Argentophilic Interactions in Two Ag I Complexes of 3-(2-(Pyridin-4-yl)ethyl)pentane-2,4-dione, a Promising Ditopic Ligand
Steven van Terwingen, Ulli Englert
Crystals · 2019
doi:10.3390/cryst9080414 (opens in a new tab)
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Abstract
Reactions of 3-(2-(pyridin-4-yl)ethyl)pentane-2,4-dione (HacacPyen) with AgPF<sub>6</sub> and AgBF<sub>4</sub> afforded cationic silver complexes [Ag(HacacPyen)<sub>2</sub>]<sup>+</sup> with essentially linear coordination of the Ag<sup>I</sup> cation by two pyridine N atoms. Rather unexpectedly, the HacacPyen ligands in the PF<sub>6</sub><sup>−</sup> salt <b>1</b> adopt the diketo form, in contrast to the uncoordinated HacacPyen molecule, whereas the corresponding BF<sub>4</sub><sup>−</sup> salt <b>2</b> and the majority of 3-substituted acetylacetones crystallizes as the enol tautomer. In both compounds <b>1</b> and <b>2</b>, complex cations aggregate <i>via</i> short Ag···Ag interactions to pairs. These contacts amount to 3.21 Å in <b>1</b> and 3.26 Å or 3.31 Å in <b>2</b>. As they are unsupported by any additional bridging ligands and correspond to the closest interionic interactions between neighbouring complex cations, they may be addressed as argentophilic interactions. The PF<sub>6</sub><sup>−</sup> anions in <b>1</b> and the BF<sub>4</sub><sup>−</sup> counter ions in <b>2</b> are involved in long and presumably electrostatic Ag···F contacts of ca. 2.9 Å. Additional coordination between Ag<sup>I</sup> and keto O atoms of symmetry-equivalent ligands occurs in <b>1</b> and leads to an extended two-periodic supramolecular structure.
Abstract licence: CC BY
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