Synthesis and Structure of Complexes of Np(V) Perchlorate and Np(V) Chloride with Urea

The crystal structure of [NpO₂{OC(NH₂)₂}₅]ClO₄·H₂O and [NpO₂Cl{OC(NH₂)₂}₄] was studied by X-ray diffraction. The electronic absorption spectra of these complexes were recorded. The coordination polyhedron of Np in both complexes is a distorted pentagonal bipyramid. There is no cation-cation interaction of neptunyl cations in these complexes.     

Synthesis of New Crystalline Pu(V) Compounds from Solutions: V. Crystal Structure of [Co(NH3)6][PuO2(C2O4)2] · 3H2O

The compound [Co(NH₃)₆][PuO₂(C₂O₄)₂] · 3H₂O was studied by single crystal X-ray diffraction. The structure contains dimeric complex anions [PuO₂(C₂O₄)₂] ₂ ⁶⁻ in which the coordination polyhedra of the Pu atoms are distorted pentagonal bipyramids sharing a common equatorial edge. In going from [Co(NH₃)₆] · [NpO₂(C₂O₄)₂] · 3H₂O to [Co(NH₃)₆][PuO₂(C₂O₄)₂] · 3H₂O, the An-O distances, both axial (in the actinyl group) and equatorial, decrease virtually isotropically. __________ Translated from Radiokhimiya, Vol. 47, No. 5, 2005, pp. 419–422. Original Russian Text Copyright ? 2005 by Grigor'ev, Antipin, Krot, Bessonov.     

Crystal structure of a double Np(V) and Co(NH3)63+ maleate, Co(NH3)6[NpO2(HL)2(H2O)3](HL)2?H2O [L = OOC(HC)2COO]

Crystal structure of a double Np(V) and Co(NH₃) ₆ ³⁺ maleate Co(NH₃)₆[NpO₂(HL)₂(H₂O)₃](HL)₂H₂O [L = OOC(HC)₂COO] was studied. The crystal structure consists of complex anions [NpO₂(HL)₂(H₂O)₃]^–, HL^– anions, [Co(NH₃)₆]³⁺ cations, and water molecules of crystallization. Hydrogen bonds in which proton donors are water molecules and hexaamminecobalt cations link structural fragments to form a 3D network. The coordination polyhedra of the Np(V) atoms are pentagonal bipyramids whose equatorial planes are formed by oxygen atoms of two HL^– anions and three water molecules. Four crystallographically independent maleate anions were identified in the structure. Two of these anions enter into the Np(V) surrounding, and their coordination capacity is 1.Translated from Radiokhimiya, Vol. 46, No. 6, 2004, pp. 521–523.Original Russian Text Copyright © 2004 by Charushnikova, Krot, Starikova.     

Synthesis and properties of Np(VI) and Pu(VI) monophthalates

Neptunium(VI) and plutonium(VI) monophthalates were prepared and characterized. The complexes AnO₂ (COO)₂C₆H₄ 2H₂O were isolated from cold solutions, and AnO₂ (COO)₂C₆H₄ 1.33H₂O, from hot solutions. NpO₂ (COO)₂C₆H₄ b. 2H₂O and PuO₂ (COO)₂C₆H₄ 2H₂O crystalize in the triclinic and monoclinic systems, respectively. The complexes AnO₂(COO)₂C₆H₄ 1.33H₂O are isostructural and crystallize in the rhombohedral system. The thermal behavior of these complexes was studied. Their IR and electronic absorption spectra were recorded. The properties of these complexes were compared to those of known U(VI) monophthalates.Translated from Radiokhimiya, Vol. 46, No. 5, 2004, pp. 389–395.Original Russian Text Copyright © 2004 by Krot, Bessonov, Grigorev, Charushnikova, Makarenkov.     

