Synthesis, Molecular, and Supramolecular Structures of Two Azide-Bridged Cd(II) and Cu(II) Coordination Polymers
Two 1D coordination polymers were synthesized by reaction of two ligands, 2-amino-4-picoline (<b>2A4Pic</b>) and quinoline-6-carboxylic acid (<b>Qu-6-COOH</b>) with two metal (II) nitrate (M = Cd and Cu) in the presence of azide as a linker. The synthesized metal complexes &l...
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MDPI AG
2023-03-01
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| Series: | Symmetry |
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| author | Mezna Saleh Altowyan Eman M. Fathalla Jörg H. Albering Assem Barakat Morsy A. M. Abu-Youssef Saied M. Soliman Ahmed M. A. Badr |
| author_facet | Mezna Saleh Altowyan Eman M. Fathalla Jörg H. Albering Assem Barakat Morsy A. M. Abu-Youssef Saied M. Soliman Ahmed M. A. Badr |
| author_sort | Mezna Saleh Altowyan |
| collection | DOAJ |
| description | Two 1D coordination polymers were synthesized by reaction of two ligands, 2-amino-4-picoline (<b>2A4Pic</b>) and quinoline-6-carboxylic acid (<b>Qu-6-COOH</b>) with two metal (II) nitrate (M = Cd and Cu) in the presence of azide as a linker. The synthesized metal complexes <b>[Cd(2A4Pic)<sub>2</sub>(N<sub>3</sub>)<sub>2</sub>]<sub>n</sub></b>; (<b>1</b>) and <b>[Cu(Qu-6-COO)(N<sub>3</sub>)(H<sub>2</sub>O)]<sub>n</sub></b>; (<b>2</b>) were isolated in single crystals and their X-ray structures revealed a 1D polymeric structure. Due to symmetry considerations, the asymmetric formula is half a [Cd(2A4Pic)<sub>2</sub>(N<sub>3</sub>)<sub>2</sub>] unit for <b>1</b> and one [Cu(Qu-6-COO)(N<sub>3</sub>)(H<sub>2</sub>O)] unit for <b>2</b>. In complex <b>1</b>, the Cd(II) is hexa-coordinated with two <b>2A4Pic</b> molecules and four μ(1,1) azide units. Hence, the CdN<sub>6</sub> coordination environment has a slightly distorted octahedral geometry. In <b>2</b>, the Cu(II) is hexa-coordinated with three different ligands (<b>Qu-6-COO¯</b>, <b>H<sub>2</sub>O</b> and μ(1,1) <b>N<sub>3</sub>¯</b>) where all are connectors between the crystallographically related Cu(II) sites. Additionally, complex <b>2</b> distorted CuN<sub>2</sub>O<sub>4</sub> octahedral geometry. In both complexes, the polymer arrays are connected by N…H hydrogen bonds and π–π stacking interactions. Based on Hirshfeld analysis, the percentages of N…H contacts are 43.1 and 27.4% for <b>1</b> and <b>2</b>, respectively, while %C...C are 5.6 and 9.3%, respectively. Analysis of Cu-N, Cu-O, and Cd-N bonds using DFT calculations showed predominantly closed-shell coordination interactions with little covalent characters. Additionally, the negatively charged ligand groups were found to compensate the positive charge of the central metal ion to a larger extent than the electrically neutral ligands. |
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| last_indexed | 2024-03-11T05:50:39Z |
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| spelling | doaj.art-d9b68348e28342488773383f7d415b822023-11-17T14:08:33ZengMDPI AGSymmetry2073-89942023-03-0115361910.3390/sym15030619Synthesis, Molecular, and Supramolecular Structures of Two Azide-Bridged Cd(II) and Cu(II) Coordination PolymersMezna Saleh Altowyan0Eman M. Fathalla1Jörg H. Albering2Assem Barakat3Morsy A. M. Abu-Youssef4Saied M. Soliman5Ahmed M. A. Badr6Department of Chemistry, College of Science, Princess Nourah bint Abdulrahman University, P.O. Box 84428, Riyadh 11671, Saudi ArabiaDepartment of Chemistry, Faculty of Science, Alexandria University, P.O. Box 426, Ibrahimia, Alexandria 21321, EgyptGraz University of Technology, Mandellstr. 