Polar protic solvent-trapping polymorphism of the HgII-hydrazone coordination polymer: Experimental and theoretical findings

A novel series of HgII coordination polymers with a general formula [HgL(N)3]n·n(solv) (HL = 2-pyridinecarbaldehyde isonicotinoylhydrazone; n(solv) = 0.5H2O (1), 2MeOH (2), EtOH (3), PrOH (4) and 0.5BuOH (5)) was prepared and characterized by elemental analysis, IR spectroscopy and single crystal X-ray diffraction. The crystal structure of HL, elucidated by X-ray diffraction, comprises two independent molecules in the asymmetric unit cell, each of which is stabilized by an intramolecular hydrogen bond formed between the carbohydrazide hydrogen atom and the 2-pyridyl nitrogen atom. Crystal structures of 1-5 each reveal a similar 1D zigzag metal-organic chain [HgL(N)3]n, where the organic ligands bridge metal centers. These chains are extended into distinct 2D supramolecular nets by strong hydrogen bonds with the solvent molecules and/or short Hg⋯N supramolecular contacts. These networks were topologically classified as the hcb in 1 and fes in 2-5 underlying nets. On comparing the H-bonding patterns, it can be concluded that the lattice water molecules in 1 and methanol molecules in 2 form H-bonding interactions with the O and amide N atoms of L in the former structure and the O atom of L in the latter structure. In the remaining coordination compounds, the lattice solvent prefers the azide N atom for H-bonding. Furthermore, the existence of Hg⋯N interactions in 2-5 and their absence in 1 clearly highlights the importance of the size and polarity of the solvents on the self-assembly generation of HgII coordination polymers. A broad network of intermolecular π⋯π stacking interactions, formed between the pyridyl fragments, provide further reinforcement of crystal packing patterns in the structures of HL and 2-5. DFT based charge and energy decomposition scheme (ETS-NOCV) was applied to characterize the obtained polymers. © 2017 The Royal Society of Chemistry.

Mahmoudi G. 1, 2 , Khandar A.A.3 , White J.4 , Mitoraj M.P.5 , Jena H.S.6 , Der Voort P.V. , Qureshi N.7 , Kirillov A.M.8 , Robeyns K.9 , 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 Inorganic Chemistry Department, RUDN University, Miklukho-Maklaya str. 6, Moscow, 117198, Russian Federation
  • 3 Department of Inorganic Chemistry, Faculty of Chemistry, University of Tabriz, P.O. Box 51666-16471, Tabriz, Iran
  • 4 BIO-21 Molecular Science and Biotechnology, University of Melbourne, Parkville, VIC 3052, Australia
  • 5 Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, R. Ingardena 3, Cracow, 30-060, Poland
  • 6 COMOC-Center for Ordered Materials, Organometallics and Catalysis, Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281-S3, Ghent, 9000, Belgium
  • 7 Department of Chemistry, Karakoram International University, Gilgit-Baltistan, Pakistan
  • 8 Centro de Química Estrutural, Complexo i, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais 1049-001, Lisbon, Portugal
  • 9 Institute of Condensed Matter and Nanosciences, Université Catholique de Louvain, Place L. Pasteur 1, Louvain-la-Neuve, 1348, Belgium
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