LiMnF4 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(4), one F(5), and one F(8) atom to form LiF4 tetrahedra that share corners with two equivalent Mn(1)F6 octahedra, corners with two equivalent Mn(2)F6 octahedra, and corners with two equivalent Mn(3)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 13-66°. In the second Li site, Li(2) is bonded to one F(10), one F(2), one F(3), and one F(9) atom to form LiF4 tetrahedra that share corners with two equivalent Mn(1)F6 octahedra, corners with three equivalent Mn(2)F6 octahedra, and  a cornercorner with one Mn(3)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 42-59°. In the third Li site, Li(3) is bonded to one F(11), one F(12), one F(6), and one F(7) atom to form LiF4 tetrahedra that share  a cornercorner with one Mn(2)F6 octahedra, corners with two equivalent Mn(1)F6 octahedra, and corners with two equivalent Mn(3)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 14-55°. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one F(1), one F(11), one F(12), one F(4), and two equivalent F(3) atoms to form MnF6 octahedra that share corners with two equivalent Li(1)F4 tetrahedra, corners with two equivalent Li(2)F4 tetrahedra, corners with two equivalent Li(3)F4 tetrahedra,  an edgeedge with one Mn(1)F6 octahedra, and  an edgeedge with one Mn(3)F5 trigonal bipyramid. In the second Mn site, Mn(2) is bonded to one F(10), one F(2), one F(5), one F(6), one F(8), and one F(9) atom to form distorted MnF6 octahedra that share  a cornercorner with one Li(3)F4 tetrahedra, corners with two equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(2)F4 tetrahedra, and  an edgeedge with one Mn(3)F5 trigonal bipyramid. In the third Mn site, Mn(3) is bonded to one F(10), one F(11), one F(4), one F(5), and one F(7) atom to form MnF5 trigonal bipyramids that share  a cornercorner with one Li(2)F4 tetrahedra, corners with two equivalent Li(1)F4 tetrahedra, corners with two equivalent Li(3)F4 tetrahedra,  an edgeedge with one Mn(1)F6 octahedra, and  an edgeedge with one Mn(2)F6 octahedra. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one Li(1) and one Mn(1) atom. In the second F site, F(2) is bonded in a distorted bent 120 degrees geometry to one Li(2) and one Mn(2) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(2) and two equivalent Mn(1) atoms. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one Mn(3) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Li(1), one Mn(2), and one Mn(3) atom. In the sixth F site, F(6) is bonded in a linear geometry to one Li(3) and one Mn(2) atom. In the seventh F site, F(7) is bonded in a linear geometry to one Li(3) and one Mn(3) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one Li(1) and one Mn(2) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one Li(2) and one Mn(2) atom. In the tenth F site, F(10) is bonded in a trigonal planar geometry to one Li(2), one Mn(2), and one Mn(3) atom. In the eleventh F site, F(11) is bonded in a trigonal planar geometry to one Li(3), one Mn(1), and one Mn(3) atom. In the twelfth F site, F(12) is bonded in a bent 150 degrees geometry to one Li(3) and one Mn(1) atom.