11/III, A-8010 Graz, AustriaDepartment 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, EgyptDepartment 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, EgyptTwo 1D coordination polymers were synthesized by reaction of two ligands, 2-amino-4-picoline (<b>2A4Pic</b>) and quinoline-6-carboxylic acid (<b>Qu-6-COOH</b>) with two metal (II) nitrate (M = Cd and Cu) in the presence of azide as a linker. The synthesized metal complexes <b>[Cd(2A4Pic)<sub>2</sub>(N<sub>3</sub>)<sub>2</sub>]<sub>n</sub></b>; (<b>1</b>) and <b>[Cu(Qu-6-COO)(N<sub>3</sub>)(H<sub>2</sub>O)]<sub>n</sub></b>; (<b>2</b>) were isolated in single crystals and their X-ray structures revealed a 1D polymeric structure. Due to symmetry considerations, the asymmetric formula is half a [Cd(2A4Pic)<sub>2</sub>(N<sub>3</sub>)<sub>2</sub>] unit for <b>1</b> and one [Cu(Qu-6-COO)(N<sub>3</sub>)(H<sub>2</sub>O)] unit for <b>2</b>. In complex <b>1</b>, the Cd(II) is hexa-coordinated with two <b>2A4Pic</b> molecules and four μ(1,1) azide units. Hence, the CdN<sub>6</sub> coordination environment has a slightly distorted octahedral geometry. In <b>2</b>, the Cu(II) is hexa-coordinated with three different ligands (<b>Qu-6-COO¯</b>, <b>H<sub>2</sub>O</b> and μ(1,1) <b>N<sub>3</sub>¯</b>) where all are connectors between the crystallographically related Cu(II) sites. Additionally, complex <b>2</b> distorted CuN<sub>2</sub>O<sub>4</sub> octahedral geometry. In both complexes, the polymer arrays are connected by N…H hydrogen bonds and π–π stacking interactions. Based on Hirshfeld analysis, the percentages of N…H contacts are 43.1 and 27.4% for <b>1</b> and <b>2</b>, respectively, while %C...C are 5.6 and 9.3%, respectively. Analysis of Cu-N, Cu-O, and Cd-N bonds using DFT calculations showed predominantly closed-shell coordination interactions with little covalent characters. Additionally, the negatively charged ligand groups were found to compensate the positive charge of the central metal ion to a larger extent than the electrically neutral ligands.https://www.mdpi.com/2073-8994/15/3/619coordination polymerazidepyridinequinolineHirshfeld |
| spellingShingle | Mezna Saleh Altowyan Eman M. Fathalla Jörg H. Albering Assem Barakat Morsy A. M. Abu-Youssef Saied M. Soliman Ahmed M. A. Badr Synthesis, Molecular, and Supramolecular Structures of Two Azide-Bridged Cd(II) and Cu(II) Coordination Polymers Symmetry coordination polymer azide pyridine quinoline Hirshfeld |
| title | Synthesis, Molecular, and Supramolecular Structures of Two Azide-Bridged Cd(II) and Cu(II) Coordination Polymers |
| title_full | Synthesis, Molecular, and Supramolecular Structures of Two Azide-Bridged Cd(II) and Cu(II) Coordination Polymers |
| title_fullStr | Synthesis, Molecular, and Supramolecular Structures of Two Azide-Bridged Cd(II) and Cu(II) Coordination Polymers |
| title_full_unstemmed | Synthesis, Molecular, and Supramolecular Structures of Two Azide-Bridged Cd(II) and Cu(II) Coordination Polymers |
| title_short | Synthesis, Molecular, and Supramolecular Structures of Two Azide-Bridged Cd(II) and Cu(II) Coordination Polymers |
| title_sort | synthesis molecular and supramolecular structures of two azide bridged cd ii and cu ii coordination polymers |
| topic | coordination polymer azide pyridine quinoline Hirshfeld |
| url | https://www.mdpi.com/2073-8994/15/3/619 |
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