LiMnOF2 crystallizes in the monoclinic Pc space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(7), and two equivalent F(1) atoms to form LiOF3 tetrahedra that share  a cornercorner with one Mn(2)O4F2 octahedra,  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Mn(4)F6 octahedra,  a cornercorner with one Mn(3)F6 pentagonal pyramid, corners with two equivalent Li(1)OF3 tetrahedra, and  an edgeedge with one Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 18-59°. In the second Li site, Li(2) is bonded to one O(3), one F(4), and two equivalent F(2) atoms to form LiOF3 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Mn(4)F6 octahedra, corners with three equivalent Mn(2)O4F2 octahedra,  a cornercorner with one Mn(3)F6 pentagonal pyramid, and corners with two equivalent Li(2)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 51-60°. In the third Li site, Li(3) is bonded to one O(4), one F(5), and two equivalent F(3) atoms to form LiOF3 tetrahedra that share  a cornercorner with one Mn(4)F6 octahedra,  a cornercorner with one Mn(2)O4F2 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with three equivalent Mn(3)F6 pentagonal pyramids, and corners with two equivalent Li(3)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 53-65°. In the fourth Li site, Li(4) is bonded to one O(2), one F(8), and two equivalent F(6) atoms to form LiOF3 tetrahedra that share  a cornercorner with one Mn(4)F6 octahedra,  a cornercorner with one Mn(2)O4F2 octahedra, corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one Mn(3)F6 pentagonal pyramid, corners with two equivalent Li(4)OF3 tetrahedra, and  an edgeedge with one Mn(3)F6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 28-62°. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)OF3 tetrahedra,  a cornercorner with one Li(2)OF3 tetrahedra, corners with two equivalent Li(3)OF3 tetrahedra, corners with two equivalent Li(4)OF3 tetrahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with three equivalent Mn(2)O4F2 octahedra. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form MnO4F2 octahedra that share  a cornercorner with one Li(1)OF3 tetrahedra,  a cornercorner with one Li(3)OF3 tetrahedra,  a cornercorner with one Li(4)OF3 tetrahedra, corners with three equivalent Li(2)OF3 tetrahedra, edges with three equivalent Mn(1)O6 octahedra, and  an edgeedge with one Li(1)OF3 tetrahedra. In the third Mn site, Mn(3) is bonded to one F(3), one F(4), one F(5), one F(6), one F(7), and one F(8) atom to form distorted MnF6 pentagonal pyramids that share  a cornercorner with one Li(1)OF3 tetrahedra,  a cornercorner with one Li(2)OF3 tetrahedra,  a cornercorner with one Li(4)OF3 tetrahedra, corners with three equivalent Li(3)OF3 tetrahedra, edges with three equivalent Mn(4)F6 octahedra, and  an edgeedge with one Li(4)OF3 tetrahedra. In the fourth Mn site, Mn(4) is bonded to one F(5), one F(8), two equivalent F(4), and two equivalent F(7) atoms to form MnF6 octahedra that share  a cornercorner with one Li(3)OF3 tetrahedra,  a cornercorner with one Li(4)OF3 tetrahedra, corners with two equivalent Li(1)OF3 tetrahedra, corners with two equivalent Li(2)OF3 tetrahedra, edges with two equivalent Mn(4)F6 octahedra, and edges with three equivalent Mn(3)F6 pentagonal pyramids. There are four inequivalent O sites. In the first O site, O(1) is bonded in a T-shaped geometry to one Li(1), one Mn(1), and one Mn(2) atom. In the second O site, O(2) is bonded to one Li(4), one Mn(2), and two equivalent Mn(1) atoms to form a mixture of distorted edge and corner-sharing OLiMn3 tetrahedra. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(2), one Mn(1), and one Mn(2) atom. In the fourth O site, O(4) is bonded to one Li(3), one Mn(2), and two equivalent Mn(1) atoms to form a mixture of distorted edge and corner-sharing OLiMn3 tetrahedra. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a T-shaped geometry to two equivalent Li(1) and one Mn(2) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to two equivalent Li(2) and one Mn(2) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to two equivalent Li(3) and one Mn(3) atom. In the fourth F site, F(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Mn(3), and two equivalent Mn(4) atoms. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(3), one Mn(3), and one Mn(4) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to two equivalent Li(4) and one Mn(3) atom. In the seventh F site, F(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(3), and two equivalent Mn(4) atoms. In the eighth F site, F(8) is bonded in a T-shaped geometry to one Li(4), one Mn(3), and one Mn(4) atom.
