Two new polymorphic mononuclear complexes, with analogous structural formula (C6H9N2)2[Zn(H2O)6](SO4)2·2H2O, of zinc(II) templated by 2-amino-6-methylpyridinium ligand have been discovered. These polymorphic hybrid crystals, which differ only in terms of their crystal structures, were prepared in one-step synthesis under ambient conditions and investigated for their thermal and catalytic properties. Single-crystal X-ray diffraction of the obtained materials revealed that polymorphs 1 and 2 crystallise in the triclinic system, space group P[1 with combining macron]. In an effort to further explore the form diversity of these compounds, the structural arrangements and intermolecular interactions such as hydrogen-bonding and π⋯π interactions are discussed from which supramolecular assembly was formed. Meanwhile, these new polymorphic forms can be described as the stacking of 3D layers where the interlayer distances are 13.23 and 12.59 Å for 1 and 2, respectively. The thermal behaviour of the precursors checked by TG-DTA analysis for both zinc sulfate polymorphs and variable temperature powder X-ray diffraction (VT-PXRD) show successive intermediate crystalline anhydrous phases upon dehydration in 1. The catalytic activity of both polymorphic structures has been tested in the acetalisation reaction of aldehydes as a benchmark process. Interestingly, both complexes showed excellent activity with almost total conversion in many examples and using MeOH as solvent and as the unique source of acetalisation.

Consejo Superior de Investigaciones Científicas (CSIC, PIE-201580I010) and Diputación General de Aragón (DGA) (Research Group E-104) are acknowledged for financial support of our research.

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