Crystal structure of Na<Subscript>3</Subscript>(NH<Subscript>4</Subscript>)<Subscript>2</Subscript>[Ir(SO<Subscript>3</Subscript>)<Subscript>2</Subscript>Cl<Subscript>4</Subscript>]·4H<Subscript>2</Subscript>O

The complex Na₃(NH₄)₂[Ir(SO₃)₂Cl₄]·4H₂O was examined with single crystal X-ray diffraction and IR spectroscopy. Crystal data: a = 7.3144(4) Å, b = 10.0698(5) Å, c = 12.3748(6) Å, β = 106.203(1)°, V = 875.26(8) ų, space group P2₁/c, Z = 2, d _calc = 2.547 g/cm³. In the complex anion two trans SO ₃ ^2? groups are coordinated to iridium through the S atom. The splitting of O-H bending vibrations of crystallization water molecules and N-H ones of the ammonium cation is considered in the context of different types of interactions with the closest neighbors in the structure.     

Synthesis and Structure of [Co(NH<Subscript>3</Subscript>)<Subscript>6</Subscript>]<Subscript>2</Subscript>[W<Subscript>4</Subscript>Se<Subscript>4</Subscript>(CN)<Subscript>12</Subscript>]·8.5H<Subscript>2</Subscript>O

The compound [Co(NH₃)₆]₂[W₄Se₄(CN)₁₂]·8.5H₂O was obtained by evaporating an aqueous ammonia solution of K₆[W₄Se₄(CN)₁₂]·6H₂O and CoCl₂·6H₂O complexes. The starting Co(II) of CoCl₂·6H₂O transforms into [Co(NH₃)₆]³⁺ when exposed to air in a water-ammonia medium. Crystal data: triclinic crystal system, a = 10.7750(8) Å, b = 12.2843(9) Å, c = 19.6539(14) Å; α = 90.213(2)°, β = 99.910(2)°, γ = 114.737(1)°, V = 2319.1(3) ų, space group , Z = 2, D _x = 2.633 g/cm³.Original Russian Text Copyright © 2004 by I. V. Kalinina, Z. A. Starikova, F. M. Dolgushin, D. G. Samsonenko, and V. P. Fedin__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 905–908, September–October, 2004.     

Crystal structure of Cs[(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH)] · H<Subscript>2</Subscript>O

Single crystals of Cs[(UO₂)₂(C₂O₄)₂(OH)] · H₂O were synthesized and structurally studied using X-ray diffraction. The compound crystallizes in monoclinic space group P2₁/m, Z = 2, with the unit cell parameters a = 5.5032(4) Å, b = 13.5577(8) Å, c = 9.5859(8) Å, β = 97.012(3)°, V = 709.86(9) ų, R = 0.0444. The main building units of crystals are [(UO₂)₂(C₂O₄)₂(OH)]^? layers of the A₂K ₂ ⁰² M² (A = UO ₂ ²⁺ , K⁰² = C₂O ₄ ^2? , and M² = OH^?) crystal-chemical family. Uranium-containing layers are linked into a three-dimensional framework via electrostatic interactions with outer-sphere cations and hydrogen bonds with water molecules.     

Synthesis and crystal structure of [Cr(NH<Subscript>3</Subscript>)<Subscript>5</Subscript>Cl][PdCl<Subscript>4</Subscript>]·H<Subscript>2</Subscript>O

Synthesis and investigation of a binary complex salt [Cr(NH₃)₅Cl][PdCl₄]·H₂O is reported. The compound is isostructural with [Rh(NH₃)₅Cl][PdCl₄]·H₂O studied earlier; it was characterized by element analysis and powder and single crystal X-ray diffraction. Crystal data for H₁₇Cl₅N₅OPdCr: a = 7.8668(12) Å, b = 10.9703(16) Å, c = 16.048(2) Å, = 102.469(3)°, space group P2₁/c, Z = 4, V = 1352.3(3)ų, d _calc = 2.155 g/cm³.Original Russian Text Copyright © 2004 by I. A. Baidina, P. E. Plyusnin, S. V. Korenev, K. V. Yusenko, Yu. V. Shubin, and S. A. GromilovTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 549–552, May–June 2004.     