LiMnOF2 crystallizes in the monoclinic Pc space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(7), and two equivalent F(1) atoms to form LiOF3 tetrahedra that share  a cornercorner with one Mn(2)O4F2 octahedra,  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Mn(4)F6 octahedra,  a cornercorner with one Mn(3)F6 pentagonal pyramid, corners with two equivalent Li(1)OF3 tetrahedra, and  an edgeedge with one Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 18-59°. The Li(1)-O(1) bond length is 1.95 Å. The Li(1)-F(7) bond length is 1.99 Å. There is one shorter (1.95 Å) and one longer (2.01 Å) Li(1)-F(1) bond length. In the second Li site, Li(2) is bonded to one O(3), one F(4), and two equivalent F(2) atoms to form LiOF3 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Mn(4)F6 octahedra, corners with three equivalent Mn(2)O4F2 octahedra,  a cornercorner with one Mn(3)F6 pentagonal pyramid, and corners with two equivalent Li(2)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 51-60°. The Li(2)-O(3) bond length is 1.98 Å. The Li(2)-F(4) bond length is 2.04 Å. There is one shorter (1.96 Å) and one longer (1.98 Å) Li(2)-F(2) bond length. In the third Li site, Li(3) is bonded to one O(4), one F(5), and two equivalent F(3) atoms to form LiOF3 tetrahedra that share  a cornercorner with one Mn(4)F6 octahedra,  a cornercorner with one Mn(2)O4F2 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with three equivalent Mn(3)F6 pentagonal pyramids, and corners with two equivalent Li(3)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 53-65°. The Li(3)-O(4) bond length is 1.98 Å. The Li(3)-F(5) bond length is 1.87 Å. There is one shorter (1.84 Å) and one longer (1.86 Å) Li(3)-F(3) bond length. In the fourth Li site, Li(4) is bonded to one O(2), one F(8), and two equivalent F(6) atoms to form LiOF3 tetrahedra that share  a cornercorner with one Mn(4)F6 octahedra,  a cornercorner with one Mn(2)O4F2 octahedra, corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one Mn(3)F6 pentagonal pyramid, corners with two equivalent Li(4)OF3 tetrahedra, and  an edgeedge with one Mn(3)F6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 28-62°. The Li(4)-O(2) bond length is 1.96 Å. The Li(4)-F(8) bond length is 1.88 Å. There is one shorter (1.80 Å) and one longer (1.86 Å) Li(4)-F(6) bond length. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)OF3 tetrahedra,  a cornercorner with one Li(2)OF3 tetrahedra, corners with two equivalent Li(3)OF3 tetrahedra, corners with two equivalent Li(4)OF3 tetrahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with three equivalent Mn(2)O4F2 octahedra. The Mn(1)-O(1) bond length is 1.85 Å. The Mn(1)-O(3) bond length is 1.87 Å. There is one shorter (1.98 Å) and one longer (2.07 Å) Mn(1)-O(2) bond length. There is one shorter (2.01 Å) and one longer (2.03 Å) Mn(1)-O(4) bond length. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form MnO4F2 octahedra that share  a cornercorner with one Li(1)OF3 tetrahedra,  a cornercorner with one Li(3)OF3 tetrahedra,  a cornercorner with one Li(4)OF3 tetrahedra, corners with three equivalent Li(2)OF3 tetrahedra, edges with three equivalent Mn(1)O6 octahedra, and  an edgeedge with one Li(1)OF3 tetrahedra. The Mn(2)-O(1) bond length is 1.91 Å. The Mn(2)-O(2) bond length is 1.93 Å. The Mn(2)-O(3) bond length is 1.92 Å. The Mn(2)-O(4) bond length is 1.93 Å. The Mn(2)-F(1) bond length is 1.95 Å. The Mn(2)-F(2) bond length is 1.96 Å. In the third Mn site, Mn(3) is bonded to one F(3), one F(4), one F(5), one F(6), one F(7), and one F(8) atom to form distorted MnF6 pentagonal pyramids that share  a cornercorner with one Li(1)OF3 tetrahedra,  a cornercorner with one Li(2)OF3 tetrahedra,  a cornercorner with one Li(4)OF3 tetrahedra, corners with three equivalent Li(3)OF3 tetrahedra, edges with three equivalent Mn(4)F6 octahedra, and  an edgeedge with one Li(4)OF3 tetrahedra. The Mn(3)-F(3) bond length is 2.04 Å. The Mn(3)-F(4) bond length is 2.41 Å. The Mn(3)-F(5) bond length is 2.06 Å. The Mn(3)-F(6) bond length is 2.00 Å. The Mn(3)-F(7) bond length is 2.41 Å. The Mn(3)-F(8) bond length is 2.15 Å. In the fourth Mn site, Mn(4) is bonded to one F(5), one F(8), two equivalent F(4), and two equivalent F(7) atoms to form MnF6 octahedra that share  a cornercorner with one Li(3)OF3 tetrahedra,  a cornercorner with one Li(4)OF3 tetrahedra, corners with two equivalent Li(1)OF3 tetrahedra, corners with two equivalent Li(2)OF3 tetrahedra, edges with two equivalent Mn(4)F6 octahedra, and edges with three equivalent Mn(3)F6 pentagonal pyramids. The Mn(4)-F(5) bond length is 2.07 Å. The Mn(4)-F(8) bond length is 2.03 Å. Both Mn(4)-F(4) bond lengths are 2.16 Å. There is one shorter (2.14 Å) and one longer (2.22 Å) Mn(4)-F(7) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded in a T-shaped geometry to one Li(1), one Mn(1), and one Mn(2) atom. In the second O site, O(2) is bonded to one Li(4), one Mn(2), and two equivalent Mn(1) atoms to form a mixture of distorted edge and corner-sharing OLiMn3 tetrahedra. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(2), one Mn(1), and one Mn(2) atom. In the fourth O site, O(4) is bonded to one Li(3), one Mn(2), and two equivalent Mn(1) atoms to form a mixture of distorted edge and corner-sharing OLiMn3 tetrahedra. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a T-shaped geometry to two equivalent Li(1) and one Mn(2) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to two equivalent Li(2) and one Mn(2) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to two equivalent Li(3) and one Mn(3) atom. In the fourth F site, F(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Mn(3), and two equivalent Mn(4) atoms. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(3), one Mn(3), and one Mn(4) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to two equivalent Li(4) and one Mn(3) atom. In the seventh F site, F(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(3), and two equivalent Mn(4) atoms. In the eighth F site, F(8) is bonded in a T-shaped geometry to one Li(4), one Mn(3), and one Mn(4) atom.