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Surface extended x-ray-absorption fine structure is used to determine the crystallographic structure of iron films grown on Cu(lOO). We show that these metastable films have structural and vibrational properties strongly dependent on their thickness and their growth temperature: Either a well-defined fee structure or an anisotropically distorted fee structure is observed. A strong reordering of the thin iron films prepared at room temperature is observed when they are coated with copper; this shows that it may be incorrect to assume that a thin film is a good simulation of an interface.