Modulation of Crystal Packing via the Tuning of Peripheral Functionality for a Family of Dinuclear Mesocates.
Benjamin H WilsonPaul E KrugerPublished in: Chemistry, an Asian journal (2020)
A family of four novel pyrazinyl-hydrazone based ligands have been synthesized with differing functionality at the 5-position of the central aromatic ring. Previous work has shown such ligands to form dinuclear triple mesocates which pack to form hexagonal channels capable of gas sorption. The effect of the peripheral functionality of the ligand on the crystal packing was investigated by synthesizing complexes 1 to 4 which feature amino, bromo, iodo and methoxy substituents respectively. Complexes 1 to 3 crystallized in the same hexagonal space group P63 /m and featured 1D channels. However, on closer inspection while the packing of 1 is mediated by hydrogen bonding interactions, the packing of complexes 2 and 3 are not, due to a subtlety different π-π stacking interaction enforced by the halogen substituent. The more bulky nature of the methoxy substituent of 4 results in the complex crystallizing in the triclinic space group P-1, featuring an entirely different crystal packing.