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.     

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.     

Reactions of 2,2′-Pyridyl with the cadmium(II) compounds: Synthesis,crystal structure,and luminescence properties of [Cd(Pic)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>] · H<Subscript>2</Subscript>O

The reactions of 2,2'-pyridyl, (2-Py)C(O)C(O)(2-Py), with the Cd(II) compounds under various conditions are studied. The medium and nature of the anions exert a decisive effect on the compositions and structures of the formed cadmium complexes. The reaction of cadmium diacetate with 2,2'-pyridyl in an aqueous-alcohol medium in air affords coordination compound [Cd(Рic)₂(H₂O)₂] · H₂O (I) (Pic^? is picolinate ion, CO₂C₅H₄N), and its crystal structure is determined. The crystals are monoclinic: space group P2₁/c, a = 7.499(1), b = 15.676(1), с = 12.719(1) Å, β = 94.79(1)°, V = 1490.0(2) Å3, Z = 4, ρ_calcd = 1.502 g/cm³. The molecular packing of compound I is a supramolecular 3D framework consisting of discrete complexes [Cd(Pic)₂(H₂O)₂] linked by hydrogen bonds O–H…O. The coordination sphere of Cd²⁺ contains two O atoms and two N atoms of the ligand and two water molecules. The coordination polyhedron of Cd²⁺ is a distorted octahedron.     

Crystal structure and quantum chemical investigation of [Cd(NTO)<Subscript>4</Subscript>Cd(H<Subscript>2</Subscript>O)<Subscript>6</Subscript>] · 4H<Subscript>2</Subscript>O

[Cd(NTO)₄Cd(H₂O)₆] •4H₂O was synthesized by mixing the aqueous solution of 3-nitro-1, 2,4-triazol-5-one (NTO) and cadmium carbonate. The single crystal structure was determined by a four-circle X-ray diffractometer. The crystal is monoclinic, space group C2/c with crystal parameters of a = 2.1229(3) nm, b = 0.6261(8) nm, = 2.1165(3) nm, β= 90.602 (3)°, V= 2.977(6) nm₃, Z = 4, D_c = 2.055 g • cm_-3, μ = 15.45 cm_-1 and F(000) = 1824. 2523 observable independent reflections with F₀4σ(F₀) were used for the determination and refinement of the crystal structure. Lorentz-polarization and absorption correction were applied. The final R is 0.0282 and wR = 0.0792. The analytical results show that the Cd⁺² has two kinds of coordinate bonds in one crystal. One Cd⁺² coordinates with 4 NTO anions and another coordinates with 6 water molecules to form a binucleate complex with a structure of tetrahedron and tetragonal bipyramid, respectively. By using SCF-PM3-MO method, the electron structure of cadmium complex of NTO has been calculated. The analysis of the calculated results shows that when [Cd(NTO)₄Cd(H₂O)₆] • 4H₂O is heated, the crystallization waters will be dissociated first and the ligand waters second and NO₂ group has priority of leaving when NTO⁻ is decomposed. Analysis of the energy level and composition of localized molecular orbitals indicates that both the two Cd²⁺ bond to the coordinating atom with 5s     

Synthesis,crystal structure and DNA-binding studies of the complex [Co(C<Subscript>10</Subscript>H<Subscript>9</Subscript>N<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>] · 3H<Subscript>2</Subscript>O

A novel binuclear Cobalt(II) complex with N-(2-propionic acid)-salicyloyl hydrazone (C₁₀H₁₀N₂O₄, H₃L) was prepared and characterized. The crystal structure of [Co(C₁₀H₉N₂O₄)₂] · 3H₂O was determined by X-ray single-crystal diffractometry. The Co²⁺ ion is six-coordinated by the carboxyl and acyl O atoms and azomethine N atoms of two tridentate N-(2-propionicacid)-salicyloyl hydrazone ligands, which form two stable five-numbered rings sharing one side in the keto form. The coordination environment around the Co²⁺ ion might be described as a distorted octahedron. Abundant hydrogen bonds of the types O-H…N and O-H…O between the water molecules and ligands not only form the three-dimensional network, but also provide an extrastability for the crystal. The complex was studied for the interaction with calf thymus DNA by electronic absorption titration and emission titration. The results show that the complex is bound to calf thymus DNA mainly by intercalation. The article is published in the original.     

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.     

