Pb⋯X (X = N, S, I) tetrel bonding interactions in Pb(II) complexes: X-ray characterization, Hirshfeld surfaces and DFT calculations

Ghodrat Mahmoudi; Saikat Kumar Seth; Antonio Bauzá; Fedor I. Zubkov; Atash V. Gurbanov; Jonathan White; Vladimir Stilinović; Thomas Doert; Antonio Frontera

doi:10.1039/C8CE00110C

Pb⋯X (X = N, S, I) tetrel bonding interactions in Pb(ii) complexes: X-ray characterization, Hirshfeld surfaces and DFT calculations†

Ghodrat Mahmoudi,

*^a Saikat Kumar Seth,

^bc Antonio Bauzá,

^c Fedor I. Zubkov,

^d Atash V. Gurbanov,

^ef Jonathan White,

^g Vladimir Stilinović,^h Thomas Doert

ⁱ and Antonio Frontera

*^c

Author affiliations

* Corresponding authors

^a Department of Chemistry, Faculty of Science, University of Maragheh, P.O. Box 55181-83111, Maragheh, Iran
E-mail: mahmoudi_ghodrat@yahoo.co.uk

^b Department of Physics, Jadavpur University, Kolkata 700032, India

^c Departament de Química, Universitat de les Illes Balears, Crta. de Valldemossa km 7.5, 07122 Palma (Baleares), Spain
E-mail: toni.frontera@uib.es

^d Organic Chemistry Department, Faculty of Science, Peoples' Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St., Moscow, Russian Federation

^e Department of Organic Chemistry, Baku State University, Z. Khalilov str. 23, Baku, AZ 1148, Azerbaijan

^f Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049–001 Lisboa, Portugal

^g BIO-21 Molecular Science and Biotechnology, University of Melbourne, Parkville, Victoria 3052, Australia

^h Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000 Zagreb, Croatia

ⁱ Department of Chemistry and Food Chemistry, Dresden University of Technology, Helmholtzstrasse 10, 01069 Dresden, Germany

Abstract

Four new Pb(II) complexes of nicotinoylhydrazone and picolinoylhydrazone-based ligands and three different anionic co-ligands (acetate, thiocyanate and iodide) have been synthesized and characterized by structural, analytical and spectroscopic methods. The ligands coordinate to the Pb(II) metal center in a tridentate fashion via two nitrogen and one oxygen donor atoms either in mono-deprotonated or in neutral forms. Single-crystal X-ray crystallography reveals that the molecular complexes aggregate into larger entities depending upon the anion coordinated to the metal centre. The Pb(II) center is hemidirectionally coordinated and, consequently, it is sterically ideal for establishing tetrel bonding interactions. Consequently, in the crystal structures of all the complexes, the Pb participates in short contacts with nitrogen, iodide or sulphur atoms. These contacts are shorter than the sums of the van der Waals radii and larger than the sums of the covalent radii, therefore they can be defined as non-covalent tetrel bonding interactions. They interconnect the covalently bonded units (monomers or dimers) into supramolecular assemblies (1D infinite chains and 3D structures). Hirshfeld surface analysis and fingerprint plots have been used to analyse the contribution of contacts involving the Pb atom. We have analysed the interesting supramolecular assemblies observed in the solid state of all four complexes by means of DFT calculations and characterized them using Bader's theory of atoms-in-molecules.

This article is part of the themed collection: 1st International Conference on Noncovalent Interactions

CrystEngComm

Pb⋯X (X = N, S, I) tetrel bonding interactions in Pb(ii) complexes: X-ray characterization, Hirshfeld surfaces and DFT calculations†

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Pb⋯X (X = N, S, I) tetrel bonding interactions in Pb(II) complexes: X-ray characterization, Hirshfeld surfaces and DFT calculations

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