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Complexes of BiCl3 with hydrazone derived ligands: a Möbius-like discrete metal chelate versus a salt-like porous polymeric structure

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Abstract

In this work we have synthesized and characterized a new helical complex of BiCl3, namely [Bi(LI)Cl3], fabricated with an extremely bulky ligand, 1,2-diphenyl-1,2-bis((phenyl(pyridin-2-yl)methylene)hydrazono)ethane (LI). The same reaction of BiCl3 with N′-(4-hydroxybenzylidene)isonicotinohydrazide (HLII) has allowed us to obtain a salt-like porous polymeric structure ([H2LII]2[BiCl5]·EtOH)n. As evidenced from the single crystal X-ray analysis data, complex [Bi(LI)Cl3] is a Möbius-like discrete metal chelate, where the BiIII atom is seven-coordinated in a distorted pentagonal bipyramidal N4Cl3 geometry and the organic ligand LI adopts a helical twist conformation. The structure of compound ([H2LII]2[BiCl5]·EtOH)n comprises monoprotonated non-coordinated organic molecules [H2LII]+ counterbalanced by a [BiCl5]2− anionic fragment, which, in turn, forms a 1D zig-zag polymeric chain. The organic molecules are arranged in a centrosymmetric fashion yielding a hydrogen bonded tetramer with a rectangular cavity of dimensions 7.55 × 9.02 Å. The tetramers are stacked through weak intermolecular interactions, yielding 1D infinite channels. Thus, complex ([H2LII]2[BiCl5]·EtOH)n was found to be a porous organic–inorganic hybrid compound. By using DFT calculations we have analyzed and rationalized the molecular electrostatic potential (MEP) surfaces and, through the quantum theory of the “atoms-in-molecules” (QTAIM) computational tool, the hydrogen bonding interactions observed in the solid state of both crystal structures, focusing on the competition between O–H⋯O and N–H⋯O hydrogen bonds in ([H2LII]2[BiCl5]·EtOH)n.

Graphical abstract: Complexes of BiCl3 with hydrazone derived ligands: a Möbius-like discrete metal chelate versus a salt-like porous polymeric structure

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Supplementary files

Article information


Submitted
22 Feb 2020
Accepted
06 May 2020
First published
06 May 2020

New J. Chem., 2020, Advance Article
Article type
Paper

Complexes of BiCl3 with hydrazone derived ligands: a Möbius-like discrete metal chelate versus a salt-like porous polymeric structure

F. Akbari Afkhami, G. Mahmoudi, B. Miroslaw, F. Qu, A. Gupta, A. Frontera, F. I. Zubkov, E. Zangrando and D. A. Safin, New J. Chem., 2020, Advance Article , DOI: 10.1039/D0NJ00930J

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