Reaction of [Pt(NH<Subscript>3</Subscript>)<Subscript>4</Subscript>]Cl<Subscript>2</Subscript>·H<Subscript>2</Subscript>O and NH<Subscript>4</Subscript>ReO<Subscript>4</Subscript> in alkaline aqueous solution at 190°C (under pressure)

Reactions of thermolysis under pressure of tetraammineplatinum(II) chloride and ammonium perrhenate in alkaline aqueous solution were studied. The products formed at the thermolysis in a pressure reactor were investigated. A model of platinum and rhenium ions reduction to metallic state by inner sphere ammonia from [Pt(NH₃)₄]Cl₂ is suggested.     

Magnetic properties of a linear trinuclear manganese compound [Mn<Subscript>3</Subscript>(PhCO<Subscript>2</Subscript>)<Subscript>6</Subscript>(Bipy)<Subscript>2</Subscript>] · H<Subscript>2</Subscript>O

The reaction of the trinuclear oxo-centered mixed-valence complex [Mn₃O(O₂CPh)₆(Py)₂(H₂O)] with 2,2′-bipyridyl (Bipy) and another potential tripodal ligand affords the title compound [Mn₃(PhCO₂)₆(Bipy)₂] · H₂O in good yield. The X-ray crystallographic diffraction study reveals that three mangenese ions are arranged in a linear mode with Mn_center-Mn_terminal and Mn_terminal-Mn_terminal diatances of 3.588 and 7.176 Å, respectively. Molar magnetic susceptibility of the compound gradually decreases from 12.23 (300 K) to 4.45 cm³ K mol^?1 (2 K). Taking into account the structure of this compound, the data in the 2.0–300 K range were fit to the appropriate theoretical expression to give J = ?2.73 cm^?1, ρ = 2.07%, N _a = ?0.0004 cm³ mol^?1, g = 1.992, and R ² = 0.99996. The magnetization versus external magnetic field measurements at 2 K shows that the ground state is S _T = 5/2.     

Crystal Structure of Neptunium(V) Acetate [(NpO<Subscript>2</Subscript>)<Subscript>2</Subscript>(OOCCH<Subscript>3</Subscript>)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)] ⋅ 2H<Subscript>2</Subscript>O

A new neptunium(V) complex [(NpO₂)₂(CH₃COO)₂(H₂O)] ? 2H₂O was synthesized and its crystal structure was determined. The unit cell parameters are: a = 24.007(10) Å, b = 6.779(3) Å, c = 8.076(3) Å, space group Pnma, Z = 4, V = 1314.2(9) ų, R = 0.049, wR(F²) = 0.105. The crystal structure of the compound is composed of neutral [(NpO₂)₂(CH₃COO)₂(H₂O)] layers and molecules of the water of crystallization. Each of the crystallographically independent neptunoyl ions performs a bidentate function thus forming a composite system of cation-cation bonds.     

Structure and thermal properties of double complex salts [RuNO(NH<Subscript>3</Subscript>)<Subscript>4</Subscript>(H<Subscript>2</Subscript>O)]<Subscript>2</Subscript>[MCl<Subscript>4</Subscript>]Cl<Subscript>4</Subscript>·2H<Subscript>2</Subscript>O,M = Pt,Pd

Double complex salts (DCS) [RuNO(NH₃)₄(H₂O)]₂[MCl₄]Cl₄·2H₂O, M = Pt (I) and Pd (II), are prepared and characterized using IR spectroscopy, single crystal and powder X-ray diffraction, and thermogravimetric analysis. Crystalline phases of I and II are isostructural (P2(1)/n space group) and have the following crystallographic characteristics: a = 6.689 Å, b = 15.609 Å, c = 12.348 Å, V = 1289.1 ų, Z = 2, d _x = 2.425 g/cm³ (I) and a = 6.637 Å, b = 15.521 Å, c = 12.244 Å, V = 1261.2 ų, Z = 2, d _x = 2.255 g/cm³ (II). The thermolysis of the obtained DCS in the hydrogen atmosphere affords two-phase mixtures of limited solid solutions of the metals: hcp for ruthenium-based ones and fcc for Pt or Pd based solutions. On decomposition in the helium atmosphere the products contain a minor amount of RuO₂. For the phases obtained during thermolysis the parameters are determined and the compositions are estimated. The heating of I to 400°C in the helium-air atmosphere yields a nanocrystalline composite Pt+RuO₂ with CSR of ～20 nm.     

