Crystallization of salts M3[NpO4(OH)2]·nH2O (M = Na, K, Rb, Cs) from concentrated alkali solutions at low temperatures. Synthesis and structure of a new Np(VII) compound, Na3[NpO4(OH)2]·6H2O

Precipitation of salts M₃[NpO₄(OH)₂]·nH₂O (M = Na, K, Rb, Cs) from concentrated alkali solutions at low temperatures (about ?10°C) was studied. From solutions with [OH^?] > 9.5 M, these compounds are isolated as coarse black crystals in high yield without impurity of other phases. The K, Rb, and Cs salts crystallize in the form of the previously studied compounds K₃[NpO₄(OH)₂]·2H₂O and M₃[NpO₄(OH)₂]·3H₂O (M = Rb, Cs). In the case of Na, a new hydrate Na₃[NpO₄(OH)₂]·6H₂O was obtained, and its crystal structure was determined. Crystals of the hexahydrate consist of centrosymmetrical tetragonal-bipyramidal anions [NpO₄(OH)₂]^3?, crystallographically independent Na(1) and Na(2) cations, and water molecules. The coordination surrounding of the Np atom is characterized by noticeable difference (Δ = 0.0203 Å) in the Np-O bond lengths in the equatorial plane of the bipyramid. The [NpO₄(OH)₂]^3? anions are combined with the Na(2) cations to form infinite chains [Na(2)NpO₄(OH)₂(H₂O)₂]^2? in such a manner that the lateral edges of the anion are simultaneously the lateral edges of the Na(2) coordination polyhedron. Incorporation of one of the two crystallographically independent O atoms of the NpO₄ group into the Na(2) coordination surrounding is responsible for a noticeable difference in the Np-O bond lengths in the equator of the [NpO₄(OH)₂]^3? anion. The types of hydrogen bonding in the structures of Na3[NpO₄(OH)₂]·nH₂O (n = 0, 2, 4, 6) are compared.     

Synthesis and Structure of the Np(VII) Complex with Guanidinium,Li[C(NH<Subscript>2</Subscript>)<Subscript>3</Subscript>]<Subscript>2</Subscript>[NpO<Subscript>4</Subscript>(OH)<Subscript>2</Subscript>]·6H<Subscript>2</Subscript>O

The previously unknown Np(VII) compound Li[C(NH₂)₃]₂[NpO₄(OH)₂]·6H₂O (I), containing organic cations, was synthesized and studied by single crystal X-ray diffraction. In contrast to the relatively numerous structurally characterized salts of [NpO₄(OH)₂]^3– anions with Na⁺, K⁺, Rb⁺, and Cs⁺ cations, which were prepared only from strongly alkaline media, crystals of I were isolated from solutions with a very low concentration of OH^– ions (about 0.1 M). The compound is relatively stable in storage in the dry form, but is strongly hygroscopic. In the structure of I, there are two independent Np(VII) atoms with the oxygen surrounding in the form of tetragonal bipyramids. In contrast to the other salts of the [NpO₄(OH)₂]^3– anions with singlecharged alkali metal cations, the C(NH₂) ₃ ⁺ ions and hydrated Li⁺ ions in I interact with the oxygen surrounding of Np(VII) only via hydrogen bonds of types O_w–H···O and N–H···O with the formation of a three-dimensional H-bond network.     

Synthesis and structure of actinide(VII) compounds Rb3NpO4(OH)2·3H2O and Rb3PuO4(OH)2·3H2O

Actinide(VII) salts Rb₃[NpO₄(OH)₂]·3H₂O (I) and Rb₃[PuO₄(OH)₂]·3H₂O (II) were prepared as single crystals and examined by X-ray diffraction. The compounds are isostructural and crystallize in the monoclinic system, space group C2/c, Z = 4; unit cell parameters: a = 12.1544(3), b = 10.9942(2), c = 7.789(2) ?, ?? = 91.0930(11)° for I and a = 12.1254(3), b = 10.9506(2), c = 7.7699(2) ?, ?? = 90.8253(12)° for II. The main structural elements of I and II are centrosymmetrical anions [AnO₄(OH)₂]^3? forming together with water molecules, owing to strong hydrogen bonding, chains oriented along [101]. In [AnO₄(OH)₂]^3? anions, the central An(VII) atom has a tetragonal-bipyramidal oxygen surrounding. The An-O(OH) interatomic distances decrease in going from I to II owing to actinide contraction by a factor of ??2 more strongly than the An-O bond lengths in the equatorial planes of the bipyramids. The previously studied structure of Cs₃[NpO₄(OH)₂]·3H₂O (III) was refined.     

