The effect of the coordination orientation of N atoms on polymeric structures: synthesis and characterization of one‐ and two‐dimensional CuII coordination polymers based on 4‐amino‐3‐(pyridin‐2‐yl)‐5‐[(pyridin‐3‐ylmethyl)sulfanyl]‐1,2,4‐triazole

Three new one‐ (1D) and two‐dimensional (2D) Cu^II coordination polymers, namely polybis{μ₂‐4‐amino‐3‐(pyridin‐2‐yl)‐5‐(pyridin‐3‐ylmethyl)sulfanyl]‐1,2,4‐triazole}copper(II)] bis(methanesulfonate) tetrahydrate], {Cu(C₁₃H₁₂N₅S)₂](CH₃SO₃)₂·4H₂O}_n ( 1 ), catena‐polycopper(II)‐bis{μ₂‐4‐amino‐3‐(pyridin‐2‐yl)‐5‐(pyridin‐4‐ylmethyl)sulfanyl]‐1,2,4‐triazole}] dinitrate methanol disolvate], {Cu(C₁₃H₁₂N₅S)₂](NO₃)₂·2CH₃OH}_n ( 2 ), and catena‐polycopper(II)‐bis{μ₂‐4‐amino‐3‐(pyridin‐2‐yl)‐5‐(pyridin‐4‐ylmethyl)sulfanyl]‐1,2,4‐triazole}] bis(perchlorate) monohydrate], {Cu(C₁₃H₁₂N₅S)₂](ClO₄)₂·H₂O}_n ( 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 H₂O 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.