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Argentophilic Interactions in Two AgI Complexes of 3-(2-(Pyridin-4-yl)ethyl)pentane-2,4-dione, a Promising Ditopic Ligand

Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany
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Crystals 2019, 9(8), 414; https://doi.org/10.3390/cryst9080414
Received: 27 June 2019 / Revised: 2 August 2019 / Accepted: 5 August 2019 / Published: 9 August 2019
(This article belongs to the Section Crystal Engineering)
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Abstract

Reactions of 3-(2-(pyridin-4-yl)ethyl)pentane-2,4-dione (HacacPyen) with AgPF6 and AgBF4 afforded cationic silver complexes [Ag(HacacPyen)2]+ with essentially linear coordination of the AgI cation by two pyridine N atoms. Rather unexpectedly, the HacacPyen ligands in the PF6 salt 1 adopt the diketo form, in contrast to the uncoordinated HacacPyen molecule, whereas the corresponding BF4 salt 2 and the majority of 3-substituted acetylacetones crystallizes as the enol tautomer. In both compounds 1 and 2, complex cations aggregate via short Ag···Ag interactions to pairs. These contacts amount to 3.21 Å in 1 and 3.26 Å or 3.31 Å in 2. 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 PF6 anions in 1 and the BF4 counter ions in 2 are involved in long and presumably electrostatic Ag···F contacts of ca. 2.9 Å. Additional coordination between AgI and keto O atoms of symmetry-equivalent ligands occurs in 1 and leads to an extended two-periodic supramolecular structure. View Full-Text
Keywords: ditopic ligands; argentophilic interactions; keto-enol tautomrism; coordination chemistry; metal-organic frameworks ditopic ligands; argentophilic interactions; keto-enol tautomrism; coordination chemistry; metal-organic frameworks
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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van Terwingen, S.; Englert, U. Argentophilic Interactions in Two AgI Complexes of 3-(2-(Pyridin-4-yl)ethyl)pentane-2,4-dione, a Promising Ditopic Ligand. Crystals 2019, 9, 414.

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