Synthesis and X-ray diffraction study of monohydrates of rubidium and cesium salts of Np(VII) and Pu(VII)

The compounds Rb₃[AnO₄(OH)₂]·H₂O and Cs₃[AnO₄(OH)₂]·H₂O, where An = Np or Pu, were prepared as single crystals by crystallization from alkaline solutions of Np(VII) and Pu(VII) in the course of their drying at 70–75°C. The crystals were subjected to X-ray diffraction analysis. All the compounds are isostructural and contain An atoms in the form of [AnO₄(OH)₂]^3? anions in which the oxygen surrounding of the An atoms is a slightly distorted tetragonal bipyramid. The averaged An-O distances in the equatorial planes of the bipyramids vary insignificantly (within 1.884–1.892 Å), tending to slightly decrease in going from Np to Pu. This trend is more pronounced for averaged An-OH distances, which vary in the range 2.328–2.368 Å. That is, as in the case of the other previously studied An(VII) compounds, the actinide contraction is mainly manifested in shortening of the An-OH distances. One of the features of Rb₃[AnO₄(OH)₂]·H₂O and Cs₃[AnO₄(OH)₂]·H₂O structures, as compared with the trihydrates, is the lack of the symmetry center in [AnO₄(OH)₂]^3? anions.     

Synthesis and Structure of Mixed-Cation Salts with [NpO<Subscript>4</Subscript>(OH)<Subscript>2</Subscript>]<Superscript>3–</Superscript> Anions

Mixed-cation salts of the general composition NaM₂[NpO₄(OH)₂]·4H₂O, where M = Rb (I, II) and Cs (III), were synthesized and structurally characterized. The compounds differ from each other in the structural organization. The Np central atom in [NpO₄(OH)₂]^3– anions has oxygen surrounding in the form of a tetragonal bipyramid with the O atoms of hydroxide ions in the apical positions. The hydrated Na⁺ cations have oxygen surrounding in the form of a distorted octahedron. In the structure of I, there are two independent Rb cations with 10- and 12-vertex coordination polyhedra, and in the structures of II and III the framework of large cations is built of 12-vertex Rb and Cs polyhedra. The coordination polyhedra of the Np and Na atoms, sharing a common edge (I, III), or chains of the coordination polyhedra of the Np and Na atoms, sharing common vertices (II), are accommodated in the channels of the frameworks. Hydrogen bonds influence the crystal packing and the geometric characteristics of the [NpO₄(OH)₂]^3– anions.     

New data on sodium salts of Np(VII) and Pu(VII)

A new Pu(VII) compound, Na₃[PuO₄(OH)₂]·2H₂O, was prepared by X-ray diffraction analysis, and its structure was studied. To reveal the character of actinide contraction in going from Np(VII) to Pu(VII), the geometric parameters of the tetragonal-bipyramidal surrounding of Pu(VII) in the [PuO₄(OH)₂]³⁻ anion were compared with those of Np(VII) in the previously studied isostructural compound Na₃[NpO₄(OH)₂]·2H₂O. To reveal the specific feature of hydrogen bonding in crystals of the general composition Na₃[NpO₄(OH)₂]·nH₂O (n = 0, 2, 4), the structure of the compound Na₃[NpO₄(OH)₂]·4H₂O studied previously by the photographic method was refined. The effect of hydrogen bonds on the geometric characteristics of the coordination polyhedra of the Np and Na atoms was considered.     

