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Kinetic control of zinc cyamelurate crystal formations

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Abstract

The dynamic combinatorial library (DCL) of cyamelurates consists of 17 tautomers of cyameluric acid and their ions, as well as metal aqua complexes. That leads to a variety of compounds in the Zn(NO3)2 – K3(C6N7O3) – H2O system. All compounds are obtained with impurity amorphous and crystalline phases, which complicates their study. In this work, metastable phases of zinc, nickel, and iron cyamelurates were obtained and their crystal structures were determined for the first time. Kinetic control of chemical reactions allowed us to isolate two zinc cyamelurate metastable phases. The metastable compound K2Zn(C6N7O3H)2∙8H2O is formed immediately after mixing the precursor solutions, and after two hours, it is converted to another metastable compound Zn(C6N7O3H)∙5H2O. Due to hydrate isomerization, after 12 hours in the mother liquor, the latter transforms into a thermodynamically stable compound of the same composition. The features of the synthesis and crystalline structure of zinc cyamelurates can be interpreted from the standpoint of the nonclassical nucleation theory. The crystal structures of the synthesized compounds K2Zn(C6N7O3H)2∙8H2O, Zn(C6N7O3H)∙5H2O, and Zn(C6N7O3H2)2∙8H2O allowed us to conclude that decomposition of supersaturated zinc solution leads to the formation of double electric micelles (DEM). They can be considered nanoreactors playing an important role in crystal nucleation.

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Data availability

The datasets generated and analyzed during the current study are available in Cambridge Crystallographic Data Centre, CCDC numbers 2010959, 2010962, and 2011516 [https://www.ccdc.cam.ac.uk/].

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Funding

This work was supported by Russian Foundation for Basic Research (grant 20-08-00097) and by M.V. Lomonosov Moscow State University Program of Development. X-ray and SAXS investigation were performed using equipment of Center of Joint use of IPCE RAS.

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Authors and Affiliations

  1. Department of Chemistry, M.V. Lomonosov Moscow State University, 1-3 Leninskie Gory, Moscow, Russian Federation, 119991

    Albina S. Isbjakowa, Vladimir V. Chernyshev, Victor A. Tafeenko, Igor K. Kudryavtsev & Leonid A. Aslanov

  2. A. N. Frumkin Institute of Physical Chemistry and Electrochemistry RAS, 31 Leninsky Prospect, Moscow, Russian Federation, 119071

    Vladimir V. Chernyshev & Andrei A. Shiryaev

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  1. Albina S. Isbjakowa
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  2. Vladimir V. Chernyshev
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  5. Igor K. Kudryavtsev
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  6. Leonid A. Aslanov
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Contributions

A. S. Isbjakowa, chemical syntheses and analyzes

V. V. Chernyshev, powder methods of crystal structure determinations

V. A. Tafeenko, single crystal methods of crystal structure determination

A. A. Shiryaev, small-angle X-ray scattering

I. K. Kudryavtsev, analysis of kinetic and thermodynamic control

L. A. Aslanov, setting a scientific problem and choosing objects of research, supervision of research, analysis of results, writing of manuscript

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Correspondence to Leonid A. Aslanov.

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Isbjakowa, A.S., Chernyshev, V.V., Tafeenko, V.A. et al. Kinetic control of zinc cyamelurate crystal formations. Struct Chem 32, 719–729 (2021). https://doi.org/10.1007/s11224-020-01721-7

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