Synthesis and properties of bis(tetra(n-butyl)ammonium)mu-carbido-di(halophthalocyaninato(2-)ferrates( IV)); Crystal structure of bis(tetra(n-butyl)ammonium)mu-carbido-di(fluorophthalocyaninato(2-)ferrate (IV)) trihydrate [German]

摘要

mu-Carbido-di(pyridinephthalocyaninato(2-)- iron(IV)) reacts with tetra(n-butyl)ammonium halide ((Bu4N)-Bu-n)X) in solution (X = F) or in a melt (X = Cl, Br) to yield bis(tetra(n-butyl)ammonium mu-carbido-di(halophthalocyaninato(2-)ferrat(IV)). The fluoro-complex salt crystallizes as a trihydrate monoclinically in the space group P12(1)1 with the following cell parameters: a = 15.814(1) Angstrom; b = 22.690(5) Angstrom; c = 25.127(3) Angstrom; beta = 98.27(1)degrees, Z = 4. The Fe atoms are almost in the centre (Ct) of the (N-iso)(4) planes (N-iso: isoindoline-N atom) with a Fe-Ct distance of 0.053(1) Angstrom. The average Fe-N-iso distance is 1.939(4) Angstrom, the Fe-(mu-C) distance 1.687(4) Angstrom and the Fe-F distance 2.033(2) Angstrom. The Fe-(mu-C)-Fe core is linear (179.5(3)degrees). The pc(2)-ligands are staggered (phi = 42(1)degrees) with a convex distortion. The asymmetric Fe-(mu-C)-Fe stretch (in cm(-1)) is observed in the IR spectra at 917 (X = F), 918 (Cl) and 920 (Br) and the symmetric Fe-(p-C)-Fe stretch at 476 cm(-1) in the resonance Raman spectra. The IR active asymmetric Fe-X stretch (in cm(-1)) absorbs at 336 (X = F), 203 (Cl), 182 (Br), respectively. [References: 22]