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|Title:||Spodium bonding and other non-covalent interactions assisted supramolecular aggregation in a new mercury(II) complex of a nicotinohydrazide derivative|
Gurbanov, A. V.
Babashkina, M. G.
Safin, D. A.
|Citation:||Spodium bonding and other non-covalent interactions assisted supramolecular aggregation in a new mercury(II) complex of a nicotinohydrazide derivative / G. Mahmoudi, E. Zangrando, B. Miroslaw, et al. — DOI 10.1016/j.ica.2021.120279 // Inorganica Chimica Acta. — 2021. — Vol. 519. — 120279.|
|Abstract:||In this work we report a new Hg(II) coordination compound [Hg(HL)(SCN)2], which was readily obtained from a mixture of Hg(SCN)2 and N'-(1-(pyridin-2-yl)ethylidene)nicotinohydrazide (HL). The metal cation is chelated by the organic ligand in a N,N',O tridentate manner through the 2-Py and amide nitrogen donors, and carbonyl oxygen atom. The coordination sphere is filled by the sulfur donors of two thiocyanate anions, thus yielding a pentacoordinated geometry, which is best described as being about 64% along the pathway of distortion from the ideal square pyramidal toward trigonal bipyramidal structure. In addition, the metal center forms two types of the Hg⋯N spodium bonds, which are formed with the 3-Py nitrogen atom of a symmetry related molecule and with the nitrogen atom of one thiocyanate ligand of another molecular unit. These Hg⋯N spodium bonds enlarge the coordination environment of the metal cation in between a capped trigonal prism close to pentagonal bipyramid. In addition a 1D zig-zag-like polymeric chain is formed, which is further reinforced by bilateral C–H⋯O hydrogen bonds. These chains are interlinked through N–H⋯N hydrogen bonds and additionally glued by π⋯π interactions between the 2-Py rings. Thus, considering all the Hg⋯N spodium and N–H⋯N hydrogen bonds, a supramolecular 2D layer is formed with a binodal 3,4-connected hcb topology. The 2D layers are interlinked through a myriad of π⋯π interactions. According to the Hirshfeld surface analysis, the crystal packing of [Hg(HL)(SCN)2] is mainly characterized by intermolecular H⋯H, H⋯C, H⋯N and H⋯S contacts comprised from 15.9 to 22.3%, followed by less significant H⋯O, C⋯C, C⋯N, N⋯S and Hg⋯N contacts comprised from 2.8 to 6.3%. The intermolecular H⋯C, H⋯N, H⋯O, H⋯S and C⋯C contacts are highly favoured in the molecular surface of [Hg(HL)(SCN)2], while the N⋯S contacts are less favoured, and remaining contacts are significantly impoverished. Finally, density functional theory (DFT) calculations at the PBE0/def2-TZVP level of theory have been used to evaluate and characterize the Hg⋯N spodium bonds, including molecular electrostatic potential (MEP), quantum theory of atoms in molecules (QTAIM) and noncovalent interaction plot (NCIPlot) computational tools. © 2021 Elsevier B.V.|
DENSITY FUNCTIONAL THEORY
CARBONYL OXYGEN ATOMS
MOLECULAR ELECTROSTATIC POTENTIALS
QUANTUM THEORY OF ATOMS IN MOLECULES
|metadata.dc.description.sponsorship:||This work has been partially supported by the Fundação para a Ciência e a Tecnologia ( FCT ) 2020–2023 multiannual funding to Centro de Quimica Estrutural (project UIDB/00100/2020). AVG acknowledges the FCT and Instituto Superior Técnico (DL 57/2016 and L 57/2017 Program, Contract no: IST-ID/110/2018). This research was partially funded by MICIU/AEI, grant number CTQ2017-85821-R, FEDER funds.|
|Appears in Collections:||Научные публикации, проиндексированные в SCOPUS и WoS CC|
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