Two isomers Ba5Mg4C54O48H114 and Pb5Mg4C54O48H114
- 20 July 2022
- journal article
- research article
- Published by Walter de Gruyter GmbH in Zeitschrift für Kristallographie - Crystalline Materials
- Vol. 237 (8-9), 351-359
- https://doi.org/10.1515/zkri-2021-2074
Abstract
There are reported two related structures of Ba5Mg4C54O48H114 (dodeca(aqua-6κ 3O,7κ 3O,8κ 3O,9κ 3O)-tris(μ2-propanoato-1:6κ 2O,1κO′)-tris(μ-propanoato-2:7κ 2O,2κO′-tris(μ-propanoato-3:8κ 2O,3κO′)-tris(μ-propanoato-4:9κ 2O,4κO′)-hexakis(μ3-propanoato-1:5κ 2O,2:5κ 2O′;1:5κ 2O,3:5κ 2O′;1:5κ 2O,4:5κ 2O′;2:5κ 2O,3:5κ 2O′;2:5κ 2O,4:5κ 2O′;3:5κ 2O,4:5κ 2O′)-pentabarium tetramagnesium), (I), and Pb5Mg4C54O48H114 (dodeca(aqua-1κ 3O,2κ 3O,3κ 3O,4κ 3O)-hexakis(μ3-propanoato-1:5κ 2O,2:5κ 2O′;1:5κ 2O,3:5κ 2O′;1:5 κ 2O,4:5κ 2O′;2:5κ 2O,3:5κ 2O′;2:5κ 2O,4:5κ 2O′;3:5κ 2O,4:5κ 2O′)tetramagnesium lead(II) tris(propanoato-κ 2O,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 . The structure (II) comprises the complex cation {Pb(C3H5O2)6[Mg(H2O)3]4}4+ with the symmetry and four anions [tris(propanoato-κ 2O,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 Owater‒H⋯Opropanoate 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-κ 2O,O′)plumbate(II)]− has a constitution with unusually prominent stereochemical activity of the 6s 2 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
Funding Information
- Grant Agency of the Czech Republic (Project No. 19-28594X)
This publication has 21 references indexed in Scilit:
- Structurally characterized magnesium carboxylates with tuned melting pointsPolyhedron, 2004
- Bond-valence parameters for solidsActa crystallographica Section B, Structural science, crystal engineering and materials, 1991
- X-Ray Crystal Structure Analysis of Ca2Pb(CH3CH2CO2)6in the Paraelectric and the Ferroelectric PhasesJournal of the Physics Society Japan, 1990
- The structure and spontaneous polarisation of the ferroelectric phase of dicalcium strontium propionateJournal of Physics C: Solid State Physics, 1982
- The structure and optical activity of the paraelectric phase of dicalcium strontium propionateJournal of Physics C: Solid State Physics, 1981
- The structure of and disorder in dicalcium barium propionateActa Crystallographica Section B: Structural Science, Crystal Engineering and Materials, 1980
- Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenidesActa Crystallographica Section A, 1976
- Effect of Hydrostatic Pressure on the Phase Transitions in Ferroelectric Ca2Sr(C2H5COO)6 and Ca2Pb(C2H5COO)6Journal of the Physics Society Japan, 1975
- Phase Transitions in Crystalline Divalent Metal Dicalcium Propionates. II. Proton Magnetic Resonance InvestigationBulletin of the Chemical Society of Japan, 1968
- Phase Transitions in Crystalline Divalent Metal Dicalcium Propionates. I. Calorimetric and Dielectric Investigations of Strontium- and Lead Dicalcium PropionatesBulletin of the Chemical Society of Japan, 1965