Anton V. Savchenkov

Trinuclear {Sr[UO2L3]2(H2O)4} and pentanuclear {Sr[UO2L3]4}2− uranyl monocarboxylate complexes (L-acetate or n-butyrate ion)

Crystals of two acetate complexes, Cs2{Sr[UO2L3]4} (1) and [Sr(H2O)6][UO2L3]2{Sr(H2O)4[UO2L3]2}2 (2), and one n-butyrate complex, {Sr(H2O)4[UO2L3]2}·2H2O (3), of uranium(VI), where L is a corresponding monocarboxylate ion, were studied by means of FTIR spectroscopy and single crystal X-ray analysis. The structure of 1 contains pentanuclear anionic complexes, {Sr[UO2L3]4}2−, bonded in a three dimensional framework by electrostatic interactions with Cs+ cations. The structure of 2, in addition to ‘typical’ uranyl triacetate complexes of [UO2L3]− and [Sr(H2O)6]2+ cations, contains neutral trinuclear complexes, {Sr(H2O)4[UO2L3]2}. The structure of 3 with n-butyrate ions consists of neutral complexes of {Sr(H2O)4[UO2L3]2} and molecules of crystallized water. Analysis of intermolecular interactions in 2 and 3 by means of two independent approaches (molecular Voronoi–Dirichlet polyhedra and molecular Hirshfeld surfaces) revealed that discrete complex groups are connected with one another mostly due to H/O hydrogen bonds and H/H dispersion interactions. A dynamic balance among mono- and poly-nuclear complexes in aqueous solutions containing R2+ and [UO2L3]− ions is proposed. The effect of the alkyl chain and the nature of the R2+ cation on the balance is discussed.

X-Ray diffraction and IR-spectroscopic studies of UO2(n-C3H7COO)2(H2O)2 and Mg(H2O)6[UO2(n-C3H7COO)3]2

Single crystals of UO2(n-C3H7COO)2(H2O)2 (I) and Mg(H2O)6[UO2(n-C3H7COO)3]2 (II) are synthesized. Their IR-spectroscopic and X-ray diffraction studies are performed. Crystals I are monoclinic, a = 9.8124(7) Å, b = 19.2394(14) Å, c = 12.9251(11) Å, β = 122.423(1)°, space group P21/c, Z = 6, and R = 0.0268. Crystals II are cubic, a = 15.6935(6) Å, space group

Synthesis, crystal structure, and IR spectral study of Na[(UO2)(C3H7COO)3] · 0.25H2O and K[(UO2)(C3H7COO)3]

Pa\bar 3

Electronic structure of cesium butyratouranylate(VI) as derived from DFT-assisted powder X-ray diffraction data.

, Z = 4, and R = 0.0173. The main structural units of I and II are [UO2(C3H7COO)2(H2O)2] molecules and [UO2(C3H7COO)3]− anionic complexes, respectively, which belong to AB201M21 (I) and AB301 (II) crystal chemical groups of uranyl complexes (A = UO22+, B01 = C3H7COO−, and M1 = H2O). A crystal chemical analysis of UO2L2 · nH2O compounds, where L is a carboxylate ion, is performed.

Synthesis and X-ray Crystallography of [Mg(H2O)6][AnO2(C2H5COO)3]2 (An = U, Np, or Pu)

Synthesis, IR spectral study and X-ray diffraction analysis of single crystals of Na[(UO2)(C3H7COO)3] · 0.25H2O (I) and K[(UO2)(C3H7COO)3] (II) were carried out. Compound I is monoclinic, unit cell parameters are: a = 13.5671(15) Å, b = 20.070(2) Å, c = 13.6139(15) Å, β = 106.839(2)°, space group P21, Z = 8, R = 0.0493. Compound II is orthorhombic, unit cell parameters are: a = 17.1325(9) Å, b = 19.6966(11) Å, c = 21.9686(11) Å, space group P212121, Z = 16, R = 0.0563. Mononuclear groups [UO2(C3H7COO)3]− related to the A301 crystal-chemical group (A = UO22+, B01 = C3H7COO−) of uranyl complexes are the uranium-containing structural units of crystals I and II. The data of IR spectral study agree well with X-ray diffraction data.

