Synthesis and crystal structures of two new complexes [M(OH2)(HDPA)2]·3H2O (M = Mn, Co)

Two new transition metal complexes of [M(OH₂)(HDPA)₂]·3H₂O (M=Mn(1); M=Co(2)) (H₂DPA, 2,6-pyridine-dicarboxylic acid) have been prepared at room temperature from the reaction of MCl₂·6H₂O (M=Mn or Co) and H₂DPA in the mixed solvent of H₂O and EtOH in the presence of piperazine, and were characterized by X-ray analysis, elemental analysis. X-ray analysis reveals that the coordination geometries of Mn²⁺ and Co²⁺ are of octahedron and severely distorted square-based pyramid, respectively. Crystal data: [Mn(OH₂)(HDPA)₂]·3H₂O (1), Mr=459.23, monoclinic, P2(1)/n, a=7.0056(3), b=(23.8125(12), c=10.7444(3) ?, β=99.834(2)°, Z=4, V=1766.28(13) ?³, R ₁=0.0586, wR ₂=0.1448 [I>2σ(I)]; Co(OH₂)(HDPA)₂]·3H₂O (2), Mr=463.22, monoclinic, P2(1)/n, a=7.0014(2), b=23.8346(7), c=10.7212(4) ?, β=99.8540(10)°, Z=4, V=1762.71(10) ?³, R ₁=0.0474, wR ₂=0.1366 [I>2σ(I)].     

Crystal structures of two local anesthetics: Dibucaine·HCl·H2O and Dimethisoquin·HCl·H2O

The crystal structures of the tertiary amine local anesthetics dibucaine hydrochloride monohydrate (C₂₀H₂₉N₃O₂·HCl·H₂O) and dimethisoquin hydrochloride monohydrate (C₁₇H₂₄N₂O·HCl·H₂O) have been determined. Dibucaine forms crystals inP2₁/c witha=10.669(3),b = 35.981(5),c= 11.417(2) Å,= 89.654(3) ° andZ= 8. Dimethisoquin crystallizes in the space groupP¯1 witha = 5.338(6),b=7.579(8),c= 22.336(24) Å,a = 85.513(1), = 87.447(1), =84.863(1) °, andZ=2. Intensity data were collected with an automatic diffractometer, using CuK for dibucaine and MoK for dimethisoquin. The structures were solved using direct methods and refined by full-matrix least-squares procedures to final values ofR= 12.8% for dibucaine andR = 8.8% for dimethisoquin. The structures of both local anesthetics feature planar fused ring systems and extended side chains, one of which contains the tertiary amine that forms hydrogen bonds with other local anesthetic molecules and the chlorine and solvent atoms. The possible sites of action of the anesthetics in the cell membrane are discussed on the basis of these structures.     

Preparation and studies of new crystals in the K3H(SO4)2-(NH4)3H(SO4)2-H2O system

To elucidate the effect of isomorphic substitution on the kinetics of phase transitions, single crystals of (K _x (NH₄)_1?x ) _m H _n (SO₄)_{(m + n)/2} · yH₂O solid solutions are grown from the K₃H(SO₄)₂-(NH₄)₃H(SO₄)₂-H₂O system, whose end members are known to undergo superprotonic phase transitions of fundamentally different kinetics. The chemical composition of the single crystals grown is determined by energy dispersive X-ray microanalysis. The thermal and optical behavior of (K,NH₄)₉H₇(SO₄)₈ · H₂O single crystals is studied in the temperature range 295–420 K and the crystal structure at 295 K is determined. A comparison of the results of the studies with data for crystal K₉H₇(SO₄)₈ · H₂O published earlier shows that the substitution of ammonium for potassium atoms lowers the temperature of the structural phase transition by 8 K.     

Elastic properties of the dithionates Na2S2O6 · 2 H2O,K2S2O6, Rb2S2O6, CaS2O6 · 4H2O and SrS2O6 · 4 H2O

Single crystals of the title compounds having optical quality and dimensions of several cm were grown from aqueous solutions. The elastic and thermoelastic constants were determined from ultrasonic resonance frequencies of thick plates. The true point symmetry of K₂S₂O₆ and Rb₂S₂O₆, which is screened by a hexagonal hypermorphy, could be clearly revealed to be trigonal (32) by the existence of the elastic constant c₁₄. In the case of CaS₂O₆ · 4H₂O and SrS₂O₆ · 4H₂O the constant c₁₄ of the specimens appeared too small to confirm the trigonal symmetry group required from electrooptic and non-linear optic effects unambiguously. The isotypy of K₂S₂O₂ and Rb₂S₂O₆ as well as that of CaS₂O₆ · 4H₂O and SrS₂O₆ · 4H₂O is confirmed by their elastic behaviour. The mean elastic stiffness of dithionates is closely related to that of the corresponding sulphates. In the vicinity of the second-order phase transition of K₂S₂O₆ near 235 K weak anomalies of the temperature derivatives of the longitudinal elastic stiffnesses are observed.     

