Tetrahedral oxyanions-assisted supramolecular assemblies of pyridine-based tectons into hydrogen-bonding networks

• Four 3D supramolecular salts have been prepared.
• Pyridine-based L1 and L2 show preference for tetrahedral oxyanions.
• Robust hydrogen bonds generate various supramolecular frameworks.
• Distinctive substructures arise from H2PO4− anions in salts 1.

The systematic research has been done into structural variations of supramolecular architectures by the self assembly of two pyridine-based potential anion receptors, 1-(4-pyridyl)piperazine (L1) and 4-pyrrolidinopyridine (L2), and different inorganic acids (HCl, HBr, HI, HNO3, HClO4, HIO4, H2SO4 and H3PO4). The formation of four fascinating salts, i.e. (H2L12+)·(H2PO4−)2 (1), (H2L12+)·(ClO4−)2 (2), (HL2+)·(ClO4−) (3) and (HL2+)·(IO4−) (4), indicates that N-heterocyclic L1 and L2 are prone to cocrystallize with tetrahedral oxyanions and anionic topologies play a crucial role in the crystallization process. Structural analyses reveal that various intermolecular ring motifs have been generated by robust hydrogen-bonding interactions in compounds 1–4. In particular, interesting substructures were observed in H2PO4− from salts 1 due to its polytopic potential hydrogen-bonding donor and acceptor oxygen atoms, including ring motifs, 1D ribbons and 2D supramolecular framework. Much to our surprise, crystal 4 proves to be a member of few supramolecular salts crystallizing with IO4− anion according to the Cambridge Structure Database (CSD).

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