Li3MnF5 crystallizes in the orthorhombic P2_12_12_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one F(1), one F(3), one F(4), and two equivalent F(2) atoms. In the second Li site, Li(2) is bonded in a distorted see-saw-like geometry to one F(1), one F(3), one F(4), and one F(5) atom. In the third Li site, Li(3) is bonded to one F(2), one F(3), one F(4), and two equivalent F(5) atoms to form distorted LiF5 trigonal bipyramids that share corners with six equivalent Mn(1)F7 pentagonal bipyramids and corners with two equivalent Li(3)F5 trigonal bipyramids. Mn(1) is bonded to one F(2), one F(4), one F(5), two equivalent F(1), and two equivalent F(3) atoms to form distorted MnF7 pentagonal bipyramids that share corners with six equivalent Li(3)F5 trigonal bipyramids and edges with two equivalent Mn(1)F7 pentagonal bipyramids. There are five inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), and two equivalent Mn(1) atoms to form distorted FLi2Mn2 trigonal pyramids that share corners with two equivalent F(1)Li2Mn2 trigonal pyramids and corners with four equivalent F(2)Li3Mn trigonal pyramids. In the second F site, F(2) is bonded to one Li(3), two equivalent Li(1), and one Mn(1) atom to form distorted FLi3Mn trigonal pyramids that share corners with two equivalent F(2)Li3Mn trigonal pyramids and corners with four equivalent F(1)Li2Mn2 trigonal pyramids. In the third F site, F(3) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), and two equivalent Mn(1) atoms. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Mn(1) atom. In the fifth F site, F(5) is bonded in a distorted see-saw-like geometry to one Li(2), two equivalent Li(3), and one Mn(1) atom.
Li3MnF5 crystallizes in the orthorhombic P2_12_12_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one F(1), one F(3), one F(4), and two equivalent F(2) atoms. The Li(1)-F(1) bond length is 1.95 Å. The Li(1)-F(3) bond length is 2.13 Å. The Li(1)-F(4) bond length is 2.18 Å. There is one shorter (1.95 Å) and one longer (1.99 Å) Li(1)-F(2) bond length. In the second Li site, Li(2) is bonded in a distorted see-saw-like geometry to one F(1), one F(3), one F(4), and one F(5) atom. The Li(2)-F(1) bond length is 2.01 Å. The Li(2)-F(3) bond length is 2.07 Å. The Li(2)-F(4) bond length is 1.89 Å. The Li(2)-F(5) bond length is 1.98 Å. In the third Li site, Li(3) is bonded to one F(2), one F(3), one F(4), and two equivalent F(5) atoms to form distorted LiF5 trigonal bipyramids that share corners with six equivalent Mn(1)F7 pentagonal bipyramids and corners with two equivalent Li(3)F5 trigonal bipyramids. The Li(3)-F(2) bond length is 1.91 Å. The Li(3)-F(3) bond length is 2.26 Å. The Li(3)-F(4) bond length is 1.97 Å. There is one shorter (1.96 Å) and one longer (2.14 Å) Li(3)-F(5) bond length. Mn(1) is bonded to one F(2), one F(4), one F(5), two equivalent F(1), and two equivalent F(3) atoms to form distorted MnF7 pentagonal bipyramids that share corners with six equivalent Li(3)F5 trigonal bipyramids and edges with two equivalent Mn(1)F7 pentagonal bipyramids. The Mn(1)-F(2) bond length is 2.08 Å. The Mn(1)-F(4) bond length is 2.26 Å. The Mn(1)-F(5) bond length is 2.12 Å. There is one shorter (2.18 Å) and one longer (2.26 Å) Mn(1)-F(1) bond length. There is one shorter (2.32 Å) and one longer (2.39 Å) Mn(1)-F(3) bond length. There are five inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), and two equivalent Mn(1) atoms to form distorted FLi2Mn2 trigonal pyramids that share corners with two equivalent F(1)Li2Mn2 trigonal pyramids and corners with four equivalent F(2)Li3Mn trigonal pyramids. In the second F site, F(2) is bonded to one Li(3), two equivalent Li(1), and one Mn(1) atom to form distorted FLi3Mn trigonal pyramids that share corners with two equivalent F(2)Li3Mn trigonal pyramids and corners with four equivalent F(1)Li2Mn2 trigonal pyramids. In the third F site, F(3) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), and two equivalent Mn(1) atoms. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Mn(1) atom. In the fifth F site, F(5) is bonded in a distorted see-saw-like geometry to one Li(2), two equivalent Li(3), and one Mn(1) atom.