Complexes of An(VI) with Cyclobutanecarboxylic Acid Anions and Outer-Sphere Alkali Metal Cations

New complexes of hexavalent actinides with cyclobutanecarboxylic acid (Hcbc) anions, Na₄[NpO₂· (cbc)₃]₄·H₂O (I), K[NpO₂(cbc)₃] (II), Cs[NpO₂(cbc)₃] (III), and Cs[PuO₂(cbc)₃] (IV), cbc = C₄H₇(COO)^–, were synthesized and studied by single crystal X-ray diffraction. The structures of I–IV are based on the anionic complexes [AnO₂(cbc)₃]^– surrounded by alkali metal cations. The AnO ₂ ²⁺ cation in the anionic complex is bonded with three chelating C₄H₇COO^– anions, and the coordination polyhedron (CP) of An is a hexagonal bipyramid with the O atoms of the AnO ₂ ²⁺ cations in apical positions. The coordination number (CN) of the alkali metal cations in the structures of II–IV is the same and equal to 6; the coordination surrounding of the K⁺ and Cs⁺ cations is constituted by the O atoms of six C₄H₇COO^– anions. The crystal structures of II–IV are examples of cubic 3-connected networks (10,3) built of alkali metal and actinide cations. In the structure of I, there are four kinds of crystallographically different NpO ₂ ²⁺ and Na⁺ cations. The coordination surrounding of the NpO ₂ ²⁺ cations differs only in the conformational characteristics of the C₄H₇COO^– ligands. Four independent Na⁺ cations differ from each other in the structure of the coordination surrounding. The CPs of the Na(1) and Na(4) atoms can be described as distorted octahedra (CN 6); that of Na(3), as a trigonal prism (CN 6); and that of Na(2), as a tetragonal pyramid (CN 5) with one of the basal vertices occupied by the Ow(1) atom of a water molecule. In the structure of I, the configuration of the network formed by the Na and Np cations differs from the cubic 3-connected network found in the structures of II–IV.     

New quaternary alkali metal,rare earth (3+) thiophosphate,K2SmP2S7 with both [P2S6]4− and [PS4]3− anions

A new quaternary alkali metal, rare earth thiophosphate was synthesized by the ceramic method and characterized by single crystal X-ray diffraction: K₂SmP₂S₇ crystallizes in the monoclinic space group C2 (no. 5) with the unit cell parameters a = 22.746(5) Å, b = 6.7362(13) Å, c = 8.9004(18) Å, β = 99.68(3)°, V = 1344.3(5) Å³ and Z = 2. The phase K₂SmP₂S₇ can be better described as K₄Sm₂[PS₄]₂[P₂S₆] because it contains in the crystal structure both discrete anions [PS₄]^3? and [P₂S₆]^4?. The crystal structure consists of infinite chains of ¹_∞[SmPS₄] that are linked together through the ethane-like [P₂S₆]^4? anions to form two-dimensional layers. The packing of K₂SmP₂S₇ is formed by layers of ²_∞[Sm₂[PS₄]₂[P₂S₆]]^4? separated by K⁺ cations. K₂SmP₂S₇ was characterized by Raman and Fourier transform infrared (FTIR) spectroscopy and SEM-EDX microprobe analyses. The optical band gap of K₂SmP₂S₇ was determined by UV–vis diffuse reflectance measurements to be 2.59 eV.     

Synthesis and crystal structure of a new Np(V) oxalate, Na4(NpO2)2(C2O4)3·6H2O

A new oxalate complex, Na₄(NpO₂)₂(C₂O₄)₃·6H₂O, with the Np:C₂O₄ ratio of 2:3 was synthesized and studied by single crystal X-ray diffraction. In the crystal, the NpO ₂ ⁺ cations and oxalate anions are bound in open networks [(NpO₂)₂(C₂O₄)₃] _n ^4n- parallel to the bc plane. The Na(1) cations are accommodated in large voids of the neptunyl oxalate networks with the formation of crimped mixed-cation layers of the composition [Na₂(NpO₂)₂(C₂O₄)₃] _n ^2n- . The negative charge of the layers is compensated by the Na(2) cations arranged between the layers. The Np atoms have a pentagonal bipyramidal coordination surrounding with the equatorial plane formed by the oxygen atoms of three oxalate anions. The structure contains tridentate-bridging and tetradentate-bridging oxalate anions.     

