Two copper(II) compounds of formula [Cu₂(Hmea) ₂(mea)₂X]ClO₄ [Hmea = 2-aminoethanol and X = ClO₄ ^- (1) and SCN^- (2)] have been synthesized and characterized by X-ray diffraction studies. The copper atoms in 1 and 2 exhibit distorted square pyramidal surroundings with two nitrogen and two oxygen atoms from Hmea and mea ligands forming the basal plane (1 and 2) and a perchlorate oxygen (1) or a thiocyanate sulfur/nitrogen atom (2) in the apical position. Two crystallographically independent [Cu(Hmea)(mea)] units occur in 1 and they form a centrosymmetric supramolecular dimer through symmetrical O-H⋯O hydrogen bonds. The two perchlorate groups in 1 play different structural functions: one acts as a bridge joining two copper(II) ions via apical coordination whereas the second one is just a counterion. Two [Cu(Hmea)(mea)] units in compound 2 form a centrosymmetric dimer, the thiocyanate an ions connecting neighboring dimers through end to end coordination mode. The cryomagnetic investigation of 1 shows the occurrence of an intermediate intramolecular antiferromagnetic interaction (J = -22.3 cm ^-1, H = -JS₁ S₂) mediated by the hydrogen bonds.