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Synthesis and crystal structures of zirconium(IV) nitrate complexes (NO2)[Zr(NO3)3(H2O)3]2(NO3) 3, Cs[Zr(NO3)5], and (NH4)[Zr(NO3)5](HNO3)

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Abstract

The zirconium nitrate complexes (NO2)[Zr(NO3)3(H2O)3]2(NO3)3 (1), Cs[Zr(NO3)5] ((2), (NH4)[Zr(NO3)5](HNO3) (3), and (NO2)0.23(NO)0.77[Zr(NO3)5] ((4) were prepared by crystallization from nitric acid solutions in the presence of H2SO4 or P2O5. The complexes were characterized by X-ray diffraction. The crystal structure of 1 consists of nitrate anions, nitronium cations, and [Zr(NO3)3(H2O)3]+ complex cations in which the ZrIV atom is coordinated by three water molecules and three bidentate nitrate groups. The coordination polyhedron of the ZrIV atom is a tricapped trigonal prism formed by nine oxygen atoms. The island structures of 2 and 3 contain [Zr(NO3)5] anions and Cs+ or NH4 + cations, respectively. In addition, complex 3 contains HNO3 molecules. Complex 4 differs from (NO2)[Zr(NO3)5] in that three-fourth of the nitronium cations in 4 are replaced by nitrosonium cations NO+, resulting in a decrease in the unit cell parameters. In the [Zr(NO3)5] anion involved in complexes 2–4, the ZrIV atom is coordinated by five bidentate nitrate groups and has an unusually high coordination number of 10. The coordination polyhedron is a bicapped square antiprism.

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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 92–97, January, 2005.

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Morozov, I.V., Fedorova, A.A., Palamarchuk, D.V. et al. Synthesis and crystal structures of zirconium(IV) nitrate complexes (NO2)[Zr(NO3)3(H2O)3]2(NO3) 3, Cs[Zr(NO3)5], and (NH4)[Zr(NO3)5](HNO3). Russ Chem Bull 54, 93–98 (2005). https://doi.org/10.1007/s11172-005-0222-7

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  • DOI: https://doi.org/10.1007/s11172-005-0222-7

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