An unprecedented (3,4)-connected self-penetrating network of zinc complex: In situ formation of a tetradentate N-heterocyclic ligand under POMs-mediated hydrothermal conditions

The reaction of lacunary polyanion [α-H₂P₂W₁₂O₄₈]¹²⁻, zinc acetate, bpp (1,3-bis(4-pyridyl)propane) and BTC (1,3,5-benzenetricarboxylate) in an acidic aqueous solution led to the isolation of a new complex [Zn₃(BTC)₂(chtpy)(H₂O)₂] · 2H₂O (1), which crystallizes in the space group C2/c with a = 28.988(6) Å, b = 11.254(2) Å, c = 17.347(4) Å, V = 4682.5(2) Å³, Z = 4. X-ray diffraction analysis reveals that there exists the generation of in situ ligand through simultaneous dehydrogenative coupling and hydroxylation of an N-heterocyclic ligand in complex 1. More interestingly, it exhibits an unprecedented (3,4)-connected (8².10)₂(8³)₂(8⁴.10.12)(8⁵.10) topology which has been reported for the first time and shows self-penetrating nature at the same time.