LiMnF4 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(4), one F(5), and one F(8) atom to form LiF4 tetrahedra that share corners with two equivalent Mn(1)F6 octahedra, corners with two equivalent Mn(2)F6 octahedra, and corners with two equivalent Mn(3)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 13-66°. The Li(1)-F(1) bond length is 1.89 Å. The Li(1)-F(4) bond length is 1.96 Å. The Li(1)-F(5) bond length is 1.95 Å. The Li(1)-F(8) bond length is 1.84 Å. In the second Li site, Li(2) is bonded to one F(10), one F(2), one F(3), and one F(9) atom to form LiF4 tetrahedra that share corners with two equivalent Mn(1)F6 octahedra, corners with three equivalent Mn(2)F6 octahedra, and  a cornercorner with one Mn(3)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 42-59°. The Li(2)-F(10) bond length is 1.96 Å. The Li(2)-F(2) bond length is 1.82 Å. The Li(2)-F(3) bond length is 1.98 Å. The Li(2)-F(9) bond length is 1.81 Å. In the third Li site, Li(3) is bonded to one F(11), one F(12), one F(6), and one F(7) atom to form LiF4 tetrahedra that share  a cornercorner with one Mn(2)F6 octahedra, corners with two equivalent Mn(1)F6 octahedra, and corners with two equivalent Mn(3)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 14-55°. The Li(3)-F(11) bond length is 2.11 Å. The Li(3)-F(12) bond length is 1.92 Å. The Li(3)-F(6) bond length is 1.89 Å. The Li(3)-F(7) bond length is 1.93 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one F(1), one F(11), one F(12), one F(4), and two equivalent F(3) atoms to form MnF6 octahedra that share corners with two equivalent Li(1)F4 tetrahedra, corners with two equivalent Li(2)F4 tetrahedra, corners with two equivalent Li(3)F4 tetrahedra,  an edgeedge with one Mn(1)F6 octahedra, and  an edgeedge with one Mn(3)F5 trigonal bipyramid. The Mn(1)-F(1) bond length is 1.83 Å. The Mn(1)-F(11) bond length is 1.95 Å. The Mn(1)-F(12) bond length is 1.84 Å. The Mn(1)-F(4) bond length is 2.26 Å. There is one shorter (1.95 Å) and one longer (2.18 Å) Mn(1)-F(3) bond length. In the second Mn site, Mn(2) is bonded to one F(10), one F(2), one F(5), one F(6), one F(8), and one F(9) atom to form distorted MnF6 octahedra that share  a cornercorner with one Li(3)F4 tetrahedra, corners with two equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(2)F4 tetrahedra, and  an edgeedge with one Mn(3)F5 trigonal bipyramid. The Mn(2)-F(10) bond length is 2.19 Å. The Mn(2)-F(2) bond length is 1.91 Å. The Mn(2)-F(5) bond length is 2.39 Å. The Mn(2)-F(6) bond length is 1.85 Å. The Mn(2)-F(8) bond length is 1.85 Å. The Mn(2)-F(9) bond length is 1.91 Å. In the third Mn site, Mn(3) is bonded to one F(10), one F(11), one F(4), one F(5), and one F(7) atom to form MnF5 trigonal bipyramids that share  a cornercorner with one Li(2)F4 tetrahedra, corners with two equivalent Li(1)F4 tetrahedra, corners with two equivalent Li(3)F4 tetrahedra,  an edgeedge with one Mn(1)F6 octahedra, and  an edgeedge with one Mn(2)F6 octahedra. The Mn(3)-F(10) bond length is 1.90 Å. The Mn(3)-F(11) bond length is 2.18 Å. The Mn(3)-F(4) bond length is 1.89 Å. The Mn(3)-F(5) bond length is 1.86 Å. The Mn(3)-F(7) bond length is 1.82 Å. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one Li(1) and one Mn(1) atom. In the second F site, F(2) is bonded in a distorted bent 120 degrees geometry to one Li(2) and one Mn(2) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(2) and two equivalent Mn(1) atoms. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one Mn(3) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Li(1), one Mn(2), and one Mn(3) atom. In the sixth F site, F(6) is bonded in a linear geometry to one Li(3) and one Mn(2) atom. In the seventh F site, F(7) is bonded in a linear geometry to one Li(3) and one Mn(3) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one Li(1) and one Mn(2) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one Li(2) and one Mn(2) atom. In the tenth F site, F(10) is bonded in a trigonal planar geometry to one Li(2), one Mn(2), and one Mn(3) atom. In the eleventh F site, F(11) is bonded in a trigonal planar geometry to one Li(3), one Mn(1), and one Mn(3) atom. In the twelfth F site, F(12) is bonded in a bent 150 degrees geometry to one Li(3) and one Mn(1) atom.