Synthesis and crystal structure of complex [Mn(Imdc)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>] · 2H<Subscript>2</Subscript>O and its interaction with DNA

Under hydrothermal conditions, the complex [Mn(lmdc)₂(H₂O)₂] · 2H₂O (I) was synthesized and characterized by elemental analysis and IR spectrum (HImdc = 4,5-imidazofedicarboxylic acid). The crystal structure of I was determined by single-crystal X-ray diffraction (crystallizing in the monoclinic crystal system, P ₂/c space group, a = 11.000(2), b = 7.1281(14), c = 12.696(3) Å, β = 122.45(3), Z = 2. In I, the Mn²⁺ ion was chelated by two Imdc with one of their nitrogen atoms and a carboxylic oxygen atom, while two water molecules occupy the axial position of the Mn atom forming a distorted octahedral geometry. Three-dimensional structure of I was formed by intermolecular hydrogen bonds. UV-Vis and fluorescence spectra of I interacting with DNA show that insertion is the main binding mode between I and fish sperm DNA. Gel electrophoresis shows that I cleaves both supercoiled and circular pBR322 DNA to form a small molecular fragment.     

Synthesis and study of uranyl arsenate (UO<Subscript>2</Subscript>)<Subscript>3</Subscript>(AsO<Subscript>4</Subscript>)<Subscript>2</Subscript> · 12H<Subscript>2</Subscript>O

A method for producing synthetic troegerite of composition(UO₂)₃(AsO₄)₂ · 12H₂. Owas developed. X-ray diffraction, IR spectrometry, X-ray fluorescence analysis, and scanning calorimetry were used to study its dehydration and thermal decomposition, to solve the structgure, and to determine X-ray diffraction and IR spectroscopic characteristics.     

Synthesis and X-ray diffraction study of Li(H<Subscript>3</Subscript>O)[UO<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)] · H<Subscript>2</Subscript>O

Single crystals of Li(H₃O)[UO₂(C₂O₄)₂(H₂O)] · H₂O (I) have been synthesized and studied by X-ray diffraction. Compound I crystallizes in the monoclinic crystal system with the unit cell parameters: a = 7.1682(10) Å, b = 29.639(6) Å, c = 6.6770(12) Å, β= 112.3(7)°, space group P 2₁/c, Z = 4, R = 4.36%. Structure I contains discrete mononuclear groups [UO₂(C₂O₄)₂(H₂O)]^2? ascribed to the crystal-chemical group AB ₂ ⁰¹ M¹ (A = UO₂ ²⁺, B⁰¹ =C₂O ₄ ^2? , M¹ = H₂O), which are “cross-linked” by the lithium ions into infinite layers {Li(UO₂)(C₂O₄)₂(H₂O)₂}^? perpendicular to [010]. The hydroxonium ions are located between adjacent uranium-containing layers. A hydrogen bond system involving water molecules, oxalate ions, and hydroxonium combines the anionic layers into a three-dimensional framework.     

Synthesis and study of physicochemical properties of the magnesium heteropoly compound (NH<Subscript>4</Subscript>)<Subscript>4</Subscript>[MgMo<Subscript>6</Subscript>O<Subscript>18</Subscript>(OH)<Subscript>6</Subscript>] · 5H<Subscript>2</Subscript>O

The magnesium heteropoly compound (NH₄)₄[MgMo₆O₁₈(OH)₆] · 5H₂O (I) has been synthesized and studied by mass spectrometry, IR spectroscopy, X-ray powder diffraction, and thermogravimetry. Crystals of I are monoclinic, space group P2₁/n, a = 15.10 Å, b = 11.64 Å, c = 13.53 Å, β = 74.28°, V = 2289.31 ų, ρ_calc = 1.09 g/cm³, Z = 1.     

