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<p>Interaction of <i>A</i>(HSeO<sub>3</sub>) [<i>A</i> = K, Rb, Cs, (NH<sub>4</sub>)] and Cd<i>X</i><sub>2</sub> (<i>X</i> = Cl, Br) in aqueous solutions results in crystallization of multinary hydroselenite halides. The overwhelming majority of the products correspond to the <i>A</i>Cd(HSeO<sub>3</sub>)<i>X</i><sub>2</sub> composition and crystallize in triclinic symmetry similarly to the recently reported <i>A</i>Cu(HSeO<sub>3</sub>)<i>X</i><sub>2</sub>. Yet, the only exception is KCd(HSeO<sub>3</sub>)<sub>2</sub>Br, which expands the chemistry of the “layered hydroselenite” <i>A</i><sub><i>n</i></sub>(H<sub>2</sub>O)<sub><i>m</i></sub>[<i>M</i>(HSeO<sub>3</sub>)<sub>2</sub><i>X</i><sub><i>n</i></sub>] family (<i>M</i> = Cu, Co, Zn; <i>n</i> = 1, 2). Formation of the two possible stoichiometries of the metal hydroselenite halide frameworks, [<i>M</i>(HSeO<sub>3</sub>)<i>X</i><sub>2</sub>]<sup>–</sup> <i>vs</i>. [<i>M</i>(HSeO<sub>3</sub>)<sub>2</sub><i>X</i>]<sup>–</sup>, (<i>M</i> = Cu, Cd; <i>X</i> = Cl, Br) is likely to depend on both the synthesis conditions and the <i>r</i>(<i>A</i><sup>+</sup>)/<i>r</i>(<i>X</i><sup>–</sup>) ratio. The potassium-free substructure of the triclinic <i>A</i>Cd(HSeO<sub>3</sub>)<i>X</i><sub>2</sub> is represented by a planar net comprised of <i>trans</i>-CdO<sub>2</sub><i>X</i><sub>4</sub> octahedra and hydroselenite anions. If the dimer of anions instead of the monomer is considered a secondary building unit (SBU), the net acquires a kagome net-like topology. The potassium-free substructure of monoclinic KCd(HSeO<sub>3</sub>)<sub>2</sub>Br is represented by planar nets, and upon considering SBU = (HSeO<sub>3</sub>)<sub>2</sub> instead of (HSeO<sub>3</sub>), one obtains a simple square net.</p>

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Alkali-metal (ammonium) cadmium hydroselenite halides: an interplay of two stoichiometries

  • 期刊论文

  • 发表日期：

    2025年7月3日

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  • Dmitri O. Charkin,
  • Vasili Yu. Grishaev,
  • Vadim E. Kireev,
  • Alexander M. Banaru,
  • Sergey M. Aksenov

摘要

Interaction of A(HSeO3) [A = K, Rb, Cs, (NH4)] and CdX2 (X = Cl, Br) in aqueous solutions results in crystallization of multinary hydroselenite halides. The overwhelming majority of the products correspond to the ACd(HSeO3)X2 composition and crystallize in triclinic symmetry similarly to the recently reported ACu(HSeO3)X2. Yet, the only exception is KCd(HSeO3)2Br, which expands the chemistry of the “layered hydroselenite” An(H2O)m[M(HSeO3)2Xn] family (M = Cu, Co, Zn; n = 1, 2). Formation of the two possible stoichiometries of the metal hydroselenite halide frameworks, [M(HSeO3)X2]– vs. [M(HSeO3)2X]–, (M = Cu, Cd; X = Cl, Br) is likely to depend on both the synthesis conditions and the r(A+)/r(X–) ratio. The potassium-free substructure of the triclinic ACd(HSeO3)X2 is represented by a planar net comprised of trans-CdO2X4 octahedra and hydroselenite anions. If the dimer of anions instead of the monomer is considered a secondary building unit (SBU), the net acquires a kagome net-like topology. The potassium-free substructure of monoclinic KCd(HSeO3)2Br is represented by planar nets, and upon considering SBU = (HSeO3)2 instead of (HSeO3), one obtains a simple square net.