Formation of Two Kinds of Columnar Crystal Structures of Saddle-Shape Metal Complex [Ni(tmtaa)] Induced by Halogen Substitution

Abstract A series of halogen substituted nickel tmtaa (tmtaa: 7,16-dihydro-6,8,15,17-tetramethyldibenzo-[b,i][1,4,8,11] tetraazacyclotetradecine) complexes ([Ni(tmtaa-4X)], X = F, Cl, Br, I) have been prepared and characterized by X-ray crystallographic structure analysis. It was found that [Ni(tmtaa-4F)] formed one-dimensional stacked structure, [Ni(tmtaa-4Cl)] exhibited polymorphism, and [Ni(tmtaa-4Br)] and [Ni(tmtaa-4I)] incorporated crystallization solvent in its crystals. In particular, crystal to crystal phase transition was observed in [Ni(tmtaa-4Br)].