Cation-cation interaction in mixed-valent An(IV)/Np(V) tribromoacetates [An(NpO2)(H2O)3(CBr3COO)5]·CBr3COOH·nH2O,An = Th(IV), Np(IV)

The structure of new mixed-valent An(IV)/Np(V) compounds [An(NpO₂)(H₂O)₃(CBr₃COO)₅]·CBr₃COOH·nH₂O, where An(IV) = Th and Np, was studied. Two independent Np(V) atoms have the coordination surrounding in the form of pentagonal bipyramids with the O atoms of NpO ₂ ⁺ dioxocations in apical positions; the equatorial planes of the bipyramids are constituted by the O atoms of five CBr₃COO^? ions. Two independent An(IV) atoms have the oxygen surrounding in the form of distorted tricapped trigonal prisms (CN = 9) constituted by the O atoms of four CBr₃COO^? ions, two NpO ₂ ⁺ cations, and three water molecules. Eight of ten independent CBr₃COO^? anions link the An⁴⁺ and NpO ₂ ⁺ cations in the bidentate bridging fashion into electrically neutral chains [An(NpO₂)(H₂O)₃(CBr₃COO)₅]n, and two CBr₃COO^? anions interact with two independent NpO ₂ ⁺ dioxocations in the monodentate fashion. CBr₃COOH and water molecules are located between the layers. In the [An(NpO₂)(H₂O)₃(CBr₃COO)₅]n chains, NpO ₂ ⁺ cations alternate with An⁴⁺ cations, and mixed-valent An(IV)/Np(V) cation-cation interaction arises, in which each NpO ₂ ⁺ cation acts as a bidentate ligand and An⁴⁺ acts as coordination center for two dioxocations. [Th(NpO₂)(H₂O)₃(CBr₃COO)₅]·CBr₃COOH·2H₂O is the first example of a Th(IV) compound in which cation-cation bonds with the NpO ₂ ⁺ ions are present.     

Crystal structure of mixed-valent Np(IV)/Np(V) chloride, [Np(NpO2)6(H2O)8(OH)Cl9]·H2O

A new mixed-valent Np(IV)/Np(V) chloride, [Np(NpO₂)₆(H₂O)₈(OH)Cl₉]·H₂O, was synthesized, and its crystal structure was determined. The crystals consist of NpO ₂ ⁺ and Np⁴⁺ cations, of Cl^? and OH^? anions, of coordination-bonded water molecules, and of water molecules of crystallization. The Np(V) atom, Np(1), has pentagonal bipyramidal coordination surrounding with O atoms in the apical position and with the equatorial plane formed by three Cl^? anions, O atom of the adjacent NpO ₂ ⁺ cation, and O atom of water molecule. The mutual coordination of the neptunyl(V) ions, cation-cation (CC) interaction, links the Np(1) coordination polyhedra via common vertices into rings around sixfold axes, with the Np(V)?Np(V) distance in these fragments of 4.276 Å. The ring fragments are linked with each other via common equatorial edges of the bipyramids into layers perpendicular to c-axis. The Np(IV) atom, Np(2), has coordination surrounding in the form of tricapped trigonal prism (CN 9) with the tetragonal lateral faces formed by the O atoms of the NpO ₂ ⁺ cations and the capping positions occupied by the O atoms of two water molecules and one hydroxy group. The Np(2) atoms act in CC interactions as coordination center for six NpO ₂ ⁺ ions, with the Np(IV)?Np(V) distance of 4.183 Å. The Np(2) polyhedra are arranged in the crystal between layers of the Np(1) coordination polyhedra, linking them with each other.     

Crystal Structure of a Double Oxalate of Np(V) and Co(NH3)

The crystal structure of a dioxalate complex Co(NH₃)₆NpO₂(C₂O₄)₂·1.5H₂O was studied. The structure consists of centrosymmetrical dimeric anions [NpO₂(C₂O₄)₂] ₂ ⁶⁻ , [Co(NH₃)₆]³⁺ cations, and water molecules of crystallization. The NpO ₂ ⁺ dioxocations have close Np-O bond lengths (average 1.824 Å) and are noticeably bent (ONpO angle 175.6°). Each dioxocation in the [NpO₂(C₂O₄)₂] ₂ ⁶⁻ anion is surrounded by five oxygen atoms of three C₂O ₄ ²⁻ anions; the Np coordination polyhedra are pentagonal bipyramids sharing a common edge. __________ Translated from Radiokhimiya, Vol. 47, No. 6, 2005, pp. 495–499. Original Russian Text Copyright ? 2005 by Charushnikova, Krot, Polyakova.     

