Synthesis, structural and mass spectrometric investigations of pyridinium bis(thiosalicylato)mercurate(II)

Content Provider	Semantic Scholar
Author	Henderson, William Thomas, Jesse C. Okpareke, Obinna C. Tiekink, Edward R. T.
Copyright Year	2019
Abstract	The previously-described bis(thiosalicylato)mercury(II) complex [Hg(SC6H4-2-CO2H)2],prepared from HgCl2 and thiosalicylic acid (HSC6H4-2-CO2H) with added NaOH, dissolves in pyridine (py), from which the crystalline pyridinium salt (pyH)2[Hg(SC6H4-2-CO2)2] can be isolated as large colourless blocks. Single crystal X-ray crystallography reveals the crystal to comprise 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. These aggregates are connected into a three-dimensional architecture by a combination of C‒H…O, π…π, Hg…π and O…π interactions. (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 RHgSas 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.
Starting Page	104
Ending Page	111
Page Count	8
File Format	PDF HTM / HTML
DOI	10.1016/j.ica.2019.03.002
Volume Number	490
Alternate Webpage(s)	http://eprints.sunway.edu.my/1002/1/Synthesis%20structural%20and%20mass%20sprectrometric%20Inorganica%20Chimca%20Acta%202019%20490%20104%20accepted%20manuscript%20(002).pdf
Alternate Webpage(s)	https://doi.org/10.1016/j.ica.2019.03.002
Language	English
Access Restriction	Open
Content Type	Text
Resource Type	Article