The synthesis of a novel cyclophane (L1) consisting of a 1H-pyrazole moiety linked through methylene groups to a 1,5,9,13-tetraazadecane chain is described. As far as we know, this is one of the first reported syntheses of a [1 + 1] condensation 1H-pyrazole azamacrocyclic ligand. The crystal structures of the complexes [Cu-2(H(H(-1)L1))(H(-1)L1)](ClO4)(3)center dot 3.75H(2)O (1) and ([Cu-2(H(H(-1)L1))(0.5)(H(-1)L1)(1.5)](2)(ClO4)(3)Br-2 center dot 4.2H(2)O (2) show that Cu2+ coordination leads to formation of 2:2 Cu2+:L dinuclear dimeric complexes in which the 1H-pyrazole units lose a proton behaving as bis(monodentate) bridging ligands. Unlike previously reported complexes of [2 + 2] pyrazole azamacrocycles, the pyrazolate units in I are pointing outward from the macrocyclic cavity to bind the Cu2+ ions. Inner coordination with formation of 1:1 Cu2+:L complexes is however observed in [1 + 1] pyridine azamacrocycles as shown by the crystal structure here presented of the complex [CuL2](ClO4)(2) (3). Crystals of [Cu-3(H(-1)L1)(2)(CO3)(H2O)](ClO4)(2)center dot 8H(2)O (4) grown by evaporating aqueous solution at pH 9 containing Cu2+ and Li in 3:2 molar ratio show the presence of a further Cu2+ coordinated to the two free amine groups found in structures 1 and 2. The metal ion fills its coordination sphere capturing atmospheric CO2 as a eta(1),eta(2)-bidentate carbonate anion placed in the equatorial position and an axial water molecule, pH-metric data, UV-vis spectroscopic data, EPR measurements, and HR-ESI-MS data support that the outer coordination mode with formation of 2:2 dinuclear dimeric and 3:2 trinuclear complexes is preserved in aqueous solution.