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Title
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Spodium bonds and metal–halogen···halogen–metal interactions in propagation of monomeric units to dimeric or polymeric architectures
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Type
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JournalPaper
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Keywords
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Mercury halideManganese halideHalogen interactionsSpodium bondHirshfeld surface analysisDFT
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Abstract
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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
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Researchers
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Damir A Safin (Not In First Six Researchers), Antonio Frontera (Not In First Six Researchers), Ali Akbar Khandar (Not In First Six Researchers), Barbara Mirosław (Not In First Six Researchers), Kseniia A. Alekseeva (Fifth Researcher), Kuzma M. Pokazeev (Fourth Researcher), Marina A. Vinokurova (Third Researcher), Ghodrat Mahmoudi (Second Researcher), Vali Alizadeh (First Researcher)
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