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Pb⋯X (X = N, S, I) tetrel bonding interactions in Pb(<scp>ii</scp>) complexes: X-ray characterization, Hirshfeld surfaces and DFT calculations
- Source :
- CrystEngComm. 20:2812-2821
- Publication Year :
- 2018
- Publisher :
- Royal Society of Chemistry (RSC), 2018.
-
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.
- Subjects :
- Steric effects
chemistry.chemical_classification
Thiocyanate
010405 organic chemistry
Iodide
Supramolecular chemistry
General Chemistry
Crystal structure
010402 general chemistry
Condensed Matter Physics
01 natural sciences
0104 chemical sciences
Crystallography
symbols.namesake
chemistry.chemical_compound
chemistry
Covalent bond
Covalent radius
tetrel bond
Pb(II) complexes
crystal structure
Hirshfeld surface
DFT calculations
symbols
General Materials Science
Van der Waals radius
Subjects
Details
- ISSN :
- 14668033
- Volume :
- 20
- Database :
- OpenAIRE
- Journal :
- CrystEngComm
- Accession number :
- edsair.doi.dedup.....49501ca82f87b00f1c8475f6093140d5