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| Naji, M. |
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| Motta, Antonella |
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| Aletan, Dirar |
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| Mohamed, Tarek |
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| Ertürk, Emre |
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| Taccardi, Nicola |
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| Kononenko, Denys |
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| Petrov, R. H. | Madrid |
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| Alshaaer, Mazen | Brussels |
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| Bih, L. |
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| Casati, R. |
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| Muller, Hermance |
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| Kočí, Jan | Prague |
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| Šuljagić, Marija |
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| Kalteremidou, Kalliopi-Artemi | Brussels |
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| Azam, Siraj |
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| Ospanova, Alyiya |
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| Blanpain, Bart |
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| Ali, M. A. |
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| Popa, V. |
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| Rančić, M. |
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| Ollier, Nadège |
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| Azevedo, Nuno Monteiro |
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| Landes, Michael |
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| Rignanese, Gian-Marco |
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Grant, Emeralde P.
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article
Copper(II) and zinc(II) complexes bridged by benzenoid aromatic oxocarbon and dicarboxylate dianions
Abstract
<p>A novel series of Cu(II) and Zn(II) complexes were constructed through the bridging croconate (C<sub>5</sub>O<sub>5</sub>)<sup>2−</sup>, squarate (C<sub>4</sub>O<sub>4</sub>)<sup>2−</sup> and 2,5-pyridine-dicarboxylate (Py<sup>2,5-dc</sup>)<sup>2−</sup> dianions. These include pent- [Cu<sub>5</sub>(epdmpy)<sub>4</sub>(C<sub>5</sub>O<sub>5</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub>](ClO<sub>4</sub>)<sub>6</sub>‧12H<sub>2</sub>O (1) and tri-nuclear [Cu<sub>3</sub>(bepza)<sub>2</sub>(Py<sup>2,5-dc</sup>)<sub>2</sub>(ClO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]‧2H<sub>2</sub>O (4), dinuclear [Zn<sub>2</sub>(MeDPA)<sub>2</sub>(C<sub>4</sub>O<sub>4</sub>)(H<sub>2</sub>O)<sub>4</sub>](ClO<sub>4</sub>)<sub>2</sub> (7), and 1-D- coordination polymers (CPs) catena-{[Cu<sub>2</sub>(bpzpy)<sub>2</sub>(C<sub>5</sub>O<sub>5</sub>)](ClO<sub>4</sub>)<sub>2</sub>‧MeOH} (2) and catena-{[Zn(4,4′-bipy)(H<sub>2</sub>O)<sub>4</sub>](C<sub>5</sub>O<sub>5</sub>)(H<sub>2</sub>O)} (6) as well as the mononuclear [Cu(HBph<sup>2,2′-dc</sup>)(pmdien)]ClO<sub>4</sub> (5) have been synthesized and spectroscopically characterized as well as by single crystal X-ray crystallography. The reaction of aqueous solution Cu(ClO<sub>4</sub>)<sub>2</sub>, pymeea and C<sub>5</sub>O<sub>5</sub><sup>2−</sup> resulted in the unprecedently bis(oxalato) [Cu<sub>2</sub>(Pymeea)<sub>2</sub>(C<sub>2</sub>O<sub>4</sub>)(ClO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>] (3). In these complexes, (C<sub>5</sub>O<sub>5</sub>)<sup>2−</sup>, squarate (C<sub>4</sub>O<sub>4</sub>)<sup>2−</sup> and (Py<sup>2,5-dc</sup>)<sup>2−</sup> ligands display a variety of coordination bonding modes. In complexes 1 and 2 the croconato is binding as 1,2-bidentate-3-monodentate but in addition 5-mono-dentate semi-coordinate bonding was detected for 2, whereas in 6 as counter dianion. The bonding mode in the squarato 7 was achieved through the trans μ<sub>1,3</sub>-mono-dentate. In the di-carboxylato compounds, only five-membered chelate ring was formed in 5 via one of the carboxylate groups, whereas in 4 bridging was conducted through a mono-carboxylate and five-membered chelate ring including the second carboxylate and pyridyl nitrogen. In complexes 1–5 and 7, hydrogen bonds of type O–H⋯O and/or N–H⋯O are connecting the complex cations with the perchlorate anions/ligands to generate different dimensional supramolecular network structures, whereas in 6, the 3D network was formed through hydrogen bonding between the coordinated aqua and lattice water molecules. Non-covalent ring⋯ring interactions were also observed between pyridyl rings in complexes 1, 6 and 7, and between pyrazolyl rings as well as pyridyl ring in 2.</p>