Synthesis, structural and mass spectrometric investigations of pyridinium bis(thiosalicylato)mercurate(II)
Autor: | Edward R. T. Tiekink, William Henderson, Jesse C. Thomas, Obinna C. Okpareke |
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Rok vydání: | 2019 |
Předmět: |
Denticity
Hydrogen 010405 organic chemistry Chemistry Decarboxylation Hydrogen bond chemistry.chemical_element 010402 general chemistry 01 natural sciences 0104 chemical sciences Inorganic Chemistry chemistry.chemical_compound Crystallography Pyridine Materials Chemistry Carboxylate Pyridinium Physical and Theoretical Chemistry Single crystal |
Zdroj: | Inorganica Chimica Acta. 490:104-111 |
ISSN: | 0020-1693 |
Popis: | This work investigates the synthesis and structural properties of a hydrogen-bonded salt of the [Hg(SC6H4-2-CO2)2]2− ion. The known bis(thiosalicylato)mercury(II) complex [Hg(SC6H4-2-CO2H)2], dissolves in pyridine (py), from which the crystalline pyridinium salt (pyH)2[Hg(SC6H4-2-CO2)2] can be isolated. Single crystal X-ray crystallography reveals two distinct three-molecule aggregates, namely {Hg[SC6H4-2-C(=O)OH]2(NC5H5)2} and {Hg[SC6H4-2-C(=O)O]2(HNC5H5)2}, which differ in the location of the acidic hydrogen atoms, i.e. either compound-bound for the former species or located on the pyridinium cations in the latter. The thiolate ligands are S,O-chelating and the resultant O2S2 four-coordinate geometries are each based on a distorted disphenoidal geometry. The three-molecule aggregates are sustained by hydroxyl O H⋯N(pyridine) hydrogen bonds in the case of {Hg[SC6H4-2-C(=O)OH]2(NC5H5)2} whereas the second aggregate features charge-assisted pyridinium N H⋯O(carboxylate) hydrogen bonds. (pyH)2[Hg(SC6H4-2-CO2)2] was also characterised by negative-ion ESI mass spectrometry, where it showed appreciable stability towards capillary exit voltage-induced fragmentation. In contrast, the S-bonded monodentate thiosalicylate complexes RHg(SC6H4-2-CO2)− (R = Et, Ph or ferrocenyl) undergo facile decarboxylation at relatively low voltages, with the phenyl and ferrocenyl complexes subsequently forming RHgS− as an additional fragment ion at high voltages. Aggregate ions formed with the sodium counter-cations of the type [(RHgSC6H4-2-CO2)nNan−1]− show appreciable stability towards fragmentation. |
Databáze: | OpenAIRE |
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