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Acid‐Base Self‐Assembly Chemistry and Hydrogen Bonding Interactions Resulting in the Formation of a Tetranuclear Aggregate Containing Four Crystallographically Non‐Equivalent Fe III Centers
Author(s) -
Tanase Stefania,
Bouwman Elisabeth,
Long Gary J.,
Shahin Ahmed M.,
Mills Allison M.,
Spek Anthony L.,
Reedijk Jan
Publication year - 2004
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200400609
Subject(s) - chemistry , crystallography , hydrogen bond , stacking , dimer , molecule , ligand (biochemistry) , antiferromagnetism , base (topology) , ion , stereochemistry , inorganic chemistry , organic chemistry , mathematical analysis , biochemistry , receptor , mathematics , physics , condensed matter physics
The synthesis and characterization of a mononuclear iron( III ) complex [Fe(Hphpz)Cl(CH 3 OH)] ( 1 ) and a tetranuclear assembly of a bis(μ‐hydroxo)‐bridged dinuclear iron( III ) complex [{Fe(Hphpz) 2 (OH)} 2 ][Fe(Hphpz) 3 ] 2 ( 2 ) with the ligand 3(5)‐methyl‐5(3)‐(2‐hydroxyphenyl)pyrazole (H 2 phpz) is reported. Compound 1 is converted into 2 in a methanol solution and in the presence of a base. The asymmetric unit of 2 consists of two independent [Fe(Hphpz) 3 ] molecules and one dinuclear complex [Fe(Hphpz) 2 (OH)] 2 containing two crystallographically non‐equivalent iron( III ) ions; the three units are linked by N−H ··· O and O−H ··· O hydrogen bonding and stacking interactions to form a cluster with an approximate C 2 ‐symmetry. The Mössbauer spectra of [{Fe(Hphpz) 2 (OH)} 2 ][Fe(phpz) 3 ] 2 have been measured at 295 and 78 K and indicate the presence of four crystallographically distinct, but chemically similar iron( III ) sites. The magnetic properties of this compound originate from the weak antiferromagnetic interaction between the Fe III ions of the [Fe(phpz) 2 (OH)] 2 dimer ( J = −2.8 cm −1 ). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)