Two isomers Ba5Mg4C54O48H114 and Pb5Mg4C54O48H114

Jan Fábry; Erika Samolová; Michal Dušek

doi:10.1515/zkri-2021-2074

Published by De Gruyter (O) August 17, 2022

Two isomers Ba₅Mg₄C₅₄O₄₈H₁₁₄ and Pb₅Mg₄C₅₄O₄₈H₁₁₄

Jan Fábry , Erika Samolová and Michal Dušek

From the journal Zeitschrift für Kristallographie - Crystalline Materials

https://doi.org/10.1515/zkri-2021-2074

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Abstract

There are reported two related structures of Ba₅Mg₄C₅₄O₄₈H₁₁₄ (dodeca(aqua-6κ³O,7κ³O,8κ³O,9κ³O)-tris(μ₂-propanoato-1:6κ²O,1κO′)-tris(μ-propanoato-2:7κ²O,2κO′-tris(μ-propanoato-3:8κ²O,3κO′)-tris(μ-propanoato-4:9κ²O,4κO′)-hexakis(μ₃-propanoato-1:5κ²O,2:5κ²O′;1:5κ²O,3:5κ²O′;1:5κ²O,4:5κ²O′;2:5κ²O,3:5κ²O′;2:5κ²O,4:5κ²O′;3:5κ²O,4:5κ²O′)-pentabarium tetramagnesium), (I), and Pb₅Mg₄C₅₄O₄₈H₁₁₄ (dodeca(aqua-1κ³O,2κ³O,3κ³O,4κ³O)-hexakis(μ₃-propanoato-1:5κ²O,2:5κ²O′;1:5κ²O,3:5κ²O′;1:5 κ²O,4:5κ²O′;2:5κ²O,3:5κ²O′;2:5κ²O,4:5κ²O′;3:5κ²O,4:5κ²O′)tetramagnesium lead(II) tris(propanoato-κ²O,O′)plumbate(II)), (II). The title structures are compositional isomers which crystallize in the same space group type. The structure of (I) comprises molecules with symmetry 4 ‾ 3 m . The structure (II) comprises the complex cation {Pb(C₃H₅O₂)₆[Mg(H₂O)₃]₄}⁴⁺ with the symmetry 4 ‾ 3 m and four anions [tris(propanoato-κ²O,O′)plumbate(II)]⁻, [Pb(C₃H₅O₂)₃]⁻ , with 3m symmetry. The central cations Ba1²⁺ and Pb1²⁺ in (I) and in the cation {Pb(C₃H₅O₂)₆[Mg(H₂O)₃]₄}⁴⁺ of the structure (II), respectively, have similar structural features which are comparable to the environment of the Ba²⁺ cation in BaCa₂(C₃H₅O₂)₆ [Stadnicka, K. & Glazer, A. M. (1980). Acta Cryst. B36, 2977–2985]. The molecules in (I) and the ions in (II) are interconnected by O_water‒H⋯O_propanoate hydrogen bonds of a moderate strength. The ethyl chains are disordered which is common in propanoates. However, there are unprecedented features in the title structures: 1) The central atom Pb1²⁺ is the first known example of a Pb²⁺ cation which is surrounded by six carboxylates in a bidentate bridging mode, i.e. by 12 oxygens. 2) The anion [tris(propanoato-κ²O,O′)plumbate(II)]⁻ has a constitution with unusually prominent stereochemical activity of the 6s² electron pair of the cation Pb²⁺ completing the coordination to the tetrahedral one. Thus, its formula can be expressed as [Pb^[ψ−4t](C₃H₅O₂)₃]⁻. 3) In both title structures, there are propanoate molecules with disordered carboxylate oxygens.

Keywords: positional disorder of the carboxylate oxygens; positional disorder of the ethyl chains; propanoates; stereochemical 6s2 lone pair activity in Pb2+

Corresponding author: Jan Fábry, Institute of Physics, Academy of Sciences of the Czech Republic, Na Slovance 2, 182 21 Praha 8, Czech Republic, E-mail: fabry@fzu.cz

Funding source: Grant Agency of the Czech Republic

Award Identifier / Grant number: Project No. 19-28594X

Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: This work was supported by the Czech Science Foundation (Project No. 19-28594X) which was granted to the Institute of Physics of the Academy of Sciences of the Czech Republic.
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Supplementary Material

The online version of this article offers supplementary material (https://doi.org/10.1515/zkri-2021-2074).

Received: 2021-12-08

Accepted: 2022-06-09

Published Online: 2022-08-17

Published in Print: 2022-09-27

Two isomers Ba₅Mg₄C₅₄O₄₈H₁₁₄ and Pb₅Mg₄C₅₄O₄₈H₁₁₄

Abstract

References

Supplementary Material

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