Powell, Robyn E, Lees, Martin R, Tizzard, Graham J and Koningsbruggen, Petra J van (2022). FeIII in a high-spin state in bis(5-bromosalicylaldehyde 4-ethylthiosemicarbazonato-κ3O,N1,S)ferrate(III) nitrate monohydrate, the first example of such a cationic FeIII complex unit. Acta Crystallographica Section C: Structural Chemistry, 78 (Pt 1), pp. 63-69.
Abstract
The synthesis and crystal structure (100 K) of the title compound, [Fe(C 10H 11BrN 3OS) 2]NO 3·H 2O, is reported. The asymmetric unit consists of an octahedral [Fe III(HL)2] +cation, where HL -is H-5-Br-thsa-Et or 5-bromosalicylaldehyde 4-ethylthiosemicarbazonate(1-) {systematic name: 4-bromo-2-[(4-ethylthiosemicarbazidoidene)methyl]phenolate}, a nitrate anion and a noncoordinated water molecule. Each HL -ligand binds via the thione S, the imine N and the phenolate O atom, resulting in an Fe IIIS2N 2O 2chromophore. The ligands are orientated in two perpendicular planes, with the O and S atoms in cis and the N atoms in trans positions. This [Fe(HL)2](anion)·H2O compound contains the first known cationic Fe IIIentity containing two salicylaldehyde thiosemicarbazone derivatives. The Fe IIIion is in the high-spin state at 100 K. In addition, a comparative IR spectroscopic study of the free ligand and the ferric complex is presented, demonstrating that such an analysis provides a quick identification of the degree of deprotonation and the coordination mode of the ligand in this class of metal compounds. The variable-temperature magnetic susceptibility measurements (5-320 K) are consistent with the presence of a high-spin Fe IIIion with a zero-field splitting D = 0.439 (1) cm -1
Publication DOI: | https://doi.org/10.1107/S2053229621013462 |
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Divisions: | College of Engineering & Physical Sciences > School of Infrastructure and Sustainable Engineering > Chemical Engineering & Applied Chemistry College of Engineering & Physical Sciences > Aston Institute of Materials Research (AIMR) College of Engineering & Physical Sciences |
Additional Information: | This is the author's accepted manuscript of the publication: Powell, R. E., Lees, M. R., Tizzard, G. J. & Koningsbruggen, P. J. van (2022). Acta Cryst. C78, 63-69. https://scripts.iucr.org/cgi-bin/paper?S2053229621013462 |
Uncontrolled Keywords: | Carbazone,Crystal structure,High spin,Iron(III),Magnetic susceptibility,Tautomerism,Condensed Matter Physics,Physical and Theoretical Chemistry,Inorganic Chemistry,Materials Chemistry |
Publication ISSN: | 2053-2296 |
Last Modified: | 30 Sep 2024 12:57 |
Date Deposited: | 21 Jan 2022 14:49 |
Full Text Link: | |
Related URLs: |
https://onlinel ... 053229621013462
(Publisher URL) http://www.scop ... tnerID=8YFLogxK (Scopus URL) |
PURE Output Type: | Article |
Published Date: | 2022-01-04 |
Published Online Date: | 2021-12-30 |
Accepted Date: | 2021-12-20 |
Submitted Date: | 2021-09-06 |
Authors: |
Powell, Robyn E
Lees, Martin R Tizzard, Graham J Koningsbruggen, Petra J van ( 0000-0001-9366-1913) |