Crystal Nanoarchitectonics and Characterization of the Octahedral Iron(III)–Nitrate Complexes with Isomer Dimethylurea Ligands
Author:
Béres Kende Attila12ORCID, Homonnay Zoltán3, Bereczki Laura14, Dürvanger Zsolt56ORCID, Petruševski Vladimir M.7ORCID, Farkas Attila8ORCID, Kótai László19ORCID
Affiliation:
1. Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, H-1117 Budapest, Hungary 2. György Hevesy PhD School of Chemistry, ELTE Eötvös Loránd University, H-1117 Budapest, Hungary 3. Institute of Chemistry, ELTE Eötvös Loránd University, H-1117 Budapest, Hungary 4. Centre for Structural Science, Research Centre for Natural Sciences, H-1117 Budapest, Hungary 5. ELKH-ELTE Protein Modelling Research Group, H-1117 Budapest, Hungary 6. Structural Chemistry and Biology Laboratory, Institute of Chemistry, ELTE Eötvös Loránd University, H-1117 Budapest, Hungary 7. Faculty of Natural Sciences and Mathematics, Ss. Cyril and Methodius University, MK-1000 Skopje, North Macedonia 8. Department of Organic Chemistry and Technology, Faculty of Chemical Technology and Biotechnology, Budapest University of Technology and Economics, H-1111 Budapest, Hungary 9. Deuton-X Ltd., H-2030 Érd, Hungary
Abstract
Three octahedral iron(III) nitrate complexes with dimethylated urea ligand isomers, [hexakis(N,N’-dimethylurea-O)iron(III)] nitrate (compound 1), trans-[diaquatetrakis(N,N-dimethylurea-O)iron(III)] nitrate (compound 2), and [hexakis(N,N-dimethylurea-O)iron(III)] nitrate trihydrate (compound 3) were prepared and characterized with single crystal X-ray diffraction, IR, Raman and UV–Vis methods. In compounds 1 and 3, six dimethylurea ligands coordinate to the central FeIII ion via the oxygen in octahedral geometry and the ligands are arranged in a propeller-like manner, dividing the complex cations into two sides. In compound 1, the dimethylurea propellers screw in the opposite direction on the two sides of the complex and in compound 3, they are arranged with the same handedness on the two sides. The complexes have helical chirality. The two sides of the complex cations differ not only in the rotation direction of the ligands but also in the hydrogen bond formation. On one side of the complex cation, the ligands form intermolecular hydrogen bonds only with the crystal waters, meanwhile on the other side of the complex, the ligands form hydrogen bonds only with the nitrate ions. In compound 2, [Fe(N,N-dimethylurea)4(H2O)2]3+ cations form layers that are separated by interconnected NO3− ions forming a hydrogen bonding system and connecting the complex cations A-s and B-s. The three crystallographically different nitrate ions each form four hydrogen bonds in a way that they have one bidentate O atom and two monodentate O atoms; however, the anions differ in their hydrogen bonding. The spectroscopic characteristics of compound 2 were determined by IR measurements on the deuterated compound 2 as well.
Funder
European Regional Development Fund National Research, Development, and Innovation Fund European Union State of Hungary
Subject
Inorganic Chemistry,Condensed Matter Physics,General Materials Science,General Chemical Engineering
Reference49 articles.
1. Thermally Induced Solid-Phase Quasi-Intramolecular Redox Reactions of [Hexakis(urea-O)iron(III)] Permanganate: An Easy Reaction Route to Prepare Potential (Fe,Mn)Ox Catalysts for CO2 Hydrogenation;Homonnay;Inorg. Chem.,2022 2. Synthesis, structure, and Mössbauer spectroscopic studies on the heat-induced solid-phase redox reactions of hexakis(urea-O)iron(III) peroxodisulfate;Homonnay;J. Mater. Res.,2023 3. Bereczki, L., Petruševski, V.M., Franguelli, F.P., Béres, K.A., Farkas, A., Holló, B.B., Czégény, Z., Szilágyi, I.M., and Kótai, L. (2022). [Hexaamminecobalt(III)] Dichloride Permanganate—Structural Features and Heat-Induced Transformations into (CoII,MnII)(CoIII,MnIII)2O4 Spinels. Inorganics, 10. 4. Franguelli, F.P., Kováts, É., Czégény, Z., Bereczki, L., Petruševski, V.M., Barta Holló, B., Béres, K.A., Farkas, A., Szilágyi, I.M., and Kótai, L. (2022). Multi-Centered Solid-Phase Quasi-Intramolecular Redox Reactions of [(Chlorido)Pentaamminecobalt(III)] Permanganate—An Easy Route to Prepare Phase Pure CoMn2O4 Spinel. Inorganics, 10. 5. Octaammine EuII and YbII Azides and Their Thermal Decompositions to the Nitrides;Mogk;Eur. J. Inorg. Chem.,2016
|
|