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CRYSTAL STRUCTURE OF COORDINATION COBALT(II) AND ZINC(II) POLYMERS WITH 1,4-DIAZABICYCLO[2.2.2]OCTANE N,N′-DIOXIDE

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Abstract

Four cobalt(II) and zinc(II) cationic metal-organic frameworks (MOFs) based on bridging 1,4-diazabicyclo[2.2.2]octane N,N′-dioxide (odabco) are synthesized. In a mixture of N,N-dimethyl formamide (DMF) and water acidified with nitric acid, [Co(odabco)3](NO3)2 compound (I) is obtained. The synthesis in a mixture of dimethyl acetamide (DMA), acetic acid, and water results in the formation of [Co2(odabco)3(OAc)2](NO3)2 (II, OAc– - acetate) MOF containing coordinated acetate anions. In DMF acidified with hydrochloric acid, [Zn2(odabco)3Cl2](NO3)2·DMF·2H2O, compound (III) containing coordinated chloride anions is obtained. In a mixture of DMA and water acidified with nitric acid, [Zn(odabco)2](NO3)2(Hodabco)NO3·0.83H2O MOF (IV) is synthesized. The structures of I-IV are determined by single crystal X-ray diffraction. In all structures, odabco acts as a bridging ligand forming cationic layered (II, III) or 3D (I, IV) coordination lattices and protonated guest chains {–Hodabco+–}n in IV. The cavities in the lattices of I-IV have total solvent-accessible volumes of 10%, 11%, 28%, and 56% respectively and accomodate \(\text{NO}_3^{-}\) counterions. Compounds I and II are the first examples of coordination polymers based on Co2+ and the odabco ligand. The influence of the synthetic conditions of I-IV on their structure is analyzed in comparison to each other and the previously published examples of structures with this ligand.

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Funding

The work was supported by Russian Scientific Foundation grant No. 22-23-20179, https://rscf.ru/project/22-23-20179/ and the Government of the Novosibirsk Oblast’ (Agreement No. p-22).

The analytical service was supported by project No. 121031700321-3 of the Ministry of Science and Higher Education of the Russian Federation.

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Authors and Affiliations

  1. Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia

    K. D. Abasheeva, P. A. Demakov, D. N. Dybtsev & V. P. Fedin

  2. Novosibirsk State University, Novosibirsk, Russia

    K. D. Abasheeva

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  1. K. D. Abasheeva
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Correspondence to V. P. Fedin.

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Russian Text © The Author(s), 2022, published in Zhurnal Strukturnoi Khimii, 2022, Vol. 63, No. 8, 99095.https://doi.org/10.26902/JSC_id97415

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Abasheeva, K.D., Demakov, P.A., Dybtsev, D.N. et al. CRYSTAL STRUCTURE OF COORDINATION COBALT(II) AND ZINC(II) POLYMERS WITH 1,4-DIAZABICYCLO[2.2.2]OCTANE N,N′-DIOXIDE. J Struct Chem 63, 1349–1357 (2022). https://doi.org/10.1134/S0022476622080169

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