Pentacoordinate Mixed-Ligand Zn(II) Complexes with Flufenamato and Niflumato Ligands: Crystal Structure, Spectral Characterization and Biological Properties

Abstract

Mixed-ligand complexes featuring a carboxylato ligand and bidentate chelate N,N′-donor ligands along with a single halogenido ligand are rarely subjected to studies despite their interesting physical, chemical and biological properties. A direct synthesis involving non-steroidal anti-inflammatory drugs flufenamic acid and niflumic acid and sterically hindering N,N′-donor ligands (neocuproine and 2,2′-biquinoline) has been used to prepare mononuclear mixed-ligand zinc complexes with a composition of [ZnCl(flu)(neo)] (1A and 1B) and [ZnCl(nif)(biq)] (2). Single-crystal X-ray diffraction data have shown that the carboxylate binding mode differs in the two polymorphs 1A and 1B, which form molecules of same composition, and the deviations in molecular geometry are further reflected in their supramolecular structures. The inter- and intramolecular interactions and their contributions to the stability of the crystal structures has been investigated by Hirshfeld surface analysis. The spectral properties of the prepared complexes in solid-state and solution have been analyzed. Additionally, the interaction with the biomacromolecules (fish sperm DNA, human and bovine serum albumins), studied by fluorescence assays, showed a stronger binding of 1A and 1B in comparison with 2.