The solvent-free reaction of 5-fluorobenzimidazole (FbimH) and ferrocene, adapting a previously described method for the preparation of iron azolates, yields colorless crystals of around 400 μm in size (Fig. ). Structure determination through single crystal X-ray diffraction reveals a laminar material of formula [Fe(Fbim)2], denoted as MUV-1-F (MUV = Material of the University of Valencia), consisting in distorted tetrahedral Fe(II) centers connected by Fbim -bridges, thus forming a neutral layered coordination polymer extended in the ab plane (Fig. ), as also found in the isostructural systems MUV-1-X. The inner part of the layers, i.e. the core, is composed by Fe(II) centres which are "sandwiched" by benzimidazoles, which serve as an organic protection, resulting in a stable and robust material. In each layer the Fe(II) centers form a square lattice with a metal-metal distance of 5.9 Å (Fig. ). The metal centers are connected via benzimidazolate, which coordinate with the two nitrogen heteroatoms, each to a different Fe(II), with a Fe-N bond distance of 2.036(1) Å. These bonds define the short pathway Fe-N-C-N-Fe. The ligands which connect these metallic nodes shape an angle of 47.7° between the ab plane formed by the square lattice and the tilt of the ligand (Fig. ). The position of the fluorine atom in the ligand is indistinguishable between the 5th and 6th position due to the deprotonation of the benzimidazole. These two positions provoke a disorder in the crystal structure, originating an infinite number of possibilities for the stacking of the layers.