We have re-investigated the structure and vibrational spectroscopy of the iconic molecule iron pentacarbonyl, Fe­(CO)5, in the solid state by neutron scattering methods. In addition to the known C2/c structure, we find that Fe­(CO)5 undergoes a displacive ferroelastic phase transition at 105 K to a P1̅ structure. We propose that this is a result of certain intermolecular contacts becoming shorter than the sum of the van der Waals radii, resulting in an increased contribution of electrostatic repulsion to these interactions; this is manifested as a strain that breaks the symmetry of the crystal. Evaluation of the strain in a triclinic crystal required a description of the spontaneous strain in terms of a second-rank tensor, something that is feasible with high-precision powder diffraction data but practically very difficult using strain gauges on a single crystal of such low symmetry. The use of neutron vibrational spectroscopy (which is not subject to selection rules) has allowed the observation of all the fundamentals below 700 cm–1 for the first time. This has resulted in the re-assignment of several of the modes. Surprisingly, density functional theory calculations that were carried out to support the spectral assignments provided a poor description of the spectra.