Browsing by Author "Smith, BA"

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    Intermolecular interactions in solid-state metalloporphyrins and their impacts on crystal and molecular structures
    (ACS Publications, 2014-10-23) Hunter, SC; Smith, BA; Hoffmann, CM; Wang, XP; Chen, YS; McIntyre, GJ; Xue, ZL
    A variable-temperature (VT) crystal structure study of [Fe(TPP)Cl] (TPP2– = meso-tetraphenylporphyrinate) and Hirshfeld surface analyses of its structures and previously reported structures of [M(TPP)(NO)] (M = Fe, Co) reveal that intermolecular interactions are a significant factor in structure disorder in the three metalloporphyrins and phase changes in the nitrosyl complexes. These interactions cause, for example, an 8-fold disorder in the crystal structures of [M(TPP)(NO)] at room temperature that obscures the M–NO binding. Hirshfeld analyses of the structure of [Co(TPP)(NO)] indicate that the phase change from I4/m to P1̅ leads to an increase in void-volume percentage, permitting additional structural compression through tilting of the phenyl rings to offset the close-packing interactions at the interlayer positions in the crystal structures with temperature decrease. X-ray and neutron structure studies of [Fe(TPP)Cl] at 293, 143, and 20 K reveal a tilting of the phenyl groups away from being perpendicular to the porphyrin ring as a result of intermolecular interactions. Structural similarities and differences among the three complexes are identified and described by Hirshfeld surface and void-volume calculations.© 2014, American Chemical Society.