Molecular and Supramolecular Structures of Cd(II) Complexes with Hydralazine-Based Ligands; A New Example for Cyclization of Hydrazonophthalazine to Triazolophthalazine
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 [C...
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MDPI AG
2021-07-01
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| Online Access: | https://www.mdpi.com/2073-4352/11/7/823 |
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| author | Saied M. Soliman Raghdaa A. Massoud Hessa H. Al-Rasheed Ayman El-Faham |
| author_facet | Saied M. Soliman Raghdaa A. Massoud Hessa H. Al-Rasheed Ayman El-Faham |
| author_sort | Saied M. Soliman |
| collection | DOAJ |
| description | 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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| spelling | doaj.art-f4e053e426aa40969ee5f574c44dfcb12023-11-22T03:33:40ZengMDPI AGCrystals2073-43522021-07-0111782310.3390/cryst11070823Molecular and Supramolecular Structures of Cd(II) Complexes with Hydralazine-Based Ligands; A New Example for Cyclization of Hydrazonophthalazine to TriazolophthalazineSaied M. Soliman0Raghdaa A. Massoud1Hessa H. Al-Rasheed2Ayman El-Faham3Department of Chemistry, Faculty of Science, Alexandria University, P.O. Box 426, Ibrahimia, Alexandria 21321, EgyptDepartment of Chemistry, Faculty of Science, Alexandria University, P.O. Box 426, Ibrahimia, Alexandria 21321, EgyptDepartment of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi ArabiaDepartment of Chemistry, Faculty of Science, Alexandria University, P.O. Box 426, Ibrahimia, Alexandria 21321, EgyptMolecular 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.https://www.mdpi.com/2073-4352/11/7/823Cd(II)hydrazonophthalazinetriazolophthalazineHirshfeldtautomerismcationic ligand |
| spellingShingle | Saied M. Soliman Raghdaa A. Massoud Hessa H. Al-Rasheed Ayman El-Faham Molecular and Supramolecular Structures of Cd(II) Complexes with Hydralazine-Based Ligands; A New Example for Cyclization of Hydrazonophthalazine to Triazolophthalazine Crystals Cd(II) hydrazonophthalazine triazolophthalazine Hirshfeld tautomerism cationic ligand |
| title | Molecular and Supramolecular Structures of Cd(II) Complexes with Hydralazine-Based Ligands; A New Example for Cyclization of Hydrazonophthalazine to Triazolophthalazine |
| title_full | Molecular and Supramolecular Structures of Cd(II) Complexes with Hydralazine-Based Ligands; A New Example for Cyclization of Hydrazonophthalazine to Triazolophthalazine |
| title_fullStr | Molecular and Supramolecular Structures of Cd(II) Complexes with Hydralazine-Based Ligands; A New Example for Cyclization of Hydrazonophthalazine to Triazolophthalazine |
| title_full_unstemmed | Molecular and Supramolecular Structures of Cd(II) Complexes with Hydralazine-Based Ligands; A New Example for Cyclization of Hydrazonophthalazine to Triazolophthalazine |
| title_short | Molecular and Supramolecular Structures of Cd(II) Complexes with Hydralazine-Based Ligands; A New Example for Cyclization of Hydrazonophthalazine to Triazolophthalazine |
| title_sort | molecular and supramolecular structures of cd ii complexes with hydralazine based ligands a new example for cyclization of hydrazonophthalazine to triazolophthalazine |
| topic | Cd(II) hydrazonophthalazine triazolophthalazine Hirshfeld tautomerism cationic ligand |
| url | https://www.mdpi.com/2073-4352/11/7/823 |
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