New cobalt and nickel sulfates templated with N,Nʹ-dimethyletethylenediammonium cation: synthesis, crystal structures and topological features

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Abstract

Crystals of new double sulfates (dmedaH2)[Co(H2O)6](SO4)2 (1) and (dmedaH2)[Ni(H2O)4(SO4)2] (2), as well as (dmedaH2)2(SO4)2⋅3H2O (3), where dmeda is N,Nʹ-dimethylethylenediamine, were obtained by isothermal evaporation. The compounds crystallize in the triclinic symmetry, space group P1, while compound 3 is characterized by the orthorhombic symmetry with the space group P212121. The crystal structure of 1 contains isolated octahedral cations [Co(H2O)6]2+ and SO42– tetrahedra, while the crystal structure of 2 contains complex anions trans-[Ni(H2O)4(SO4)2]2–. Structures of 1 and 2 are compared with the structures of double cobalt and nickel sulfates with ethylenediammonium, where the opposite case is observed. The formation of both aqua- and aquasulfate complexes is quite typical for cations of transition metals of the 3d series. While for double sulfates of transition metals with inorganic cations the hydration number depends to a greater extent on the synthesis temperature and the ionic radius of the monovalent metal, for double sulfates with organic cations the picture is more complex. The crystal structure of compound 3 can also be considered as pseudolayered, with the cationic layer formed only by the organic component, while the anionic layer also includes water molecules. The anionic layer contains cavities, the volume of which allows us to assume that under certain conditions they can be occupied by water molecules, which would correspond to the composition (dmedaH2)(SO4)⋅2H2O. Topological analysis of the obtained compounds showed that metal complexes with ethylenediammonium demonstrate a relatively high structural complexity of H-bonds with a lower complexity of structural units compared to N,N'-dimethylethylenediammonium.

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About the authors

D. O. Charkin

Lomonosov Moscow State University; FRC Kola Science Centre RAS

Email: aks.crys@gmail.com

Faculty of Chemistry, Lomonosov Moscow State University

Russian Federation, 1-3 Leninskie Gory, Moscow 119991; 14 Fersman str., Apatity 184209

V. E. Kireev

FRC Kola Science Centre RAS

Email: aks.crys@gmail.com
Russian Federation, 14 Fersman str., Apatity 184209

N. V. Somov

N. I. Lobachevsky State University of Nizhny Novgorod

Email: aks.crys@gmail.com
Russian Federation, Nizhny Novgorod

D. N. Dmitriev

Lomonosov Moscow State University; FRC Kola Science Centre RAS

Email: aks.crys@gmail.com

Faculty of Chemistry, Lomonosov Moscow State University

Russian Federation, 1-3 Leninskie Gory, Moscow 119991; 14 Fersman str., Apatity 184209

A. M. Banaru

Lomonosov Moscow State University; FRC Kola Science Centre RAS

Email: aks.crys@gmail.com

Faculty of Chemistry, Lomonosov Moscow State University

Russian Federation, 1-3 Leninskie Gory, Moscow 119991; 14 Fersman str., Apatity 184209

S. M. Aksenov

FRC Kola Science Centre RAS

Author for correspondence.
Email: aks.crys@gmail.com
Russian Federation, 14 Fersman str., Apatity 184209

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2. Fig. 1. General view of the crystal structure of (dmedaH2)[Co(H2O)6](SO4)2 (1) (a), features of the local environment of the Co2+ cation (b), SO4 tetrahedron (c) and the organic cation dmedaH22+ (d).

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3. Fig. 2. General view of the crystal structure of (dmedaH2)[Ni(H2O)4(SO4)2] (2) (a), features of the local environment of the Ni2+ cation (b), SO4 tetrahedron (c) and the organic cation dmedaH22+ (d).

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4. Fig. 3. General view of the crystal structure of (dmedaH2)2(SO4)2·3H2O (3) (a), features of the local environment of the organic cation dmedaH22+ (b).

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5. Fig. 4. Weighted Hcomb, Hedge and Hmix contributions to HSBUnet for the crystal structures of ethylenediamonium (eda) and N,N-diethylenediammonium (dmeda) sulfates with or without Co(II), Ni(II) cations (including hydrates).

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