NaPbFe2F9 crystallizes in the monoclinic C2/c space group. Na(1) is bonded to two equivalent F(1), two equivalent F(3), two equivalent F(4), and two equivalent F(5) atoms to form distorted NaF8 hexagonal bipyramids that share corners with two equivalent Fe(2)F6 octahedra, edges with two equivalent Fe(1)F6 octahedra, and edges with two equivalent Fe(2)F6 octahedra. The corner-sharing octahedral tilt angles are 46°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(5) atoms to form FeF6 octahedra that share corners with two equivalent Fe(1)F6 octahedra, corners with two equivalent Fe(2)F6 octahedra, and edges with two equivalent Na(1)F8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 19-45°. In the second Fe site, Fe(2) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form FeF6 octahedra that share corners with two equivalent Na(1)F8 hexagonal bipyramids, corners with two equivalent Fe(1)F6 octahedra, and edges with two equivalent Na(1)F8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 45°. Pb(1) is bonded in a 6-coordinate geometry to two equivalent F(3), two equivalent F(4), and two equivalent F(5) atoms. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Fe(1), and one Fe(2) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to two equivalent Fe(1) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Na(1), one Fe(2), and one Pb(1) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to one Na(1), one Fe(2), and one Pb(1) atom. In the fifth F site, F(5) is bonded in a distorted single-bond geometry to one Na(1), one Fe(1), and one Pb(1) atom.
NaPbFe2F9 crystallizes in the monoclinic C2/c space group. Na(1) is bonded to two equivalent F(1), two equivalent F(3), two equivalent F(4), and two equivalent F(5) atoms to form distorted NaF8 hexagonal bipyramids that share corners with two equivalent Fe(2)F6 octahedra, edges with two equivalent Fe(1)F6 octahedra, and edges with two equivalent Fe(2)F6 octahedra. The corner-sharing octahedral tilt angles are 46°. Both Na(1)-F(1) bond lengths are 2.53 Å. Both Na(1)-F(3) bond lengths are 2.27 Å. Both Na(1)-F(4) bond lengths are 2.80 Å. Both Na(1)-F(5) bond lengths are 2.67 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(5) atoms to form FeF6 octahedra that share corners with two equivalent Fe(1)F6 octahedra, corners with two equivalent Fe(2)F6 octahedra, and edges with two equivalent Na(1)F8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 19-45°. Both Fe(1)-F(1) bond lengths are 1.96 Å. Both Fe(1)-F(2) bond lengths are 1.96 Å. Both Fe(1)-F(5) bond lengths are 1.94 Å. In the second Fe site, Fe(2) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form FeF6 octahedra that share corners with two equivalent Na(1)F8 hexagonal bipyramids, corners with two equivalent Fe(1)F6 octahedra, and edges with two equivalent Na(1)F8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 45°. Both Fe(2)-F(1) bond lengths are 1.99 Å. Both Fe(2)-F(3) bond lengths are 1.95 Å. Both Fe(2)-F(4) bond lengths are 1.95 Å. Pb(1) is bonded in a 6-coordinate geometry to two equivalent F(3), two equivalent F(4), and two equivalent F(5) atoms. Both Pb(1)-F(3) bond lengths are 2.55 Å. Both Pb(1)-F(4) bond lengths are 2.63 Å. Both Pb(1)-F(5) bond lengths are 2.59 Å. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Fe(1), and one Fe(2) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to two equivalent Fe(1) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Na(1), one Fe(2), and one Pb(1) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to one Na(1), one Fe(2), and one Pb(1) atom. In the fifth F site, F(5) is bonded in a distorted single-bond geometry to one Na(1), one Fe(1), and one Pb(1) atom.