Three Zn( II ) complexes, namely mononuclear derivatives [Zn(H 2 L) 2 I 2 ]2CH 3 OH (1) and [Zn(H 2 L) 2 Br 2 ]
2CH 3 OH (2) and a tetranuclear cyclic compound [Zn 4 (H 2 L) 4 Cl 8 ]4CH 3 OH (3) {H 2 L = p-hydroxy-
benzaldehyde isonicotinoylhydrazone}, were synthesized using a self-assembly method and fully
characterized. Characterization included theoretical methods and single crystal X-ray diffraction. The
molecular structures of compounds 1–3 demonstrate the effect of halide ions and the binding mode of
H 2 L on self-assembly. The arrangement of the packing patterns in 1–3 is well explained by various types
of non-covalent interactions. Notably, several types of strong H-bonding, C–H O, and p p interactions
were also observed, which assist in the formation of 3D supramolecular networks. In the isostructural
compounds 1 and 2, a tripod type H-bonding interaction of H 2 L with the methanol molecules of crystal-
lization was observed. Furthermore, the terminal halide ligands exert H-bonding interactions with the
–OH/–NH and –CH moieties of H 2 L. In all compounds, the supramolecular 3D networks, driven by strong
H-bonding interactions, were simplified by topologial analysis. This showed a 6-connected framework with
a unique topology in 1 and 2, and an 8-connected framework with bcu topology in 3 (the latter is
composed of cyclic tetrazinc( II ) cluster units with 2M4-1 topology). In addition, the discussion on coordi-
nation geometries and non-covalent interactions was also supported using Hirshfeld surface analysis and
DFT calculations.