Utilizing the pyridinediimine ligand [(2,6-(PrC6H3)-Pr-i)N=CMe)(N(Pr-i)(2)C2H4)N=CMe)C5H3N] (didpa), the iron(II) complexes Fe(didpa)Br-2 (1), [Fe(Hdidpa)Br-2][PF6] (2), and [Fe(Hdidpa)CH3CN(OH)][2PF(6)] (3) were synthesized and characterized by X-ray diffraction and spectroscopic methods. The X-ray data show that the didpa scaffold is capable of forming intramolecular hydrogen bonds in the solid state located within the secondary coordination sphere of complexes 2 and 3. These hydrogen bonds are responsible for stabilizing the iron(II) hydroxo ligand in 3, which originates from H2O.