Pb⋯X (X = N, S, I) tetrel bonding interactions in Pb(ii) complexes: X-ray characterization, Hirshfeld surfaces and DFT calculations. Issue 20 (30th April 2018)

• Record Type: Journal Article
• Authors: Mahmoudi, Ghodrat; Seth, Saikat Kumar; Bauzá, Antonio; Zubkov, Fedor I.; Gurbanov, Atash V.; White, Jonathan; Stilinović, Vladimir; Doert, Thomas; Frontera, Antonio
• Is Part Of: CrystEngComm. Volume 20:Issue 20(2018)
• Page Start: 2812
• Page End: 2821
• Publication Date: 2018-04-30
• Subjects: Crystals -- Periodicals; Crystal growth -- Periodicals; Crystallography -- Periodicals; Cristaux -- Périodiques; Cristaux -- Croissance -- Périodiques; Cristallographie -- Périodiques; 548
• DOI: 10.1039/c8ce00110c
• Languages: English
• ISSNs: 1466-8033

Abstract

Abstract : We report the synthesis and X-ray characterization of four new Pb(ii ) complexes of nicotinoylhydrazone and picolinoylhydrazone-based ligands and three different anionic co-ligands (acetate, thiocyanate and iodide) exhibiting relevant tetrel bonding interactions. 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.