Extended lead(II) architectures engineered: Via tetrel bonding interactions

The evaluation of N′-(pyridin-2-ylmethylene)nicotinohydrazide (HLI) and N,N′′′-bis(1-(pyridin-2-yl)-ethylidene)carbazide (H2LII) as linker precursors in the synthesis of novel PbII extended structures is described. An equimolar one-pot reaction of PbX2 (X = NO3 -, CH3COO-) salts with HLI and H2LII in MeOH at 60 °C in a branched tube apparatus leads to heteroleptic complexes [Pb(HLI)(NO3)2]n (1), [Pb(LI)(CH3O)]n (2), [Pb2(H2LII)(NO3)4] (3) and [Pb2(HLII)(CH3COO)3]n (4), respectively. The nature of the anion in the parent PbII salt also influences the final structure. In all complexes, the PbII center exhibits a hemidirected coordination geometry with all the covalent bonds being concentrated on one hemisphere of the coordination sphere. The sterically available PbII ion participates in Pb⋯O/N tetrel bonding or Pb⋯Cg interaction as evidenced from the detailed structural and topological analysis of the described complexes. As a result of these interactions, the structures of all four compounds can be extended to a higher dimensional framework, which is further stabilized by hydrogen N-H⋯O/C-H⋯O and dihydrogen C-H⋯H-C bonds and/or π⋯π stacking interactions. The complementary Hirshfeld surface analysis of the discrete complex 3, considering covalent bonds, showed that the structure is highly dominated by H⋯X (X = O, H and C) and O⋯Y (Y = O, Pb, C and N) contacts, of which the O⋯Pb/H/N/C contacts are highly favoured. DFT based charge and energy decomposition (ETS-NOCV) calculations are performed in order to shed light on the nature of the non-covalent interactions that determine the stability of the obtained structures. © 2018 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.

Mahmoudi G. 1 , Zangrando E.2 , Mitoraj M.P.3 , Gurbanov A.V. 4, 8 , Zubkov F.I. 5 , Moosavifar M.1 , Konyaeva I.A.6, 7 , Kirillov A.M. 8 , Safin D.A.9
Royal Society of Chemistry
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  • 1 Department of Chemistry, Faculty of Science, University of Maragheh, P.O. Box 55181-83111, Maragheh, Iran
  • 2 Department of Chemical and Pharmaceutical Sciences, University of Trieste, Via L. Giorgieri 1, Trieste, 34127, Italy
  • 3 Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, R. Ingardena 3, Cracow, 30-060, Poland
  • 4 Department of Chemistry, Baku State University, Z. Khalilov Str. 23, Baku, AZ1148, Azerbaijan
  • 5 Organic Chemistry Department, Faculty of Science, Peoples' Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St., Moscow, 117198, Russian Federation
  • 6 Limited Liability Company NIOST, Kuzovlevski trakt 2, Tomsk, 634067, Russian Federation
  • 7 Department of Technology of Organic Substances and Polymer Materials, National Research Tomsk Polytechnic University, Lenin ave. 43, Tomsk, 634050, Russian Federation
  • 8 Centro de Química Estrutural, Complexo i, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais 1049-001, Lisbon, Portugal
  • 9 Institute of Chemistry, University of Tyumen, Perekopskaya Str. 15a, Tyumen, 625003, Russian Federation
anion; lead; Article; chemical binding; complex formation; covalent bond; decomposition; density functional theory; energy; hydrogen bond; molecular interaction; molecular stability; one pot synthesis; priority journal; stereospecificity; surface property; synthesis
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