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.     

Crystal structure of a Np(V) sesquioxalate,Na<Subscript>4</Subscript>(NpO<Subscript>2</Subscript>)<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>3</Subscript>·2H<Subscript>2</Subscript>O

The crystal structure of a previously unknown Np(V) sesquioxalate, Na₄(NpO₂)₂(C₂O₄)₃·2H₂O was studied. The crystal structure consists of neptunyl(V) cations, sodium cations, oxalate anions, and water molecules of crystallization. Neptunyl(V) cations and oxalate ions form anionic chains [(NpO₂)₂(C₂O₄)₃] _n ^4n? . The coordination polyhedron (CP) of Np (pentagonal bipyramid) contains two apical “yl” oxygen atoms and five equatorial O atoms of three oxalate ions. The CP of Na(1) and Na(2) cations are combined through the common edges into zigzag chains in the [010] direction. Two independent oxalate ions are tridentate and tetradentate ligands.     

Crystal structure of a Pu(VII) potassium salt,K<Subscript>3</Subscript>PuO<Subscript>4</Subscript>(OH)<Subscript>2</Subscript>·2H<Subscript>2</Subscript>O

A new Pu(VII) compound, K₃PuO₄(OH)₂·2H₂O, was synthesized, and its structure was studied by single crystal X-ray diffraction. This compound is isostructural to the previously described K₃NpO₄(OH)₂·2H₂O. The structure of the latter compound was redetermined to obtain more precise interatomic distances in the NpO₂(OH) ₂ ^3? anion. Changes in An-O bond lengths in the tetragon-bipyramidal coordination polyhedron of the compounds K₃AnO₄(OH)₂·2H₂O in going from Np(VII) to Pu(VII) were considered.     

Electrochemical behaviors of iron-based layered double hydroxide thin-films

The ordered ultrathin films based on the fabrication of Mg/Fe-LDHs ([Mg₆Fe₂(OH)₁₆CO₃·(H₂O)_4.5]_0.375) nanosheets and hexacyanoferrate(III) anions via the self-assembly procedure were prepared. The electrodes modified by the films demonstrated a couple of well-defined reversible redox peaks attributed to [Fe(CN)₆]^3?/4? and Fe^2+/3+ couples. The effects of cycle number, scan rate and Mg/Fe molar ratio on the CV performance of the thin-film electrodes were observed in K₃[Fe(CN)₆] electrolyte. The [Fe(CN)₆]^3? pillared Mg/Fe-LDHs with Mg/Fe molar ratio of 3 (LDH-(CN)-3) demonstrated an excellent electrochemical behavior with a potential window between ??0.2 and 1.0 V, high specific capacitance and sensitivity, indicating that the high crystallinity, large specific surface area and plentiful [Fe(CN)₆]^3? anions in interlayer spaces were necessary. Especially, the interlayer [Fe(CN)₆]^3? anions significantly affected the electrochemical behavior of the electrode, where the electrode reaction was controlled by the diffusion of [Fe(CN)₆]^3?/4? and Fe^2+/3+ couples. Under current density of 2.5 A g^?1, the optimized LDH-(CN)-3 electrode exhibited high specific capacitance of 250.81 F g^?1 with good cycling stability. This facile synthesis strategy and the good electrochemical properties indicated that the LDH-(CN)-3 was a potential economical alternative material for supercapacitor application.     

Synthesis and Structure of Mixed-Cation Salts with [PuO<Subscript>4</Subscript>(OH)<Subscript>2</Subscript>]<Superscript>3–</Superscript> Anions

Mixed-cation salts of the composition NaM₂[PuO₄(OH)₂]·4H₂O, where M = Rb (I) and Cs (III), and NaRb₅[PuO₄(OH)₂]₂·6H₂O (II) were synthesized and structurally characterized. The central Pu atom in [PuO₄(OH)₂]^3– anions has oxygen surrounding in the form of a tetragonal bipyramid with oxygen atoms of hydroxide ions in apical positions. The hydrated Na⁺ cations have oxygen surrounding in the form of a distorted octahedron. In the structure of I, there are two independent Rb⁺ cations with 10- and 12-vertex coordination polyhedra (CPs), and in the structure of II, three independent Rb⁺ cations with the 12-, 11-, and 13-vertex CPs. In the structure of III, the Cs⁺ cation has a 12-vertex CP. Frameworks of large Rb⁺ or Cs⁺ cations can be distinguished in the structure. The CPs of the Pu and Na atoms (I, III) sharing a common edge or the isolated CPs of the Pu and Na atoms (II) are incorporated in these frameworks. Hydrogen bonds influence the crystal packing and the geometric characteristics of the [PuO₄(OH)₂]^3– anions.     

