Experimental and theoretical study of Pb⋯S and Pb⋯O σ-hole interactions in the crystal structures of Pb(ii) complexes. Issue 40 (23rd September 2019)

• Record Type: Journal Article
• Authors: Velásquez, Juan D.; Mahmoudi, Ghodrat; Zangrando, Ennio; Gurbanov, Atash V.; Zubkov, Fedor I.; Zorlu, Yunus; Masoudiasl, Ardavan; Echeverría, Jorge
• Is Part Of: CrystEngComm. Volume 21:Issue 40(2019)
• Page Start: 6018
• Page End: 6025
• Publication Date: 2019-09-23
• Subjects: Crystals -- Periodicals; Crystal growth -- Periodicals; Crystallography -- Periodicals; Cristaux -- Périodiques; Cristaux -- Croissance -- Périodiques; Cristallographie -- Périodiques; 548
• DOI: 10.1039/c9ce00959k
• Languages: English
• ISSNs: 1466-8033

Abstract

Abstract : The crystal structures of two novel Pb(ii ) hemidirected compounds present considerably strong Pb⋯S σ-hole bonding as the main intermolecular interactions. Abstract : We report here the synthesis of two new Pb(ii ) compounds in which the lead center is coordinated by organic ligands via S and O donor atoms. Remarkably, in both compounds the Pb coordination is hemidirectional, which facilitates the approach of extra donors to establish interactions at longer distances. Such interactions are of σ-hole nature between the Pb and O/S atoms, acting as Lewis acid and bases, respectively. Interestingly, the Pb⋯S/O distances are closer to the sum of the covalent radii than to the van der Waals ones, which suggests a considerably strong interaction. We have performed a structural analysis of the crystal structures as well as a theoretical analysis based on DFT calculations to gain deeper insight into the origin and features of these σ-hole interactions. Moreover, the nature of the Pb⋯S/O interactions have been further analysed by means of AIM, MEP and NBO calculations.