Syntheses, Crystal Structures, and Nonlinear Optical Activity of Cs 2 Ba[AnO 2 (C 2 H 5 COO) 3 ] 4 (An = U, Np, Pu) and Unprecedented Octanuclear Complex Units in KR 2 (H 2 O) 8 [UO 2 (C 2 H 5 COO) 3 ] 5 (R = Sr, Ba).

X-ray diffraction was applied to the elucidation of crystal structures of single crystals of Cs2 Ba[AnO2 (C2 H5 COO)3 ]4 , where An = U(I), Np(II), Pu(III), and KR2 (H2 O)8 [UO2 (C2 H5 COO)3 ]5 , where R = Sr(IV), Ba (polymorphs 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 [AnO2 (C2 H5 COO)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 (C2 H5 COO)3 ]- bind with a hydrated Sr or Ba cation to form the rare trinuclear neutral complex unit {R(H2 O)4 [UO2 (C2 H5 COO)3 ]2 }, where R = Sr, Ba. Two such trinuclear units and one typical mononuclear unit further bind with a K cation to form the unprecedented octanuclear neutral complex unit K[UO2 (C2 H5 COO)3 ]{R(H2 O)4 [UO2 (C2 H5 COO)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.