NaMnF4 is zeta iron carbide-derived structured and crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form NaF6 octahedra that share corners with four equivalent Na(1)F6 octahedra, corners with four equivalent Mn(1)F6 octahedra, and edges with two equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-65°. Mn(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form MnF6 octahedra that share corners with four equivalent Na(1)F6 octahedra, corners with four equivalent Mn(1)F6 octahedra, and edges with two equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 41-55°. There are two inequivalent F sites. In the first F site, F(2) is bonded in a distorted trigonal planar geometry to one Na(1) and two equivalent Mn(1) atoms. In the second F site, F(1) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one Mn(1) atom.
NaMnF4 is zeta iron carbide-derived structured and crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form NaF6 octahedra that share corners with four equivalent Na(1)F6 octahedra, corners with four equivalent Mn(1)F6 octahedra, and edges with two equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-65°. Both Na(1)-F(2) bond lengths are 2.34 Å. There are two shorter (2.22 Å) and two longer (2.27 Å) Na(1)-F(1) bond lengths. Mn(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form MnF6 octahedra that share corners with four equivalent Na(1)F6 octahedra, corners with four equivalent Mn(1)F6 octahedra, and edges with two equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 41-55°. Both Mn(1)-F(1) bond lengths are 1.83 Å. There are two shorter (1.88 Å) and two longer (2.15 Å) Mn(1)-F(2) bond lengths. There are two inequivalent F sites. In the first F site, F(2) is bonded in a distorted trigonal planar geometry to one Na(1) and two equivalent Mn(1) atoms. In the second F site, F(1) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one Mn(1) atom.