| Summary: | Molecular and supramolecular structures of two polymeric and one trinuclear Cd(II) complex with hydralazine-type ligands were presented. Self-assembly of <i>E</i>-1-(2-(thiophen-2-ylmethylene)hydrazinyl)phthalazine (HL) and CdCl<sub>2</sub> gave the 1D coordination polymer [Cd(H<sub>2</sub>L)Cl<sub>3</sub>]<sub>n</sub>*H<sub>2</sub>O, <b>1</b>, in which the Cd(II) ion is hexa-coordinated with one cationic monodentate ligand (H<sub>2</sub>L<sup>+</sup>) and five chloride ions, two of them acting as connectors between Cd(II) centers, leading to the formation of a 1D coordination polymer along the <i>a</i>-direction. Using DFT calculations, the cationic ligand (H<sub>2</sub>L<sup>+</sup>) could be described as a protonated HL with an extra proton at the hydrazone moiety. Repeating the same reaction by heating under reflux conditions in the presence of 1 mL saturated aqueous KSCN solution, the ligand HL underwent cyclization to the corresponding [1,2,4]triazolo[3,4-a]phthalazine-3(2H)-thione (TPT) followed by the formation of [Cd(TPT)(SCN)<sub>2</sub>]<sub>n</sub>*H<sub>2</sub>O, <b>2</b>, a 1D coordination polymer. In this complex, the Cd(II) is coordinated with one <i>NS</i>-donor TPT bidentate chelate and two bridged <i>μ(1,3)</i>-thiocyanate ions connecting the Cd(II) centers forming the 1D polymer array along the <i>b</i>-direction. Heating <i>E</i>-2-(1-(2-(phthalazin-1-yl)hydrazono)ethyl)phenol HL<sup>OH</sup> with CdCl<sub>2</sub> under reflux condition gave the trinuclear complex [Cd<sub>3</sub>(Hydralazine)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>Cl<sub>6</sub>], <b>3</b>, indicating the hydrolysis of the hydrazonophthalazine ligand HL<sup>OH</sup> during the course of the reaction. Due to symmetry considerations, there are only two different Cd(II) centers having CdN<sub>2</sub>Cl<sub>3</sub>O and CdN<sub>2</sub>Cl<sub>4</sub> coordination environments. Hirshfeld topology analysis was used to analyze the solid-state supramolecular structure of the studied complexes.
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