Li2MnF4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(4), two equivalent F(1), and three equivalent F(3) atoms to form a mixture of corner and edge-sharing LiF6 octahedra. The corner-sharing octahedral tilt angles range from 52-64°. In the second Li site, Li(2) is bonded to one F(1), two equivalent F(4), and three equivalent F(2) atoms to form a mixture of corner and edge-sharing LiF6 octahedra. The corner-sharing octahedral tilt angles range from 52-64°. Mn(1) is bonded in a 8-coordinate geometry to two equivalent F(1), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Li(2), two equivalent Li(1), and two equivalent Mn(1) atoms. In the second F site, F(2) is bonded to three equivalent Li(2) and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing FLi3Mn2 trigonal bipyramids. In the third F site, F(3) is bonded to three equivalent Li(1) and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing FLi3Mn2 square pyramids. In the fourth F site, F(4) is bonded to one Li(1), two equivalent Li(2), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing FLi3Mn2 trigonal bipyramids.
Li2MnF4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(4), two equivalent F(1), and three equivalent F(3) atoms to form a mixture of corner and edge-sharing LiF6 octahedra. The corner-sharing octahedral tilt angles range from 52-64°. The Li(1)-F(4) bond length is 2.11 Å. Both Li(1)-F(1) bond lengths are 1.92 Å. There is one shorter (2.00 Å) and two longer (2.24 Å) Li(1)-F(3) bond lengths. In the second Li site, Li(2) is bonded to one F(1), two equivalent F(4), and three equivalent F(2) atoms to form a mixture of corner and edge-sharing LiF6 octahedra. The corner-sharing octahedral tilt angles range from 52-64°. The Li(2)-F(1) bond length is 1.90 Å. Both Li(2)-F(4) bond lengths are 2.17 Å. There is one shorter (1.95 Å) and two longer (2.17 Å) Li(2)-F(2) bond lengths. Mn(1) is bonded in a 8-coordinate geometry to two equivalent F(1), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. There is one shorter (2.39 Å) and one longer (2.67 Å) Mn(1)-F(1) bond length. Both Mn(1)-F(2) bond lengths are 2.24 Å. Both Mn(1)-F(3) bond lengths are 2.22 Å. Both Mn(1)-F(4) bond lengths are 2.22 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Li(2), two equivalent Li(1), and two equivalent Mn(1) atoms. In the second F site, F(2) is bonded to three equivalent Li(2) and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing FLi3Mn2 trigonal bipyramids. In the third F site, F(3) is bonded to three equivalent Li(1) and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing FLi3Mn2 square pyramids. In the fourth F site, F(4) is bonded to one Li(1), two equivalent Li(2), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing FLi3Mn2 trigonal bipyramids.