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


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
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
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 (ORCID Profile 0000-0001-9366-1913)



Version: Accepted Version

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