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Abstract <p>New ionic polymeric compounds are synthesized by the reactions of alkali metal carbonates with 3,5-dinitro-2-pyridone (Hdnhp) in an aqueous-alcohol solution: [Li(dnhp)(H<sub>2</sub>O)]<sub><i>n</i></sub> (<b>I</b>), [Na(dnhp)(H<sub>2</sub>O)]<sub><i>n</i></sub> (<b>II</b>), [K(dnhp)(H<sub>2</sub>O)]<sub><i>n</i></sub> (<b>III</b>), and [K(dnhp)(Hdnhp)]<sub><i>n</i></sub> (<b>IV</b>). Their structures are determined by single-crystal X-ray diffraction analysis. Analysis of the structures of the synthesized compounds shows that an increase in the ionic radius of the alkali metal cation (Li−Na−K) results in a regular increase in the coordination number (5, 6, and 7/8, respectively) and a change in the polymeric architecture type: from one-dimensional polymeric chains in compounds <b>I</b> and <b>II</b> to framework structures in compounds <b>III</b> and <b>IV</b>. The stereochemically rigid 2-pyridonate ligand plays a key role in structure formation exhibiting a variable denticity and different coordination modes. Hydrogen bonds and π−π-stacking interactions provide an additional stabilization of the crystal packings in compounds <b>I</b> and <b>II</b>. The structures are compared with the earlier described rubidium and cesium polymers to trace the coordination behavior of the dnhp<sup>–</sup> anion in the alkali metal series.</p>

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Influence of the Ionic Radius of Alkali Metals on the Structures of Polymeric 3,5-Dinitro-2-pyridonates

  • 期刊论文

  • 发表日期：

    2026年1月1日

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  • M. E. Nikiforova,
  • M. A. Kiskin,
  • A. A. Sidorov,
  • I. L. Dalinger,
  • I. L. Eremenko

摘要

Abstract

New ionic polymeric compounds are synthesized by the reactions of alkali metal carbonates with 3,5-dinitro-2-pyridone (Hdnhp) in an aqueous-alcohol solution: [Li(dnhp)(H2O)]n (I), [Na(dnhp)(H2O)]n (II), [K(dnhp)(H2O)]n (III), and [K(dnhp)(Hdnhp)]n (IV). Their structures are determined by single-crystal X-ray diffraction analysis. Analysis of the structures of the synthesized compounds shows that an increase in the ionic radius of the alkali metal cation (Li−Na−K) results in a regular increase in the coordination number (5, 6, and 7/8, respectively) and a change in the polymeric architecture type: from one-dimensional polymeric chains in compounds I and II to framework structures in compounds III and IV. The stereochemically rigid 2-pyridonate ligand plays a key role in structure formation exhibiting a variable denticity and different coordination modes. Hydrogen bonds and π−π-stacking interactions provide an additional stabilization of the crystal packings in compounds I and II. The structures are compared with the earlier described rubidium and cesium polymers to trace the coordination behavior of the dnhp– anion in the alkali metal series.