title: Intermolecular interactions in solid-state metalloporphyrins and their impacts on crystal and molecular structures.
abstract: A variable-temperature (VT) crystal structure study of [Fe(TPP)Cl] (TPP(2-) = 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 P1 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.
authors.affiliation: Department of Chemistry, The University of Tennessee , Knoxville, Tennessee 37996, United States.
authors.forename: Seth C
authors.initials: SC
authors.lastname: Hunter
authors.forename: Brenda A
authors.initials: BA
authors.lastname: Smith
authors.forename: Christina M
authors.initials: CM
authors.lastname: Hoffmann
authors.forename: Xiaoping
authors.initials: X
authors.lastname: Wang
authors.forename: Yu-Sheng
authors.initials: YS
authors.lastname: Chen
authors.forename: Garry J
authors.initials: GJ
authors.lastname: McIntyre
authors.forename: Zi-Ling
authors.initials: ZL
authors.lastname: Xue
mesh_terms: D018360:Crystallography, X-Ray; D005296:Ferrous Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D008665:Metalloporphyrins / Q000138:chemical synthesis / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D013696:Temperature
chemical_list: D005296:Ferrous Compounds; D008665:Metalloporphyrins