New double complex salt [PdEn<Subscript>2</Subscript>]<Subscript>3</Subscript>[Rh(NO<Subscript>2</Subscript>)<Subscript>6</Subscript>]<Subscript>2</Subscript> · 2.67H<Subscript>2</Subscript>O: Synthesis,crystal structure,and thermal properties

The crystal structure of the double complex salt (DCS) [PdEn₂]₃[Rh(NO₂)₆]₂ ? 2.67H₂O (I) has been determined by X-ray diffraction. Crystals are triclinic, space group \(P\bar 1\), Z = 4, a = 9.2331(3) Å, b = 9.9136(4) Å, c = 13.7824(5) Å, α = 84.3230(14)°, β = 89.9655(14)°, γ = 66.7272(13)°, V = 1152.19(7) ų, ρ_calcd = 2.141 g/cm³, R = 0.0279. The thermal behavior of complex salt I has been studied in various gas atmospheres. The end product of thermolysis in reductive atmosphere is a mixture of Pd_0.45Rh_0.55 and Pd_0.95Rh_0.05 solid solutions. The end product of thermolysis in an inert atmosphere is a homogeneous Pd_0.6Rh_0.4 solid solution.     

Crystal structure and thermal properties of [Au(en)<Subscript>2</Subscript>]<Subscript>2</Subscript>[Cu(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>]<Subscript>3</Subscript>·8H<Subscript>2</Subscript>O

The crystal structure of a double complex salt of the composition [Au(en)₂]₂[Cu(C₂O₄)₂]₃·8H₂O (en = ethylenediamine) at 150 K is determined by single crystal X-ray diffraction. The crystal data for C₂₀H₄₈Au₂Cu₃N₈O₃₂ are: a = 9.1761(3) Å, b = 16.9749(6) Å, c = 13.4475(5) Å, β = 104.333(1)°, V = 2029.43(12) ų, P2₁/c space group, Z = 2, d _x = 2.450 g/cm³. It is demonstrated that the thermal decomposition of the double complex salt in a helium or hydrogen atmosphere affords the solid solution Au_0.4Cu_0.6.     

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.     

Clathrate [Zn(C<Subscript>6</Subscript>H<Subscript>5</Subscript>COO)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>] · 2CH<Subscript>3</Subscript>COOH: Synthesis and crystal structure

The clathrate [Zn(C₆H₅COO)₂(H₂O)₂] · 2CH₃COOH (I) was obtained for the first time from zinc(II) benzoate. The individuality, the unit cell parameters, and the number of “guest” molecules in complex I were determined from X-ray diffraction and derivatographic data. Its crystal structure was solved.     

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.     

Hydrothermal synthesis and crystal structure of a novel nickel(II) complex: [Ni(H<Subscript>2</Subscript>Bibzim)<Subscript>3</Subscript>Cl<Subscript>2</Subscript> · 2H<Subscript>2</Subscript>O] (H<Subscript>2</Subscript>Bibzim = 2,2-Bibenzimidazole)

A novel organic-inorganic hybrid compound based on weak intermolecular interactions formulated as Ni(H₂Bibzim)₃Cl₂ · 2H₂O (H₂Bibzim = 2,2-bibenzimidazole, formula, C₁₄H₁₀N₄) has been synthesized under hydrothermal conditions and characterized by elemental analysis, single-crystal X-ray diffraction analyses, and IR spectra. It crystallizes in the orthorhombic system, space group Pbcn, Z = 2, a = 20.8530(19), b = 15.7838(14), c = 12.3159(11) Å, V = 4053.7(6) ų, M _r = 1736.84, ρ_c = 1.423g/cm³, λ = 0.71073 Å, μ(MoK _α) = 0.664 mm^?1, F(000) = 1792, R = 0.0283 and wR = 0.0707 for 3746 observed reflections with I > 2σ(I). The complex is composed of mononuclear cations [Ni(H₂Bibzim)₃]²⁺, chlorine anions, and lattice water molecules, which are linked into a two-dimensional supramolecular architectures via hydrogen bonds and π-π-stacking interactions.     

Erbium(III) and lutecium(III) complexes [Ln(H<Subscript>2</Subscript>O)<Subscript>8</Subscript>][Cr(NCS)<Subscript>6</Subscript>] · 5H<Subscript>2</Subscript>O: Synthesis and crystal structure

[Ln(H₂O)₈][Cr(NCS)₆] · 5H₂O aqua complexes, where Ln = Er (1), Lu (2), have been found in an aqueous solution instead of binary complex salts with an organic ligand in their cation, when crystal products of the reaction between Ln(NO₃)₃ · 6H₂O (Ln = Er, Lu), K₃[Cr(NCS)₆] · 4H₂O, and 8-oxyquinoline (C₉H₇NO) were studied by X-ray diffraction. Crystals of complexes 1 and 2 are isostructural and crystallize in triclinic system, space group P\(\bar 1\), Z = 2. For complex 1: a = 9.0677(4) Å, b = 9.3115(4) Å, c = 16.9595 Å, α = 81.526(2)°, β = 86.153(2)°, γ = 83.879(2)°, V = 1406.33(10) ų, ρ_calc = 1.894 g/cm³; for complex 2: a = 9.0438(3) Å, b = 9.2880(3) Å, c = 16.9181(3) Å, α = 81.7250(10)°, β = 86.1600(10)°, γ = 83.8850(10)°, V = 1396.38(7) ų, ρ_calc = 1.926 g/cm³.     

