X-ray diffraction was applied to the elucidation of crystal structures of single crystals of Cs2Ba[AnO(2)(C2H5COO)(3)](4), where An = U(I), Np(II), Pu(III), and KR2(H2O)(8)-[UO2(C2H5COO)(3)](5), where R. = Sr(TV), Ba (polymoiphs V-a and V-b). FTIR spectra were analyzed for the uranium-containing crystals I, IV, and V-b. Isostructural cubic crystals I-III are constructed of typical mononuclear anionic complex units [AnO(2)(C2H5COO)(3)](-) and charge-balancing Cs and Ba cations. Features of actinide contraction in the six U-Np-Pu isostructural series known to date are analyzed. In crystal structures of IV and V two typical complexes [UO2(C2H5COO)(3)](-) bind with a hydrated Sr or Ba cation to form the rare trinuclear neutral complex unit {R(H2O)(4)[UO2(C2H5COO)(3)](2)}, where R = Sr, Ba. Two such tririuclear units and one typical mononuclear unit further bind with a K cation to form the unprecedented octanuclear neutral complex unit K[UO2(C2H5COO)(3)]{R(H2O)(4)[UO2(C2H5COO)(3)](2)}(2). As the derived polynuclear complexes of uranyl ion with carboxylate ligands in the crystal structures of IV and V are not the first but are rare examples, the equilibrium between mono and polynuclear complex units in aqueous solutions is discussed. The two polymorphic modifications V-a and V-b were studied at 100 K and at room temperature, respectively. Peculiarities of noncovalent interactions in crystal structures of the two polymorphs are revealed using Voronoi-Dirichlet tessellation. The nonlinear optical activity of noncentrosymmetric crystals I was estimated by its ability for second harmonic generation.