Crystal structure of Ba<Subscript>3</Subscript>[UO<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>(NCS)]<Subscript>2</Subscript> · 9H<Subscript>2</Subscript>O

Single crystals of Ba₃[UO₂(C₂O₄)₂(NCS)]₂ · 9H₂O are synthesized and studied by X-ray diffraction. The crystals are orthorhombic, space group Fddd, Z = 16, and the unit cell parameters are a = 16.253(3) Å, b = 22.245(3) Å, c = 39.031(6) Å. The main crystal structural units are mononuclear complex groups [UO₂(C₂O₄)₂NCS]^3? of the crystal-chemical family (AB ₂ ⁰¹ M¹ (A = UO ₂ ²⁺ , B⁰¹ = C₂O ₄ ^2? , M¹ = NCS^?) of the uranyl complexes linked into a three-dimensional framework by electrostatic interactions and hydrogen bonds involving oxalate ions and water molecules.     

Synthesis and crystal structure of Rb<Subscript>2</Subscript>[(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>(SeO<Subscript>4</Subscript>)] · 1.33H<Subscript>2</Subscript>O

The single crystals of Rb₂[(UO₂)₂(C₂O₄)₂(SeO₄)] · 1.33H₂O were synthesized and studied by X-ray diffraction. The crystals are monoclinic, space group P2₁/m, Z= 2, the unit cell parameters: a = 5.6537(8), b = 18.736(3), c = 9.4535(15) Å, β = 98.440(5)°, V = 990.6(3) ų, R ₁ = 0.0506. The main structural units of the crystal are infinite layers of [(UO₂)₂(C₂O₄)₂(SeO₄)]^2?, corresponding to the crystal chemical group A₂K ₂ ⁰² B² (A = UO ₂ ²⁺ , K⁰² = C₂O ₄ ^2? , B² = SeO ₄ ^2? ) of uranyl complexes. The uranium-containing layers are united into a three-dimensional framework through the electrostatic interactions with the outer-sphere rubidium ions and the hydrogen bonding system involving the outer-sphere water molecules.     

Synthesis and Crystal Structure of Nitrotriammine Complex of Nitrosoruthenium(II) [RuNO(NH<Subscript>3</Subscript>)<Subscript>3</Subscript>(NO<Subscript>2</Subscript>)(OH)]Cl·0.5H<Subscript>2</Subscript>O

Procedures for the synthesis of the [RuNO(NH_{3 3}(NO₂)(OH)]Cl·0.5H₂O complex have been developed. The compound was investigated by IR spectroscopy, and also by powder and single crystal X-ray diffraction. Crystal data for H₁₁CIN₅O_4.5Ru: a = 6.5752(7) Å, b = 11.0900(18) Å, c = 12.296(2) Å, ά = 79.692(13)°, β = 85.088(11)°, γ = 87.395(11)°, V = 878.5(2) ų, Z = 4, d _calc = 2.190 g/cm³, space group . The structure is formed by [RuNO(NH₃)₃(NO₂)(OH)]⁺] complex cations, Cl⁻ anions, and crystallization water molecules. The complex crystallizes as yellow transparent prisms belonging to the triclinic crystal system; it is soluble in water and insoluble in ethanol and acetone. The crystals are stable when kept in a closed beaker, but gradually degrade in dry air.Original Russian Text Copyright © 2004 by V. A. Emel’yanov, S. A. Gromilov, and I. A. Baidina__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 923–932, September–October, 2004.     

Synthesis and structure of the [Co(NioxH)<Subscript>2</Subscript>(Thio)<Subscript>2</Subscript>]<Subscript>2</Subscript>SO<Subscript>4</Subscript>·2H<Subscript>2</Subscript>O complex compound

A new Co(III) complex of 1,2-cyclohexanedionedioxime and thiocarbamide with an SO ₄ ^2? anion and solvation water molecules in the outer sphere has been synthesized and its structure has been defined. Orthorhombic crystals, a = 11.659(2) Å, b = 26.448(5) Å, c = 30.142(6) Å, V = 9295(3) Å ³, Z = 8, d_calc = 1.599 g/cm³, space group Pbca; final R index is 0.0578 for 8221 reflections with I > 2σ(I). In the octahedral Co(III) complex, two 1,2-cyclohexanedionedioxime residues lie in the equatorial plane, while two thiocarbamide molecules are in the axial plane. Intramolecular bonds: N-H…O and O-H…O type hydrogen bonds and π-π interactions that stabilize the complex cations. In crystal, the components are linked by N-H…O and O-H…O hydrogen bonds into a 3D framework.     

