Factors governing the three-dimensional hydrogen-bond network structure of poly(m-phenylene isophthalamide) and a series of its model compounds (4): similarity in local conformation and packing structure between a complicated three-arm model compound and the linear model compounds.

Crystal structure of a three-arm model compound of poly(m-phenylene isophthalamide) (PMIA), N,N',N' '-triphenyl trimesamide Phi(CONHPhi)(3), has been analyzed by the X-ray diffraction method. The torsional angles around the bonds connecting the amide group and the central benzene ring are 24-34 degrees , almost the same as those observed for many kinds of aromatic amide compounds, reflecting mainly the intramolecular energetic balance between the amide and benzene groups. On the other hand, the torsional angles around the bonds connecting the amide group and the outer benzene ring were found to distribute over a wide range of 2-51 degrees due to the additional effect of intermolecular interactions. This is the first example to show experimentally clearly the role of intra- and intermolecular interactions in the control of torsional angle around the benzene-amide linkage. The hydrogen bonds are formed between the amide groups of the neighboring molecules, resulting in the construction of three-dimensional network structure. The local packing structure of the three-arm compound was found to be essentially the same as those observed for PMIA and the linear model compounds, indicating a characteristic structural feature of the meta-linkage-type aromatic amide compounds. The energy calculation was made using the software Polymorph Predictor to extract the energetically most stable crystal structure, which was compared successfully with the X-ray analyzed structure.