A series of nickel(ii) thiocyanate complexes comprising various molar contents of isonicotinamide and water as ligands or co-crystallized moieties - an experimental and computational study(Article)
- aRuđer Bošković Institute, Zagreb, Croatia
- bDepartment of Chemistry, Faculty of Science, University of Zagreb, Zagreb, Croatia
- cLaboratory for Crystallography, Faculty of Mining and Geology, University of Belgrade, Belgrade, Serbia
- dInstitute of Organic Chemistry, Polish Academy of Sciences, Warsaw, Poland
Abstract
Seven complexes, [Ni(NCS)2(isn)2(H2O)2]·2H2O (1), [Ni(NCS)2(isn)2(H2O)2] (2), [Ni(NCS)2(isn)3(H2O)]·2.5H2O (3), [Ni(NCS)2(isn)3(H2O)]·3[Ni(NCS)2(isn)4]·9H2O (4), [Ni(NCS)2(isn)4]·3H2O (5), [Ni(NCS)2(isn)4]·2(isn) (6) and [Ni(NCS)2(isn)4]·1.25H2O (7), of Ni(ii) thiocyanate with isonicotinamide (isn = pyridine-4-carboxamide) and water as ligands of biological importance were prepared in aqueous solutions through crystal screening by variation of the isonicotinamide concentration. They were characterized by the single-crystal X-ray diffraction method and DFT calculations, while 1-6 were characterized also by NMR and IR spectroscopy and elemental and thermal analyses. In all complexes, the nickel atom is octahedrally coordinated with two thiocyanate N atoms but with different number of isonicotinamide N and water O atoms. The R46(12) and R46(16) hexamers were found in 1, R24(8) tetramer and R22(8) dimer in 2, while very complex hydrogen bonding ring patterns R24(8), R22(10), R34(14) and R610(24) were observed in 3. In 4, R46(16) and R66(20) hexamers were formed as well as typical head-to-head amide-amide hydrogen bond R22(8) dimers in a combination with two R34(10) tetramers. R24(8) cyclic water tetramers linked in zigzag hydrogen bonded chains, carboxamide catemer C(4) chains with the R68(24) ring and two fused rings R23(12) and R22(16) were found in 5. A 2D corrugated sheet network in the (002) planes with a combination of R44(16), R46(16), R66(24) and R68(24) rings were formed in 6. DFT calculations revealed that altered metal complex stoichiometries originate in different ligand affinities towards nickel, isn > SCN− > H2O. Only neutral complexes were investigated so the nickel : thiocyanate ratio was always 1 : 2 while the concentration of isonicotinamide strongly influenced the number of coordinated isn ligands. The final 3D crystal structures emerged as a compromise between the nucleation process, reactant ratios, ligand affinities and intermolecular interactions in the crystal packing. © 2022 The Royal Society of Chemistry.
Indexed keywords
| Engineering controlled terms: | AmidesAtomsComplexationDimersHydrogen bondsLigandsSingle crystalsThermoanalysis |
|---|---|
| Engineering uncontrolled terms | As-ligandsCarboxamidesComputational studiesDFT calculationHexamersIsonicotinamideLigand affinityMolar contentNickel thiocyanate complexesTetramers |
| Engineering main heading: | Nickel compounds |
Funding details
| Funding sponsor | Funding number | Acronym |
|---|---|---|
| Sveučilište u Zagrebu | DOK-2020-01-3482 | |
| European Commission See opportunities by EC | EC | |
| Ministarstvo Obrazovanja, Znanosti i Sporta | 119-1193079-1332 | MZOS |
| Hrvatska Zaklada za Znanost | IP-2020-02-8090 | HRZZ |
| European Regional Development Fund | KK.01.1.1.02.0016 | ERDF |
-
1
This research was financially supported by the Ministry of Science, Education and Sports of the Republic of Croatia Grants No. 119-1193079-1332, the Croatian Science Foundation (IP-2020-02-8090) and grants from the University of Zagreb for 2020 and 2021. L. H. wishes to thank the Croatian Science Foundation for a doctoral stipend through the Career Development Project for Young Researchers (DOK-2020-01-3482). L. H. and R. V. would like to thank the Zagreb University Computing Centre (SRCE) for granting computational resources on the ISABELLA cluster. We acknowledge the support of project CIuK co-financed by the Croatian Government and the European Union through the European Regional Development Fund – Competitiveness and Cohesion Operational Programme (Grant KK.01.1.1.02.0016.).
- ISSN: 14668033
- CODEN: CRECF
- Source Type: Journal
- Original language: English
- DOI: 10.1039/d2ce00847e
- Document Type: Article
- Publisher: Royal Society of Chemistry
Vianello, R.; Ruđer Bošković Institute, Zagreb, Croatia;
Popović, Z.; Department of Chemistry, Faculty of Science, University of Zagreb, Zagreb, Croatia;
© Copyright 2022 Elsevier B.V., All rights reserved.
Cited by 1 document
(2024) Journal of Pharmaceutical and Biomedical Analysis