The new enantiopure macrocyclic complexes [LnL]Cl 3· nH 2O or their racemic mixtures [Ln racL]Cl 3· nH 2O (Ln=La +3, Ce +3, Pr +3 and Eu +3) have been synthesised in a template condensation of trans-1,2-diaminocyclohexane and 2,6-diformylpyridine. The complexes have been studied by 1H and 13C NMR spectroscopy. The signal assignment was based on the COSY, NOESY and HMQC measurements. The X-ray crystal structure of [La racL]Cl 3 complex has been determined. The lanthanum ion in this complex is coordinated by six nitrogen atoms of the macrocyclic ligand and three chloride anions. The macrocycle exhibits a twist–bent conformation of approximate C 2 symmetry. On the other hand, NMR spectra of the investigated compounds in methanol–chloroform solution indicate effective D 2-symmetry that results from the fast dynamic exchange of chloride anions.