The chemistry of transition-metal complexes with unusually high coordination numbers has been of interest because of their application in catalytic and biological systems. Deprotonation of the ionogenic tetradentate ligand 6,6'-bis(1H-tetrazol-5-yl)-2,2'-bipyridine [Hbipy(ttr)] in the presence of iron(III) and tetra-n-butylammonium bromide, [n-BuN]Br, in solution resulted in the synthesis of a rare octacoordinated anionic mononuclear complex, tetra-n-butylammonium bis[6,6'-bis(tetrazol-1-id-5-yl)-2,2'-bipyridine]iron(III) methanol hemisolvate dihydrate, (CHN)[Fe(CHN)]·0.5CHOH·2HO or [n-BuN][Fe{bipy(ttr)}]·0.5CHOH·2HO (1), which has been structurally characterized by elemental analysis, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. In 1, the coordination sphere of the iron(III) ion is a distorted bis-disphenoid dodecahedron, in which the eight coordination positions are occupied by eight N atoms from two independent tetradentate [bipy(ttr)] anionic ligands, therefore forming the anionic [Fe{bipy(ttr)}] unit, with the negative charge balanced by a free [n-BuN] cation. An investigation of the magnetic properties of 1 revealed a gradual incomplete spin-crossover behaviour below 150 K.
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