Zhu Guiying, Lu Yang, Jin Guoxia, Ji Xuan, Ma Jianping
College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Functionalized Probes for Chemical Imaging in Universities of Shandong, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong Provincial Key Laboratory of Clean Production of Fine Chemicals, Shandong Normal University, Jinan 250014, People's Republic of China.
Acta Crystallogr C Struct Chem. 2019 Apr 1;75(Pt 4):443-450. doi: 10.1107/S2053229619003747. Epub 2019 Mar 26.
Three new one- (1D) and two-dimensional (2D) Cu coordination polymers, namely poly[[bis{μ-4-amino-3-(pyridin-2-yl)-5-[(pyridin-3-ylmethyl)sulfanyl]-1,2,4-triazole}copper(II)] bis(methanesulfonate) tetrahydrate], {Cu(CHNS)·4HO} (1), catena-poly[[copper(II)-bis{μ-4-amino-3-(pyridin-2-yl)-5-[(pyridin-4-ylmethyl)sulfanyl]-1,2,4-triazole}] dinitrate methanol disolvate], {Cu(CHNS)·2CHOH} (2), and catena-poly[[copper(II)-bis{μ-4-amino-3-(pyridin-2-yl)-5-[(pyridin-4-ylmethyl)sulfanyl]-1,2,4-triazole}] bis(perchlorate) monohydrate], {Cu(CHNS)·HO} (3), were obtained from 4-amino-3-(pyridin-2-yl)-5-[(pyridin-3-ylmethyl)sulfanyl]-1,2,4-triazole with pyridin-3-yl terminal groups and from 4-amino-3-(pyridin-2-yl)-5-[(pyridin-4-ylmethyl)sulfanyl]-1,2,4-triazole with pyridin-4-yl terminal groups. Compound 1 displays a 2D net-like structure. The 2D layers are further linked through hydrogen bonds between methanesulfonate anions and amino groups on the framework and guest HO molecules in the lattice to form a three-dimensional (3D) structure. Compound 2 and 3 exhibit 1D chain structures, in which the complicated hydrogen-bonding interactions play an important role in the formation of the 3D network. These experimental results indicate that the coordination orientation of the heteroatoms on the ligands has a great influence on the polymeric structures. Moreover, the selection of different counter-anions, together with the inclusion of different guest solvent molecules, would also have a great effect on the hydrogen-bonding systems in the crystal structures.
合成了三种新型的一维（1D）和二维（2D）铜配位聚合物，即聚[[双{μ-4-氨基-3-(吡啶-2-基)-5-[(吡啶-3-基甲基)硫烷基]-1,2,4-三唑}铜（II）]双（甲磺酸盐）四水合物]，{Cu(CHNS)·4HO}（1），链状聚[[铜（II）-双{μ-4-氨基-3-(吡啶-2-基)-5-[(吡啶-4-基甲基)硫烷基]-1,2,4-三唑}]二硝酸酯甲醇溶剂化物]，{Cu(CHNS)·2CHOH}（2），以及链状聚[[铜（II）-双{μ-4-氨基-3-(吡啶-2-基)-5-[(吡啶-4-基甲基)硫烷基]-1,2,4-三唑}]双（高氯酸盐）一水合物]，{Cu(CHNS)·HO}（3），它们分别由带有吡啶-3-基端基的4-氨基-3-(吡啶-2-基)-5-[(吡啶-3-基甲基)硫烷基]-1,2,4-三唑和带有吡啶-4-基端基的4-氨基-3-(吡啶-2-基)-5-[(吡啶-4-基甲基)硫烷基]-1,2,4-三唑制得。化合物1呈现二维网状结构。二维层通过甲磺酸根阴离子与骨架上氨基以及晶格中客体HO分子之间的氢键进一步连接，形成三维（3D）结构。化合物2和3表现出一维链状结构，其中复杂的氢键相互作用在三维网络的形成中起重要作用。这些实验结果表明配体上杂原子的配位取向对聚合物结构有很大影响。此外，不同抗衡阴离子的选择以及不同客体溶剂分子的加入，也会对晶体结构中的氢键体系产生很大影响。
