Intermolecular Interactions in Solid-State Metalloporphyrins and Their Impacts on Crystal and Molecular Structures
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- 作者：Seth C. Hunter ; Brenda A. Smith ; Christina M. Hoffmann ; Xiaoping Wang ; Yu-Sheng Chen ; Garry J. McIntyre ; Zi-Ling Xue
- 刊名：Inorganic Chemistry
- 出版年：2014
- 出版时间：November 3, 2014
- 年：2014
- 卷：53
- 期：21
- 页码：11552-11562
- 全文大小：862K
- ISSN：1520-510X
文摘
A variable-temperature (VT) crystal structure study of [Fe(TPP)Cl] (TPP2鈥?/sup> = 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鈥揘O binding. Hirshfeld analyses of the structure of [Co(TPP)(NO)] indicate that the phase change from I4/m to P1虆 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.
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