Crystal structure of Na<Subscript>4</Subscript>[Na<Subscript>2</Subscript>Cr<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>6</Subscript>] · 10H<Subscript>2</Subscript>O

Single crystals of the Na₄[Na₂Cr₂(C₂O₄)₆] · 10H₂O complex were synthesized for the first time. The structure of the complex was determined by X-ray diffraction analysis. The compound crystallizes in the monoclinic crystal system with the unit cell parameters a = 17.290(4) Å, b = 12.521(3) Å, c = 15.149(3) Å, β = 100.45(3)°, Z = 4, space group Cc. Anionic layers [NaCr(C₂O₄)₃] _2n ^4n? can be distinguished in the crystal structure of the complex. The Na⁺ cations and water molecules, involved in the formation of a hydrogen bond network, are located between the anionic layers.     

Thermal stability of stercorite H(NH<Subscript>4</Subscript>)Na(PO<Subscript>4</Subscript>)·4H<Subscript>2</Subscript>O

Thermogravimetric analysis has been used to determine the thermal stability of the mineral stercorite H(NH₄)Na(PO₄)·4H₂O. The mineral stercorite originated from the Petrogale Cave, Madura, Eucla, Western Australia. This cave is one of many caves in the Nullarbor Plain in the South of Western Australia. The mineral is formed by the reaction of bat guano chemicals on calcite substrates. Upon thermal treatment the mineral shows a strong decomposition at 191 °C with loss of water and ammonia. Other mass loss steps are observed at 158, 317 and 477 °C. Ion current curves indicate a gain of CO₂ at higher temperature and are attributed to the thermal decomposition of calcite impurity.     

Synthesis,Structure and Solid-Phase Transformations of Fe Nitrosyl Complex Na<Subscript>2</Subscript>[Fe<Subscript>2</Subscript>(S<Subscript>2</Subscript>O<Subscript>3</Subscript>)<Subscript>2</Subscript>(NO)<Subscript>4</Subscript>] · 4H<Subscript>2</Subscript>O

Binuclear iron nitrosyl complex Na₂[Fe₂(S₂O₃)₂(NO)₄] · 4H₂O (I) was synthesized by the reaction of iron(II) sulfate with sodium thiosulfate in the flow of NO gas. According to X-ray diffraction data, the [Fe₂(S₂O₃)₂(NO)₄]^2– anion has binuclear centrosymmetric structure with Fe atoms bonded by the µ-S atoms of thiosulfate groups. The isomeric shift for complex I =0.168(1) mm/s and quadrupole splitting E _Q =1.288 mm/s at T=80 K. When heated, complex I transforms to Na₂[Fe₂(S₂O₃)₂(NO)₄] (II), whose unit cell parameters found by X-ray diffraction method differ from those of complex I. The process of transformation of I to II was studied by calorimetric method. Complex I transforms to complex II without chemical decomposition, which was confirmed by IR and mass spectroscopy data.__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 5, 2005, pp. 323–328.Original Russian Text Copyright © 2005 by Sanina, Aldoshin, Rudneva, Golovina, Shilov, Shulga, Martynenko, Ovanesyan.     

Thermal stability of crandallite CaAl<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH)<Subscript>5</Subscript>·(H<Subscript>2</Subscript>O)

Thermogravimetry combined with evolved gas mass spectrometry has been used to characterise the mineral crandallite CaAl₃(PO₄)₂(OH)₅·(H₂O) and to ascertain the thermal stability of this ‘cave’ mineral. X-ray diffraction proves the presence of the mineral and identifies the products of the thermal decomposition. The mineral crandallite is formed through the reaction of calcite with bat guano. Thermal analysis shows that the mineral starts to decompose through dehydration at low temperatures at around 139 °C and the dehydroxylation occurs over the temperature range 200–700 °C with loss of the OH units. The critical temperature for OH loss is around 416 °C and above this temperature the mineral structure is altered. Some minor loss of carbonate impurity occurs at 788 °C. This study shows the mineral is unstable above 139 °C. This temperature is well above the temperature in the caves of 15 °C maximum. A chemical reaction for the synthesis of crandallite is offered and the mechanism for the thermal decomposition is given.