Spodium bonds and metal–halogen···halogen–metal interactions in propagation of monomeric units to dimeric or polymeric architectures

In this work we report on crystal structures of a heteroleptic coordination polymer [Hg2(HL)Cl4]n (1) where the nitrogen atom of the peripheral pyridine fragment is linked to another HgCl2 molecule and two discrete mononuclear heteroleptic complexes [Hg(HL)I2] (2) and [Mn(HL)Cl2]·MeOH (3·MeOH), which were obtained through self-assembling of N'-(1-(pyridin-2-yl)ethylidene)isonicotinohydrazide (HL) with HgCl2, HgI2 or MnCl2, respectively. HL coordinates the HgII salts in its keto-form, while MnCl2 is chelated by a zwitterionic form of HL confirmed by the solid state IR spectroscopy. The studied here ligand molecule has a tendency to involve the 4-pyridyl nitrogen atom in coordination bonding which is correlated with the ability to transfer the electric charge and production of a zwitterionic form. The crystal structure and Hirshfeld surface data analysis show a great importance of spodium bonds and metal–halogen⋯halogen–metal interactions. A prominent consequence of lack of σ- or π-hole interactions in case of MnII ion is the isolation of metal center from the external contacts. Apart form this in 3·MeOH the halogen⋯halogen interactions are absent. It seems that the σ- or π-hole regions formed at the HgII cation in 1 and 2 favor the participation of coordinated Cl or I atoms in the M–Hal⋯Hal'–M' halogen⋯halogen interactions, whereas in complex 3·MeOH there are no metal or halogen centered σ-hole interactions. Thus, the 1D coordination polymer in 1 is stabilized by the Hg⋯Cl spodium bonding. Additionally, the observed intermolecular halogen⋯halogen interactions in 1 provide cross-linking of the 1D coordination polymers, yielding a 2D supramolecular double-layered sheet. In 2 an additional contact between halogen and mercury atoms results in a dimeric unit. These dimers are linked into a 1D polymer by halogen⋯halogen interactions between metal bounded iodine atoms. The DFT theoretical studies were applied to analyze the Hg⋯X non-covalent spodium interactions that govern the formation of the 1D polymeric structure in 1 and self-assembled dimers in 2. © 2021

Alizadeh V.1 , Mahmoudi G. 2 , Vinokurova M.A. 3 , Pokazeev K.M. 3 , Alekseeva K.A. 3 , Miroslaw B.4 , Khandar A.A.5 , Frontera A.6 , Safin D.A.7, 8, 9
  • 1 Department of Petroleum Engineering, Faculty of Engineering, University of Garmsar, Garmsar, Iran
  • 2 Department of Chemistry, Faculty of Science, University of Maragheh, Maragheh, P.O. Box 55181-83111, Iran
  • 3 Organic Chemistry Department, Faculty of Science, Peoples Friendship University of Russia (RUDN University), Miklukho-Maklaya Str. 6, Moscow, 117198, Russian Federation
  • 4 Department of General and Coordination Chemistry and Crystallography, Institute of Chemical Sciences, Faculty of Chemistry, Maria Curie-Sklodowska University in Lublin, Pl. Marii Curie-Sklodowskiej 3, 20-031, Lublin, Poland
  • 5 Department of Inorganic Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, 51666-16471, Iran
  • 6 Departament de Química, Universitat de les Illes Balears, Cra. de Valldemossa km 7.5, 07122 Palma de MallorcaBaleares, Spain
  • 7 University of Tyumen, Volodarskogo Str. 6, Tyumen, 625003, Russian Federation
  • 8 Advanced Materials for Industry and Biomedicine laboratory, Kurgan State University, Sovetskaya Str. 63/4, Kurgan, 640020, Russian Federation
  • 9 Innovation Center for Chemical and Pharmaceutical Technologies, Ural Federal University named after the First President of Russia B.N. Eltsin, Mira Str. 19, Ekaterinburg, 620002, Russian Federation
DFT; Halogen interactions; Hirshfeld surface analysis; Manganese halide; Mercury halide; Spodium bond
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