) is bonded in a bent 150 degrees geometry to one Li(2) and one Mn(6) atom. In the sixteenth F site, F(16) is bonded in a bent 120 degrees geometry to one Li(2) and one Mn(5) atom.
LiMn3OF8 crystallizes in the monoclinic Pc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(11), one F(3), one F(5), and one F(6) atom to form LiF4 tetrahedra that share  a cornercorner with one Mn(2)OF5 octahedra,  a cornercorner with one Mn(3)OF5 octahedra, corners with two equivalent Mn(6)F6 octahedra, and  an edgeedge with one Mn(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 33-69°. The Li(1)-F(11) bond length is 2.05 Å. The Li(1)-F(3) bond length is 2.00 Å. The Li(1)-F(5) bond length is 1.84 Å. The Li(1)-F(6) bond length is 1.90 Å. In the second Li site, Li(2) is bonded to one F(10), one F(15), one F(16), and one F(4) atom to form LiF4 tetrahedra that share  a cornercorner with one Mn(5)F6 octahedra,  a cornercorner with one Mn(6)F6 octahedra, corners with two equivalent Mn(3)OF5 octahedra, and  an edgeedge with one Mn(5)F6 octahedra. The corner-sharing octahedral tilt angles range from 38-69°. The Li(2)-F(10) bond length is 1.98 Å. The Li(2)-F(15) bond length is 1.88 Å. The Li(2)-F(16) bond length is 1.90 Å. The Li(2)-F(4) bond length is 2.06 Å. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one F(14), one F(7), and one F(8) atom. The Mn(1)-O(1) bond length is 1.86 Å. The Mn(1)-O(2) bond length is 1.91 Å. The Mn(1)-F(14) bond length is 1.82 Å. The Mn(1)-F(7) bond length is 1.87 Å. The Mn(1)-F(8) bond length is 2.24 Å. In the second Mn site, Mn(2) is bonded to one O(1), one F(1), one F(11), one F(3), one F(6), and one F(8) atom to form MnOF5 octahedra that share corners with four equivalent Mn(6)F6 octahedra,  a cornercorner with one Li(1)F4 tetrahedra, and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 39-46°. The Mn(2)-O(1) bond length is 1.91 Å. The Mn(2)-F(1) bond length is 2.12 Å. The Mn(2)-F(11) bond length is 1.94 Å. The Mn(2)-F(3) bond length is 2.26 Å. The Mn(2)-F(6) bond length is 1.86 Å. The Mn(2)-F(8) bond length is 1.96 Å. In the third Mn site, Mn(3) is bonded to one O(2), one F(10), one F(2), one F(4), one F(5), and one F(9) atom to form MnOF5 octahedra that share corners with four equivalent Mn(5)F6 octahedra,  a cornercorner with one Li(1)F4 tetrahedra, and corners with two equivalent Li(2)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-44°. The Mn(3)-O(2) bond length is 1.93 Å. The Mn(3)-F(10) bond length is 1.93 Å. The Mn(3)-F(2) bond length is 2.21 Å. The Mn(3)-F(4) bond length is 2.24 Å. The Mn(3)-F(5) bond length is 1.88 Å. The Mn(3)-F(9) bond length is 1.90 Å. In the fourth Mn site, Mn(4) is bonded in a 5-coordinate geometry to one O(1), one O(2), one F(12), one F(13), and one F(7) atom. The Mn(4)-O(1) bond length is 2.09 Å. The Mn(4)-O(2) bond length is 2.12 Å. The Mn(4)-F(12) bond length is 2.12 Å. The Mn(4)-F(13) bond length is 2.04 Å. The Mn(4)-F(7) bond length is 2.03 Å. In the fifth Mn site, Mn(5) is bonded to one F(10), one F(13), one F(16), one F(2), one F(4), and one F(9) atom to form MnF6 octahedra that share corners with four equivalent Mn(3)OF5 octahedra,  a cornercorner with one Li(2)F4 tetrahedra, and  an edgeedge with one Li(2)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-44°. The Mn(5)-F(10) bond length is 2.20 Å. The Mn(5)-F(13) bond length is 1.90 Å. The Mn(5)-F(16) bond length is 1.85 Å. The Mn(5)-F(2) bond length is 1.90 Å. The Mn(5)-F(4) bond length is 1.93 Å. The Mn(5)-F(9) bond length is 2.10 Å. In the sixth Mn site, Mn(6) is bonded to one F(1), one F(11), one F(12), one F(15), one F(3), and one F(8) atom to form MnF6 octahedra that share corners with four equivalent Mn(2)OF5 octahedra,  a cornercorner with one Li(2)F4 tetrahedra, and corners with two equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 39-46°. The Mn(6)-F(1) bond length is 1.89 Å. The Mn(6)-F(11) bond length is 2.18 Å. The Mn(6)-F(12) bond length is 1.91 Å. The Mn(6)-F(15) bond length is 1.85 Å. The Mn(6)-F(3) bond length is 1.91 Å. The Mn(6)-F(8) bond length is 2.25 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(2), and one Mn(4) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(3), and one Mn(4) atom. There are sixteen inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Mn(2) and one Mn(6) atom. In the second F site, F(2) is bonded in a 2-coordinate geometry to one Mn(3) and one Mn(5) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(2), and one Mn(6) atom. In the fourth F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Mn(3), and one Mn(5) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one Li(1) and one Mn(3) atom. In the sixth F site, F(6) is bonded in a bent 120 degrees geometry to one Li(1) and one Mn(2) atom. In the seventh F site, F(7) is bonded in a linear geometry to one Mn(1) and one Mn(4) atom. In the eighth F site, F(8) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(2), and one Mn(6) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one Mn(3) and one Mn(5) atom. In the tenth F site, F(10) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(3), and one Mn(5) atom. In the eleventh F site, F(11) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Mn(2), and one Mn(6) atom. In the twelfth F site, F(12) is bonded in a bent 120 degrees geometry to one Mn(4) and one Mn(6) atom. In the thirteenth F site, F(13) is bonded in a bent 120 degrees geometry to one Mn(4) and one Mn(5) atom. In the fourteenth F site, F(14) is bonded in a single-bond geometry to one Mn(1) atom. In the fifteenth F site, F(15) is bonded in a bent 150 degrees geometry to one Li(2) and one Mn(6) atom. In the sixteenth F site, F(16) is bonded in a bent 120 degrees geometry to one Li(2) and one Mn(5) atom.