Crystal structure of [(C<Subscript>6</Subscript>H<Subscript>5</Subscript>)<Subscript>4</Subscript>P][Ni(B<Subscript>9</Subscript>C<Subscript>2</Subscript>H<Subscript>11</Subscript>)<Subscript>2</Subscript>]·CCl<Subscript>4</Subscript>

A new compound containing the tetraphenylphosphonium cation and the nickel(III) bisdicarbollyl anion, [(C₆H₅)₄P][Ni(B₉C₂H₁₁)₂]·CCl₄, was synthesized and investigated by XRD at room temperature (295 K). Crystal data: C₂₉H₄₂B₁₈PCl₄Ni, M = 816.69, monoclinic, space group P2/c; unit cell parameters a = 13.5873(6) Å, b = 7.1475(2) Å, c = 20.7829(8) Å, β = 94.4595(13)°, V = 2012.2(2) ų, Z = 2, d _calc = 1.348 g/cm³. The structure was solved by direct and Fourier methods and refined by the full-matrix least squares method in an anisotropic (isotropic for H) approximation to the final R ₁ = 0.0466 for 3055 I _hkl ≥ 2σ _I of 23,655 reflections collected and 5618 independent I _hkl (Bruker X8 APEX diffractometer, λMoK _α).     

Characterization and crystal structure of a new layered cadmium diphosphate: KCdHP<Subscript>2</Subscript>O<Subscript>7</Subscript>∙2H<Subscript>2</Subscript>O

A new potassium cadmium hydrogen diphosphate dihydrate, KCdHP₂O₇?2H₂O (1), has been synthesized by slow evaporation at room temperature and characterized by FT-IR, Raman, TG-DTA, and single crystal X-ray diffraction. Compound (1) crystallizes in the orthorhombic Pcmn space group with the unit cell parameters a = 6.5814(8) Å, b = 7.9428(9) Å, c = 15.961(6) Å, V = 834.4(3) Å3 and Z = 4. Its structure consists of polyhedral layers parallel to the ab plane where each CdO₆ octahedron (m position) shares four edges with three different diphosphate groups. In the Cd octahedron, two oxygen atoms residing in (m) special positions belong to coordinated water molecules. These layers are joint by K⁺ cations (4c Wyckoff position) and hydrogen bonds, leading thus to a two-dimensional framework. The structural model is supported by the bond-valence-sum validation tool as calculated valences are close to the formal oxidation numbers.     

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.     

Quantum chemical modeling of possible reactions of mononuclear iron nitrosyl complex [Fe(SC(NH<Subscript>2</Subscript>)<Subscript>2</Subscript>)<Subscript>2</Subscript>(NO)<Subscript>2</Subscript>]Cl•H<Subscript>2</Subscript>O in an aqueous solution

Possible reactions of the mononuclear iron nitrosyl complex [Fe(SC(NH₂)₂)₂(NO)₂]Сl?H₂O in an aqueous solution were studied using quantum chemical modeling. The electronic structures of the possible intermediates were examined by the NBO and AIM methods. The substitution of the thio ligand in the iron—sulfur nitrosyl complex by a water molecule and the formation of dimeric intermediate complexes were found to facilitate the NO-donation process.     

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.     

Solubility and stability of (NH<Subscript>4</Subscript>)<Subscript>2</Subscript>SO<Subscript>4</Subscript>·H<Subscript>2</Subscript>O<Subscript>2</Subscript> in organic and aqueous-organic media

Solubility and stability of (NH₄)₂SO₄·H₂O₂ in organic solvents (glycerol, ethylene glycol, TOSOL-A40 OM antifreeze), in mixtures of an organic solvent and water, and in pure water was studied. Crystallographic properties of the ammonium sulfate precipitating from aqueous-organic solvents and aqueous solutions in various time intervals and differing from ordinary (NH₄)₂SO₄ in solubility and one of crystallographic parameters were analyzed.     

Manganese(II) 9-Molybdomanganate(IV), [Mn(H<Subscript>2</Subscript>O)<Subscript>4</Subscript>]<Subscript>3</Subscript> · [MnMo<Subscript>9</Subscript>O<Subscript>32</Subscript>] · 2H<Subscript>2</Subscript>O: Synthesis,thermal analysis,IR spectra,and crystal structure

The [Mn(H₂O)₄]₃ · [MnMo₉O₃₂] · 2H₂O complex was synthesized and studied by X-ray diffraction, thermogravimetry, powder X-ray diffraction, and IR spectroscopy. The crystals are trigonal: space group R32, a = 14.811(2) Å, c = 14.232(2) Å, V = 2703.7(8) ų, M = 1848.5, Z = 3, ρ(calcd.) = 3.419 g/cm³.