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Three-dimensional supramolecular architecture based on 4,4′-methylene-bis(benzenamine) and aromatic carboxylic acid guests: Synthons cooperation, robust motifs and structural diversity

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Abstract

The two-component solid forms involving 4,4′-methylene-bis(benzenamine) included both salts and co-crystals, while 4,4′-methylene-bis(benzenamine) crystallized exclusively as a salt, in agreement with the differences in the pK a values. Many of the crystal structures displayed either the neutral or the ionic form of the carboxylic acid-amino heterosynthon, and the similarity in crystal structures between the neutral and the ionized molecules makes the visual distinction between a salt and co-crystal dependent on the experimental location of the acidic proton. A variety of supramolecular hydrogen bonded motifs involving interactions between the aza molecules and carboxylic acid groups are observed rather than just the O-H…N/O-H…O motif. The motifs are identical in all the two compounds analyzed showing the robustness of these supramolecular synthons. In all adducts, recognition between the constituents is established through either N-H…O and/or O-H…O/O-H…N pairwise hydrogen bonds. In all adducts, COOH functional groups available on 1 and 2 interact with the N-donor compounds. The COOH moieties in 1 forms only single N-H…O hydrogen bonds, whereas in 2, it forms pairwise O-H…N/N-H…O hydrogen bonds. The supramolecular architectures are elegant and simple, with stacking of networks in 2, but a rather complex network with a threefold interpenetration pattern was found in 1. Thermal stability of these compounds has been investigated by thermogravimetric analysis (TGA) of mass loss.

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Authors and Affiliations

  1. College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao, 266042, China

    Lei Wang, Lei Zhao, Meng Liu, FaQian Liu & ZhiQiang Hu

  2. Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Zhejiang Normal University, Jinhua, 321004, China

    Qiang Xiao

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  1. Lei Wang
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  2. Lei Zhao
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  3. Meng Liu
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Correspondence to Lei Wang or ZhiQiang Hu.

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Wang, L., Zhao, L., Liu, M. et al. Three-dimensional supramolecular architecture based on 4,4′-methylene-bis(benzenamine) and aromatic carboxylic acid guests: Synthons cooperation, robust motifs and structural diversity. Sci. China Chem. 55, 2523–2531 (2012). https://doi.org/10.1007/s11426-012-4701-z

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