Synthesis, Characterization and Molecular Structure of Iron(III) Complex with Tridentate Diazene Ligand Having O,N,S Donor Set: Coexistence of Octahedral and Tetrahedral Iron(III) Sites in the Asymmetric Unit

摘要

The reaction of 2-hydroxy-1-(2 '-methylthiophenylazo)naphthalene (HL) with iron(II) chloride results in the formation of a hitherto unknown complex, [Fe(L)(2)][FeCl4] (1). The azo-thioether ligand binds iron(III) center through the O-,N,S donor set to form the octahedral [Fe(L)(2)](+) cation. Solid state molecular structure of (1) has been determined by single crystal X-ray diffraction technique. Compound (1) crystallizes in the monoclinic P2(1)/c space group of unit cell dimensions a = 10.3904(19) angstrom, b = 23.735(4) angstrom, c = 15.815(3) angstrom; alpha = 90 degrees, beta = 102.248(4)degrees, gamma = 90 degrees and Z = 4. The structure was solved by direct method and refined to R-1 value 0.0975 on 3796 observed reflections. There are one octahedral cationic unit of [(FeL2)-L-III], a tetrahedral anionic unit of [(FeCl4)-Cl-III] and 0.5(C2H5OH)(2) as solvent molecules in an asymmetric unit of the crystal lattice of (1). There are two intramolecular C-H center dot center dot center dot O interactions and the crystal packing is stabilized by interionic C-H center dot center dot center dot Cl and intermolecular C-H center dot center dot center dot Cg interactions.