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Synthesis, crystal structures and optical properties of mercury(II) halide compounds with (E)-N-(pyridin-2-ylmethylidene)arylamines: Effect of ligand R-group upon structure


Basu Baul, Tushar S; Kundu, Sajal; Höpfl, Herbert; Tiekink, Edward R T; Linden, Anthony (2013). Synthesis, crystal structures and optical properties of mercury(II) halide compounds with (E)-N-(pyridin-2-ylmethylidene)arylamines: Effect of ligand R-group upon structure. Polyhedron, 55:270-282.

Abstract

A systematic series of seven mercury compounds of (E)-N-(pyridin-2-ylmethylidene)arylamine (L), where L is a variously R substituted ligand, with the formulations [HgX2L]2: X = Cl; R = 4-CH2CH3 (4), 4-OCH2CH3 (5), 4-Cl (6), 2-CO2CH3 (7), or 4-CO2CH3 (8); X = Br; R = 4-CO2CH3 (9a) and [HgX2L]: X = Br; R = 4-CO2CH3 (9b) and X = I; R = 4-CO2CH3 (10), were synthesized. All compounds have been structurally characterized by single-crystal X-ray diffraction studies and their spectroscopic (IR, NMR, UV–Vis and fluorescence) properties are described. The structural analyses reveal that compounds 4–9a are centrosymmetric binuclear compounds while compounds 9b (a polymorph of the binuclear compound 9a) and 10 are mononuclear compounds. The HgCl2 compounds are more likely to dimerize via Hg⋯Cl bridges complexed with (E)-N-(pyridin-2-ylmethylidene)arylamine ligands compared with their HgBr2 and HgI2 analogs. This feature of the structural chemistry is correlated with the enhanced Lewis acidity of the mercury in the HgCl2 compounds. Moderating the electronegativity of the substituents in L is shown to influence the strength of the Hg–N(imino) bond in HgCl2L compounds.

Abstract

A systematic series of seven mercury compounds of (E)-N-(pyridin-2-ylmethylidene)arylamine (L), where L is a variously R substituted ligand, with the formulations [HgX2L]2: X = Cl; R = 4-CH2CH3 (4), 4-OCH2CH3 (5), 4-Cl (6), 2-CO2CH3 (7), or 4-CO2CH3 (8); X = Br; R = 4-CO2CH3 (9a) and [HgX2L]: X = Br; R = 4-CO2CH3 (9b) and X = I; R = 4-CO2CH3 (10), were synthesized. All compounds have been structurally characterized by single-crystal X-ray diffraction studies and their spectroscopic (IR, NMR, UV–Vis and fluorescence) properties are described. The structural analyses reveal that compounds 4–9a are centrosymmetric binuclear compounds while compounds 9b (a polymorph of the binuclear compound 9a) and 10 are mononuclear compounds. The HgCl2 compounds are more likely to dimerize via Hg⋯Cl bridges complexed with (E)-N-(pyridin-2-ylmethylidene)arylamine ligands compared with their HgBr2 and HgI2 analogs. This feature of the structural chemistry is correlated with the enhanced Lewis acidity of the mercury in the HgCl2 compounds. Moderating the electronegativity of the substituents in L is shown to influence the strength of the Hg–N(imino) bond in HgCl2L compounds.

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Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Uncontrolled Keywords:Mercury / (E)-N-(pyridin-2-ylmethylidene)arylamine / N,N- donor ligands / 42 Spectroscopy / Structure elucidation / Crystal structure
Language:English
Date:2013
Deposited On:21 Oct 2013 08:49
Last Modified:16 Feb 2018 18:11
Publisher:Elsevier
ISSN:0277-5387
Funders:Department of Science & Technology, New Delhi, India (Grant 545 No.SR/S1/IC-03/2005,TSBB), Indo-Swiss Joint Research Programme, Joint Utilisation of Advanced 547 Facilities (Grant No. JUAF 11, TSBB, AL), University Grants Commission, New Delhi, India through 546 SAP-DSA, Phase-III, Ministry of Higher Education, Malaysia, High-Impact Research scheme (UM.C/HIR549 MOHE/SC/03)
OA Status:Green
Publisher DOI:https://doi.org/10.1016/j.poly.2013.03.025

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