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Three non-isostructural zinc(II) coordination polymers were synthesized (varying the time of reaction or the molar ratio of reagents) under mild hydrothermal conditions (T = 140°C) by mixture of zinc(II) acetate with 2-carboxyethylphosphonic acid and 1,10’-phenanthroline. All products were obtained as colorless single-crystals, but with different morphology. Their structures were determined by single-crystal X-ray diffraction, and the corresponding thermal stability is studied. Compound [Zn2(HO3PCH2CH2COO)2(C12H8N2)2(H2O)2] (ZnPF1) is monoclinic (space group P21/c) and crystallizes as discrete dimeric molecules, with one water molecule coordinated to each Zn atom, similarly to a previous reported structure [1]. Compound [Zn5(HO3PCH2CH2COO)4(C12H8N2)4(H2O)0.32] (ZnPF2) is also monoclinic (space group C2/c) and crystallizes as a tridimensional network, presenting channels in which water molecules are placed. One peculiarity of this compound is the presence of three different Zn atoms (four-five-six coordinated) in their structure. Although there are some examples in the literature which shows this feature [2-6], all of these consist in discrete molecules. Here we present the first tridimensional coordination polymer (MOF) with three Zn atoms having different coordination number. Compound [Zn6(HO3PCH2CH2COO)2(C12H8N2)1(H2O)2] (ZnPF3) is triclinic (space group P-1) and crystallizes forming 2D layered packing, with water molecules located in channels along a-axis. This compound also presents three different Zn atom in the structure (four-four-six coordinated). For these three compounds, structural features, including H-bond network and the — stacking interactions were reported and discussed here.

Synthesis, crystal structure and thermal behavior of coordination polymers based on zinc(II)