Patra Ranjan, Goldberg Israel
School of Chemistry, Sackler Faculty of Exact Sciences, Tel-Aviv University, Ramat-Aviv, 69978 Tel-Aviv, Israel.
Acta Crystallogr C. 2013 Aug;69(Pt 8):819-21. doi: 10.1107/S0108270113017204. Epub 2013 Jul 9.
The synthesis is reported of the tricarboxylic acid 3-(3,5-dicarboxybenzyloxy)benzoic acid (H₃L) and the product of its reaction under solvothermal conditions with ZnII cations, namely poly[μ₆-3-(3,5-dicarboxylatobenzyloxy)benzoato-μ₃-hydroxido-dizinc(II)], [Zn₂(C₁₆H₉O7)(OH)(C₃H₇NO)]n, the formation of which is associated with complete deprotonation of H₃L. Its crystal structure consists of a single-framework coordination polymer of the organic L³⁻ ligand with ZnII cations in a 1:2 ratio, with additional hydroxide and dimethylformamide (DMF) ligands coordinated to the ZnII centres. The ZnII cations are characterized by coordination numbers of 5 and 6, being bridged to each other by hydroxide ligands. In the polymeric framework, the carboxylate- and hydroxy-bridged ZnII cations are arranged in coordination-tessellated columns, which propagate along the a axis of the crystal structure, and each L³⁻ ligand links to seven different ZnII centres via Zn-O bonds of two different columns. The coordination framework, composed of [Zn₂(L)(OH)(DMF)]n units, forms an open architecture, the channel voids within it being filled by the zinc-coordinating DMF ligands. This report provides the first structural evidence for the formation of coordination polymers with H₃L via multiple metal-ligand bonds through its carboxylate groups.
报道了三羧酸3-(3,5-二羧基苄氧基)苯甲酸(H₃L)的合成及其在溶剂热条件下与ZnII阳离子反应的产物,即聚[μ₆-3-(3,5-二羧基苄氧基)苯甲酸根-μ₃-羟基-二锌(II)],[Zn₂(C₁₆H₉O₇)(OH)(C₃H₇NO)]n,其形成与H₃L的完全去质子化有关。其晶体结构由有机L³⁻配体与ZnII阳离子以1:2比例形成的单骨架配位聚合物组成,还有额外的氢氧根和二甲基甲酰胺(DMF)配体配位到ZnII中心。ZnII阳离子的配位数为5和6,通过氢氧根配体相互桥连。在聚合物骨架中,羧酸根和羟基桥连的ZnII阳离子排列成配位镶嵌柱,沿晶体结构的a轴延伸,每个L³⁻配体通过两个不同柱的Zn-O键连接到七个不同的ZnII中心。由[Zn₂(L)(OH)(DMF)]n单元组成的配位骨架形成了一个开放结构,其内部的通道空隙被与锌配位的DMF配体填充。本报告首次提供了通过其羧酸根基团形成具有多个金属-配体键的H₃L配位聚合物的结构证据。