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Abstract <p>The precipitation process of bismuth(III) from perchloric acid solutions upon the addition of malonic acid has been studied as a function of the molar ratio of malonate ions to bismuth in the system. A basic bismuth malonate with the composition BiOH(C<sub>3</sub>H<sub>2</sub>O<sub>4</sub>) (compound <b>I</b>) was synthesized, along with two structurally distinct but compositionally identical bismuth malonates containing a water molecule: Bi(C<sub>3</sub>H<sub>2</sub>O<sub>4</sub>)(C<sub>3</sub>H<sub>3</sub>O<sub>4</sub>)H<sub>2</sub>O (<b>II</b>) and [Bi(C<sub>3</sub>H<sub>2</sub>O<sub>4</sub>)(C<sub>3</sub>H<sub>3</sub>O<sub>4</sub>)]⋅H<sub>2</sub>O (<b>III</b>). Compound <b>I</b> was obtained in an X‑ray amorphous form, whereas the crystal structures of compounds <b>II</b> and <b>III</b> were determined by X-ray diffraction. In compound <b>II</b>, the water molecule coordinates directly to the bismuth atom as a ligand, whereas in compound <b>III</b> this is not observed. Both compounds form one-dimensional (1D) coordination polymers. Upon calcination of compounds <b>II</b> and <b>III</b> at 120°C, anhydrous bismuth malonate with the composition Bi(C<sub>3</sub>H<sub>2</sub>O<sub>4</sub>)(C<sub>3</sub>H<sub>3</sub>O<sub>4</sub>) (<b>IV</b>) is produced via dehydration. All new compounds (<b>I</b>–<b>IV</b>) were characterized by IR spectroscopy, thermal analysis, and powder X-ray diffraction, and their compositions were confirmed by elemental analysis. The structural features of polymers <b>II</b> and <b>III</b> are discussed, including a topological analysis of the electron density in Bi–O contacts, allowing for the identification of primary and secondary bonds within the coordination polyhedra.</p>

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Synthesis, Structure, and Properties of Bismuth(III) Salts with Malonic Acid

  • 期刊论文

  • 发表日期：

    2025年6月1日

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  • E. V. Timakova,
  • T. V. Rybalova,
  • I. V. Mirzaeva,
  • T. N. Drebushchak

摘要

Abstract

The precipitation process of bismuth(III) from perchloric acid solutions upon the addition of malonic acid has been studied as a function of the molar ratio of malonate ions to bismuth in the system. A basic bismuth malonate with the composition BiOH(C3H2O4) (compound I) was synthesized, along with two structurally distinct but compositionally identical bismuth malonates containing a water molecule: Bi(C3H2O4)(C3H3O4)H2O (II) and [Bi(C3H2O4)(C3H3O4)]⋅H2O (III). Compound I was obtained in an X‑ray amorphous form, whereas the crystal structures of compounds II and III were determined by X-ray diffraction. In compound II, the water molecule coordinates directly to the bismuth atom as a ligand, whereas in compound III this is not observed. Both compounds form one-dimensional (1D) coordination polymers. Upon calcination of compounds II and III at 120°C, anhydrous bismuth malonate with the composition Bi(C3H2O4)(C3H3O4) (IV) is produced via dehydration. All new compounds (I–IV) were characterized by IR spectroscopy, thermal analysis, and powder X-ray diffraction, and their compositions were confirmed by elemental analysis. The structural features of polymers II and III are discussed, including a topological analysis of the electron density in Bi–O contacts, allowing for the identification of primary and secondary bonds within the coordination polyhedra.