On the Importance of Unprecedented Lone Pair鈥揝alt Bridge Interactions in Cu(II)鈥揗alonate鈥?-Amino-5-Chloropyridine鈥揚erchlorate Ternary System

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• 作者：Monojit Mitra ; Prankrishna Manna ; Amrita Das ; Saikat Kumar Seth ; Madeleine Helliwell ; Antonio Bauz谩 ; Somnath Ray Choudhury ; Antonio Frontera ; Subrata Mukhopadhyay
• 刊名：The Journal of Physical Chemistry A
• 出版年：2013
• 出版时间：July 18, 2013
• 年：2013
• 卷：117
• 期：28
• 页码：5802-5811
• 全文大小：589K
• 年卷期：v.117,no.28(July 18, 2013)
• ISSN：1520-5215

文摘

A Cu(II)鈥搈alonate complex with formula {(C₅H₆N₂Cl)₁₂[Cu(1)(C₃H₂O₄)₂][Cu(2)(C₃H₂O₄)₂(H₂O)₂][Cu(4)(C₃H₂O₄)₂][Cu(3)(C₃H₂O₄)₂(H₂O)₂](ClO₄)₄}_n (1) [C₅H₆N₂Cl = protonated 2-amino-5-chloropyridine, C₃H₄O₄ = malonic acid, ClO₄^{鈥?/sup> = perchlorate] has been synthesized from purely aqueous media simple by mixing the reactants in their stoichiometric ratio, and its crystal structure has been determined by single-crystal X-ray diffraction. In 1, copper(II) malonate units form infinite 1D polymeric chains, which are interlinked by hydrogen bonds to generate 2D sheets. These 2D sheets are joined side by side primarily by various hydrogen bonds to form a 3D structure. A multitude of salt bridges are formed in this structure, connecting the protonated 2-amino-5-chloropyridines and the malonate ligands of the polymeric polyanion. Examining this characteristic of the solid-state architecture, we noticed several salt-bridge (sb)路路路蟺 interactions and an unexplored interaction between the lone pair (lp) of one malonate oxygen atom and a planar salt bridge. The combination of this interaction with various other weak intermolecular forces results in a remarkably extended supramolecular network combining a wide variety of interactions involving 蟺鈥搒ystems (Cl路路路蟺, 蟺路路路蟺) and salt bridges (sb路路路蟺 and lp路路路sb). We describe the energetic and geometric features of this lone pair鈥搒alt-bridge interaction and explore its impact on the resultant supramolecular organization using theoretical DFT-D3 calculations.}