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

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. © 2018 The Royal Society of Chemistry.

Mahmoudi G. 1 , Seth S.K.2, 3 , Bauzá A.3 , Zubkov F.I. 4 , Gurbanov A.V. 5, 6 , White J.7 , Stilinović V.8 , Doert T.9 , Frontera A.3
Royal Society of Chemistry
Номер выпуска
  • 1 Department of Chemistry, Faculty of Science, University of Maragheh, P.O. Box 55181-83111, Maragheh, Iran
  • 2 Department of Physics, Jadavpur University, Kolkata, 700032, India
  • 3 Departament de Química, Universitat de les Illes Balears, Crta. de Valldemossa km 7.5, Palma (Baleares), 07122, Spain
  • 4 Organic Chemistry Department, Faculty of Science, Peoples' Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St., Moscow, 117198, Russian Federation
  • 5 Department of Organic Chemistry, Baku State University, Z. Khalilov str. 23, Baku, AZ 1148, Azerbaijan
  • 6 Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, Lisboa, 1049-001, Portugal
  • 7 BIO-21 Molecular Science and Biotechnology, University of Melbourne, Parkville, VIC 3052, Australia
  • 8 Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, Zagreb, 10000, Croatia
  • 9 Department of Chemistry and Food Chemistry, Dresden University of Technology, Helmholtzstrasse 10, Dresden, 01069, Germany
Дата создания
Дата изменения
Постоянная ссылка