Distorted [Cu4(m3-OH)2] cubane type arrangements, one tetracationic and one neutral, have been achieved as [Cu2(m-H2bpmp)(m3OH)(H2O)]2(SO4)2.3H2O.CH3OH (1) and [Cu2(m-Hbpmp)(m3-OH) (m1,3-O2CCF3)]2.H2O.2CF3CO2H (2) [H3bpmp = 2,6-bis-[(3 hydroxypropylimino)methyl]-4-methylphenol] from the reactions of H3bpmp with CuSO4.5H2O and Cu(CF3CO2)2.xH2O in the presence of NEt3 in MeOH medium. Two types of apical interactions of the CuII ion with H2O and CF3CO2. induced hydroxido- bridge supported aggregation of {Cu2} precursors. In MeOH solution, the reaction of 1 with CF3CO2. resulted in 2, showing a ligand-exchange reaction, leading to different Cu...O separations in the space on the open faces of the cubane structure. Magnetic susceptibility measurements (1.8–350 K) revealed stronger antiferromagnetic interactions in 1, where the average in plane Cu–O–Cu angle is 100.4°, than for 2, having a smaller Cu–O–Cu angle of 97.2°.