Interactions of a singly negatively charged iron atom with water molecules, Fe--(H2O)(n <= 6), in the gas phase were studied by means of density functional theory. All-electron calculations were performed using the B3LYP functional and the 6-311++G(2d,2p) basis set for the Fe, O, and H atoms. In the lowest total energy states of Fe--(H2O)(n), the metal-hydrogen bonding is stronger than the metal-oxygen one, producing low-symmetry structures because the water molecules are directly attached to the metal by basically one of their hydrogen atoms, whereas the other ones are involved in a network of hydrogen bonds, which together with the Fe delta--H delta+ bonding accounts for the nascent hydration of the Fe- anion. For Fe--(H2O)(3 <= n), three-, four-, five-, and six-membered rings of water molecules are bonded to the metal, which is located at the surface of the cluster in such a way as to reduce the repulsion with the oxygen atoms. Nevertheless, internal isomers appear also, lying less than 3 or 5 kcal/mol for n = 2-3 or n = 4-6. These results are in contrast with those of classical TM+-(H2O)(n) complexes, where the direct TM+-O bonding usually produces high symmetry structures with the metal defining the center of the complex. They show also that the Fe- anions, as the TM+ ions, have great capability for the adsorption of water molecules, forming Fe--(H2O)(n) structures stabilized by Fe delta--F delta+ and H-bond interactions.