Restriction of apical coordination in the square-planar nickel(II) complexes of meso-1,5,8,12-tetramethyl-1,4,8,11-tetraazacyclotetradecane with axially oriented C-methyl groups

Crystal structures of nickel(II) complexes coordinated with cyclam-type macrocyclic tetraamine, meso-1,5,8,12-tetramethyl-1,4,8,11-tetraazacyclotetradecane (L) in two complex salts 1 and 2 have been determined by single-crystal X-ray crystallographic analysis. Complexes in both salts adopted trans-III structure, but the C-methyl groups of L adopted equatorial configuration in 1, while axial in 2. Complex 2 is the first example of complex of cyclam-type tetraamine with only axially oriented C-methyl groups. Complex in 1 adopted six-coordinated octahedral geometry with two water molecules occupying two apical sites, while in 2, apical sites were vacant resulting in four-coordinated square-planar geometry. UV–Vis spectra in various solutions also revealed the formation of octahedral six-coordinated complex for 1 but not for 2. Network of hydrogen bonds involving chloride ion, water, and N–H of L was present in crystals of both 1 and 2. Convenient synthetic paths for 1 and 2 are also presented.

Two nickel complexes coordinated with tetraaza macrocycle of different conformation were synthesized and characterized by single-crystal X-ray and spectroscopic analyses. Nickel complex with equatorially oriented C-methyl groups adopted six-coordinated octahedral geometry both in crystal and various solutions, while C-axial complex adopted strictly four-coordinated square-planar geometry.Figure optionsDownload as PowerPoint slide