This paper presents the syntheses and crystal structures of four copper(ii)-uranyl(vi) compounds [{CuIILOEt-en} 2·{(UVIO2)(NO3) 2(H2O)2}] (1), [CuII(MeCN)L OEt-pn(UVIO2)(NO3)2] (2), [(UVIO2)2(μ-H2O) 2(NO3)4]â̂™4[Cu IILOEt-py(H2O)]â̂™2MeCN (3) and {[CuIILOMe-en(UVIO2)(NO 3)]2[(UVIO2)2(μ-HO) 2(NO3)4]}n (4), where H 2LOEt-en, H2LOEt-pn, H 2LOEt-py and H2LOMe-en are 3-ethoxysalicylaldehyde-diamine (H2LOEt) or 3-methoxysalicylaldehyde-diamine (H2LOMe) ligands in which the diamine functionality are ethylenediamine, 1,3-diaminopropane, 2,3-diaminopyridine and ethylenediamine, respectively. Compound 1 is a [1 × 2 + 1 × 1] trinuclear cocrystal containing two mononuclear [CuIILOEt-en] and one mononuclear [(UVIO 2)(NO3)2(H2O)2] moiety; two coordinated water molecules interact with two O4 compartments by forming hydrogen bonds. Compound 2 is a dinuclear system in which two phenoxo oxygen atoms coordinate with the uranium(vi) centre. Compound 3 is a [2 × 1 + 1 × 4] hexanuclear cocrystal of four mononuclear [Cu IILOEt-py(H2O)] units and one dinuclear [(UVIO2)2(μ-H2O) 2(NO3)4] moiety; O-H⋯O and C-H⋯O interactions interlink the five units here. In 4, there are two dinuclear [CuIILOMe-en(UVIO2)(NO 3)]+ cations and one dinuclear [(UVIO 2)2(μ-HO)2(NO3)4] 2- anion, which are self-assembled to generate a one-dimensional topology. Interesting structural aspects including the weak interaction directed self-assemblies and most importantly, the competition between hydrogen bond and coordinate bond formation and the influence of the reactant ratio in governing that competition are discussed. The diffuse reflectance or solution transmission spectra (for the d-d band) of 1-4 and the corresponding mononuclear copper(ii) precursors are also described. © 2013 The Royal Society of Chemistry.