Mapping NO movements in crystalline [Fe(Porph)(NO)(1-MeIm)].

Orientational disorder of the distal nitrosyl (NO) ligand in iron porphyrinates is a common phenomenon. We present an analysis of multitemperature crystallographic data for the order/disorder phenomenon. The observed temperature-dependent order/disorder and variable rotational orientations of nitrosyl ligands for six different six-coordinate iron porphyrinates have been examined in terms of the nonbonded contacts found in the solid state. Favorable orientations for NO can be identified either by calculation of the close nonbonded contacts or by evaluation of the geometry-dependent potential energy using semiempirical nonbonded potential functions. The nonbonded contacts display temperature-dependent differences consistent with observed structural differences. The motion of NO appears to be controlled by intermolecular interactions that allow a limited set of orientations, and under some conditions, only a single NO orientation is allowed. In some cases, the equilibria involving the orientations of NO can be analyzed using the van't Hoff relationship, and the free energy and enthalpy of the solid-state transitions can be evaluated. The intrinsic barriers to rotation of the NO were examined using a fine-meshed series of DFT calculations. The calculations also showed the detailed effects of the variation of the NO orientation on the equatorial bond distances.