Crystal Structure of Neptunium(V) Phthalate (NpO2)2(OOC)2C6H4·4H2O

The crystal structure of (NpO₂)₂(OOC)₂C₆H₄·4H₂O [rhombic cell: a = 15.937(3), b = 26.922(5), c = 8.020(2) Å, space group Pbcn, Z = 8, V = 3441.0(12) ų, d _calc = 2.988 g cm^{- 3}, CAD4, MoK , graphite monochromator, 2934 independent reflections; R ₁ = 0.0352, wR ₂ = 0.0951] was studied. The structure consists of NpO₂ ⁺ cations, H₄C₆(COO)₂ ^{2 -} anions, and molecules of coordinated and crystallization water. The crystal lattice involves neutral layers [(NpO₂)₂(OOC)₂C₆H₄(H₂O)₃] _n parallel to the {101} plane. The dioxocations in these layers are bonded to each other to form cationic networks [the Np···Np distance is 3.911(1)-4.202(1) Å]. The coordination polyhedra of Np(1) and Np(2) are pentagonal bipyramids (CN 7). The point group of the neptunyl(V) groups is close to D _h. These groups are bidentate ligands in the cation-cation interaction. The Np = O bond lengths are 1.852(6) [Np(1)-O(1)], 1.849(7) [Np(1)-O(2)], 1.845(7) [Np(2)-O(3)], and 1.841(7) Å [Np(2)-O(4)]; the O = Np = O bond angles are 178.6(3)° [O(2)-Np(1)-O(1)] and 177.4(3)° [O(3)-Np(2)-O(4)]. The equatorial plane of the Np(1) bipyramid consists of two oxygen atoms of adjacent Np(2)O₂ ⁺ dioxocations, two water molecules, and a single oxygen atom of the phthalate anion. The equatorial plane of the Np(2) bipyramid consists of two oxygen atoms of adjacent Np(1)O₂ ⁺ dioxocations, two oxygen atom of the phthalate anion, and a single water molecule. The bond lengths in the equatorial plane of the bipyramid lie in the following ranges: Np-Oyl 2.373(7)-2.437(7) Å (average 2.397 Å) , Np-Ophth 2.360(7)-2.474(7) Å (average 2.431 Å), and Np-Owater 2.534(8)-2.558(9) Å (average 2.544 Å). The phthalate anions are tridentate bridging ligands binding neptunium atoms only within a single cationic network.     

Crystal Structure of Double Lithium Neptunium(V) Carbonate Dihydrate LiNpO2CO3·2H2O

According to the data of X-ray diffraction analysis, the structure of LiNpO₂CO₃·2H₂O is built of [LiNpO₂CO₃H₂O]_n layers, arranged perpendicularly to the [001] direction, and of crystallization water molecules. The layers are based on mixed cation-anion trigonal networks; Np(V) occurs in the hexagonalbipyramidal environment with three bidentate CO₃ ^{2 -} ions coordinated in the equatorial plane of the bipyramid. The coordination capacity of anions is 6 and 3 with regard to Np and Li, respectively.     

Synthesis and crystal structure of double Np(V) cesium oxalate CsNpO2C2O4 · nH2O

An X-ray diffraction study of CsNpO₂C₂O₄ · nH₂O was carried out. The structure consists of NpO ₂ ⁺ and Cs⁺ cations, oxalate anions, and water molecules. Dioxo cations are combined by cation-cation interaction into cyclic trimer in which each NpO ₂ ⁺ cation act as monodentate ligand. The coordination polyhedron of the Np(V) atom is a pentagonal bipyramid. The similarity of the structures of MNpO₂C₂O₄ · nH₂O (M = NH₄, Cs) based on cyclic trimers combined by oxalate ions into a three-dimensional framework was confirmed. Original Russian Text I.A. Charushnikova, N.N. Krot, I.N. Polyakova, 2006, published in Radiokhimiya, 2006, Vol. 48, No. 3, pp. 202–204.     

Electronic absorption spectra of crystalline Pu(V) compounds

Electronic absorption spectra of different crystalline Pu(V) compounds in the range 400–1200 nm were recorded. The correlation between the spectra of these compounds and their structure was discussed. The intensities of the absorption bands of solid compounds with the pentagonal bipyramidal surrounding of the Pu atom are similar to those observed in solution, whereas the centrosymmetrical hexagonal-bipyramidal surrounding is characterized by substantially decreased intensity of the absorption bands up to their complete disappearance. Comparison of the optical spectra of Pu(V) compounds with known structure and those of aqueous Pu(V) solution shows that the hydration number of PuO ₂ ⁺ is 5.