Syntheses, Crystal Structures, and Nonlinear Optical Activity of Cs2Ba[AnO2(C2H5COO)3]4 (An = U, Np, Pu) and Unprecedented Octanuclear Complex Units in KR2(H2O)8[UO2(C2H5COO)3]5 (R = Sr, Ba)

Investigation of chemical bonding and electronic structure of coordination polymers that do not form high-quality single crystals requires special techniques. Here, we report the molecular and electronic structure of the first cesium butyratouranylate, Cs[UO(2)(n-C(3)H(7)COO)(3)][UO(2)(n-C(3)H(7)COO)(OH)(H2O)], as obtained from DFT-assisted powder X-ray diffraction data because of the low quality of crystalline sample. The topological analysis of the charge distribution within the quantum theory of atoms-in-molecules (QTAIM) space partitioning and the distribution of electron localization function (ELF) is reported. The constancy of atomic domain of the uranium(VI) atom at different coordination numbers (7 and 8) and the presence of three ELF maxima in equatorial plane of an uranyl cation attributed to the 6s and 6p electrons were demonstrated for the first time. Details of methodologies applied for additional verification of the correctness of powder XRD refinement (Voronoi atomic descriptors and the Morse restraints) are discussed.

A Single Crystal X-ray Diffraction Study of Na4(UO2)4(i-C4H9COO)11(NO3)·3H2O

Synthesis and X-ray crystallography of single crystals of [Mg(H2O)6][AnO2(C2H5COO)3]2, where An = U (I), Np (II), or Pu (III), are reported. Compounds I-III are isostructural and crystallize in the trigonal crystal system. The structures of I-III are built of hydrated magnesium cations [Mg(H2O)6](2+) and mononuclear [AnO2(C2H5COO)3](-) complexes, which belong to the AB(01)3 crystallochemical group of uranyl complexes (A = AnO2(2+), B(01) = C2H5COO(-)). Peculiarities of intermolecular interactions in the structures of [Mg(H2O)6][UO2(L)3]2 complexes depending on the carboxylate ion L (acetate, propionate, or n-butyrate) are investigated using the method of molecular Voronoi-Dirichlet polyhedra. Actinide contraction in the series of U(VI)-Np(VI)-Pu(VI) in compounds I-III is reflected in a decrease in the mean An═O bond lengths and in the volume and sphericity degree of Voronoi-Dirichlet polyhedra of An atoms.

Stereochemistry of thorium in oxygen-containing compounds

X-ray diffraction was applied to the elucidation of crystal structures of single crystals of Cs2Ba[AnO2(C2H5COO)3]4, where An = U(I), Np(II), Pu(III), and KR2(H2O)8[UO2(C2H5COO)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(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 trinuclear 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.

Crystal-chemical features of baric polymorphism of actinides

Synthesis and the results of IR and single crystal X-ray diffraction study of Na4(UO2)4(i-C4H9COO)11·(NO3)·3H2O are reported. The crystals are monoclinic; the unit cell parameters at 100 K are as follows: a = 13.697(2), b = 20.285(3), c = 15.991(3) Å, β = 103.760(3)°, space group P21, Z = 2, R = 0.0650. The uraniumcontaining structural units are mononuclear moieties [UO2(i-C4H9COO)3]− and [UO2(NO3)(i-C4H9COO)2]−, belonging to crystal-chemical group AB301 (A = UO22+, B01 = i-C4H9COO− and NO3−) of uranyl complexes. The IR data are consistent with the results of the single crystal X-ray diffraction study. The influence of the carboxylate ligand volume on the structure of Na[UO2L3]·nH2O crystals (L = acetate, n-butyrate, isovalerate ion) is analyzed.

Synthesis and study of (CN3H6)2[(UO2)2(C2O4)(SeO3)2] by IR spectroscopy and X-ray diffraction

Voronoi–Dirichlet (VD) polyhedra and the method of intersecting spheres have been used to perform analysis of coordination of 198 types of crystallographically different Th(IV) atoms in the crystal structures of oxygen-containing compounds characterized with R ≤ 0.05. The volumes of VD polyhedra have been determined for the thorium atoms forming ThOn complexes in which the Th–O bond lengths (2.14–2.91 Å) are roughly independent of the CN (n), varying from 4 to 12. It has been found that the phase transition of thorianite ThO2 at elevated pressure is accompanied by a considerable distortion of the thorium VD polyhedra because of the appearance of faces corresponding to Th–Th contacts in which the interatomic distances are shorter than in thorium metal. It has been demonstrated that the baric phase transitions in thorium metal and thorianite are accompanied by similar changes in characteristics of Th VD polyhedra, which are tentatively believed to be a result of appearance of bonding 5f interactions between thorium atoms.