Dichloro(4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane)-iron(III) hexafluorophosphate

• Published in: Acta crystallographica. Section C, Crystal structure communications Vol. 62; no. Pt 11; pp. m553 - m555
• Main Authors: MCCLAIN, James M, MAPLES, Danny L, MAPLES, Randall D, MATZ, Dallas L, HARRIS, Sebastian M, NELSON, Andrew D. L, SILVERSIDES, Jon D, ARCHIBALD, Stephen J, HUBIN, Timothy J
• Format: Journal Article
• Language: English
• Published: Oxford Blackwell 01.11.2006
• Subjects: Condensed matter: structure, mechanical and thermal properties; Exact sciences and technology; Organic compounds; Physics; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; Encapsulation; Iron complexes; Organometallic compounds; Bond angle; Dinuclear complex; Oxidation; Experimental study; Fluophosphates; Monoclinic lattices; Oxo complex; Macrocycle; Crystal structure
• ISSN: 0108-2701; 1600-5759
• DOI: 10.1107/S0108270106040765

The title compound, [FeCl2(C12H26N4)]PF6, is the first mononuclear Fe3+ complex of an ethylene cross-bridged tetraaza-macrocycle to be structurally characterized. Comparison with the mononuclear Fe2+ complex of the same ligand shows that the smaller Fe3+ ion is more fully encapsulated by the cavity of the bicyclic ligand. Comparison with the mu-oxo dinuclear complex of an unsubstituted ligand of the same size demonstrates that the methyl groups of 4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane prevent dimerization upon oxidation of the metal centre. Nax -Fe3+ -Nax bond angles (ax is axial), and thus the degree of encapsulation by the ligand, are quite different between the mononuclear and dinuclear mu-oxo species, which is probably the consequence of steric considerations.