Synthesis and structure of crystalline complexes of Np(V) with 1,10-phenanthroline-2,9-dicarboxylic acid. Complexation in solution and spectral studies

Complexes of Np(V) with 1,10-phenanthroline-2,9-dicarboxylic acid, C₁₂H₆N₂(COOH)₂ (H₂PDA), of the compositions [(NpO₂)₂(PDA)(H₂O)₃]·H₂O (I), (NH₄)₂[NpO₂(PDA)]₂·3H₂O (II), and [C(NH₂)₃]₂[NpO₂·(PDA)]₂·4H₂O (III) were synthesized. The Np atoms in the crystal lattices of all the compounds have the pentagonal bipyramidal coordination surrounding, with the [C₁₂H₆N₂(COO)₂]^2? anions acting as chelate-bridging N,O-donor ligands. In the structure of I, two crystallographically independent NpO ₂ ⁺ dioxocations participate in the cation-cation interaction leading to the formation of tetrameric cation-cation complexes. The nonequivalence of the Np atoms is manifested in splitting of the main absorption band of Np(V) in the electronic spectrum of solid compound I. The structures of II and III are based on dimeric anionic complexes [NpO₂(C₁₂H₆N₂(COO)₂)] ₂ ^2? . Only one kind of complexes, NpO₂(PDA)^?, was detected in the solution, and high value of the concentration stability constant β, ～10¹² L mol^?1, is due to tetradentate coordination of the ligand.     

Crystal Structure of Double Co(NH3)6 3 + Np(V) Malonates Co(NH3)6(NpO2C3H2O4)2A·H2O (A = OH and NO3)

X-ray diffraction analysis of Co(NH₃)₆(NpO₂C₃H₂O₄)₂NO₃·H₂O (I) and Co(NH₃)₆(NpO₂· C₃H₂O₄)₂OH·H₂O (II) showed that they consist of [NpO₂C₃H₂O₄] _n ^{n -} infinite anionic chains, [Co(NH₃)₆]^{3 +} cations, NO₃ ^- (I) and OH^- (II) anions, and molecules of crystallization water. The anionic chain structure is similar to that in the known compound Co(NH₃)₆(NpO₂C₃H₂O₄)₂C₃H₃O₄. Neptunium(V) atoms occur in hexagonal-bipyramidal environment. The coordination capacity of malonate anions is 6, and they simultaneously coordinate three neptunyl(V) cations NpO₂ ⁺ in the chain.     

Synthesis and single crystal X-ray diffraction study of U(VI), Np(VI), and Pu(VI) perchlorate hydrates

The compounds [AnO₂(H₂O)₅](ClO₄)₂ (An = Np, Pu) and [NpO₂(ClO₄)₂(H₂O)₃] were prepared as single crystals, which were studied by X-ray diffraction at 100 K. The structural type at room temperature was determined. The low-temperature modification of [UO₂(H₂O)₅](ClO₄)₂ was found and structurally studied. The coordination polyhedra in [AnO₂(H₂O)₅]²⁺ are weakly distorted pentagonal bipyramids with averaged interatomic distances An-O of 1.754, 1.744, and 1.732 Å in the “yl” groups and of 2.415, 2.416, and 2.409 Å in the equatorial planes for U, Np, and Pu, respectively. Hence, in the complex cations [AnO₂(H₂O)₅]²⁺ the actinide contraction is manifested only in regular shortening of the An-O interatomic distances in the “yl” groups. The compound [NpO₂(ClO₄)₂(H₂O)₃], isostructural to its known uranyl analog, appeared to be the first, proved by single crystal X-ray diffraction, example of a compound with coordination interaction between the perchlorate ion and the neptunyl(VI) cation.