Vacuum-ultraviolet absorption of interstitial O2 and H2O molecules in SiO2 glass

Vacuum-ultraviolet (VUV) absorption of O₂ and H₂O molecules incorporated in interstitial voids in SiO₂ glass by thermal annealings was examined. Interactions of the interstitial molecules with the surrounding SiO₂ glass network lead to a redshift of the VUV absorption band of interstitial O₂, while a blueshift of that of interstitial H₂O, both accompanied by an increase in the intensity of the absorption bands. The Coulomb repulsion, London dispersion, and hydrogen bonding are the main interactions responsible for the modification of the VUV absorption bands.     

Synthesis,transformation to octahedron‐like crystals,and gas‐sensing property of six‐horned nanospheres of Cu2O

Single‐crystal six‐horned nanospheres of Cu₂O with a diameter of 760 nm in average were prepared in aqueous solution of CuCl₂and NaOH by using ascorbic acid as the reductant in the presence of sodium dodecyl benzenesulfonate (SDBS) at room temperature. The horn grows along the <100> direction, which is consistent with the protuberant direction of an apex of octahedron. The formation process of six‐horned nanospheres included two steps: the formation of Cu₂O nanospheres via Ostwald ripening process, and the appearance of horns on the surface of nanospheres under low concentration of SDBS. As increasing the concentration of SDBS, the six‐horned nanospheres could be transformed into octahedron‐like Cu₂O. And at the same concentration of SDBS, keeping the volume ratio of water and ethanol in mixed solutions as 1:1, Cu₂O octahedra were obtained. Moreover, gas‐sensing property showed that six‐horned nanospheres of Cu₂O had higher sensitivity compared with Cu₂O nanospheres and Cu₂O octahedra to ethanol gas (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Glass-ceramics in the system BaO/TiO2(ZrO2)/Al2O3/B2O3 and their thermal expansion

Glasses in the system BaO/TiO₂(ZrO₂)/Al₂O₃/B₂O₃ were melted from the raw materials with and without the addition of platinum. They were crystallized in two steps at 720 and 780 °C. TiO₂ does not act as nucleating agent in this system, but widely prevents crystallization. Samples additionally doped with platinum show the crystallization of BaAl₂B₂O₇. However, samples containing equimolar quantities of TiO₂ and ZrO₂ showed the crystallization of this phase without the addition of platinum. The thermal expansion coefficients of samples with TiO₂-concentration ⩽7 mol% or TiO₂/ZrO₂-concentrations ⩽5 mol% exhibit zero or even slightly negative thermal expansion coefficients.     

Crystallization kinetics of MgSO4 · 7 H2O in presence of tenside

The effect of sodium dodecyl sulfate (SDS) on crystallization kinetics and crystal habit of MgSO₄ · 7 H₂O from aqueous solutions at 25 °C was investigated in batch experiments. It highly depends on the supersaturation level. Both increasing supersaturation and rising concentration of the tenside promote the production of needle-like crystals but the influence of the driving force is much more pronounced. SDS increases the crystallization rate and the linear crystal growth rate in length direction of the crystals. To a high degree it also influences properties of the crystallizing solution such as surface tension and viscosity.     

Synthesis and crystal growth of sillenite phases in the Bi2O3 ‐ TiO2 ‐ Nb2O5 system

The synthesis of Bi₂O₃‐Nb₂O₅ sillenite phase (BNbO) and the solubility of this phase with Bi₁₂TiO₂₀ was investigated by solid‐state reaction synthesis and niobium doped Bi₁₂TiO₂₀ (BTO:Nb) crystals were grown by the Top Seeded Solution Growth (TSSG) technique. The structures of polycrystalline compounds were checked by X‐ray powder diffraction method at room temperature. The correct composition of the sillenite phase stabilized with niobium was determined as Bi₁₂[Nb_0.17Bi_0.83]O_19.7 (BNbO) with unit cell parameter a = 10.261(2) Å. The system BTO‐BNbO is poorly soluble, but niobium doped BTO crystals were grown from the liquid composition 10Bi₂O₃ : xTiO₂ : (1‐x)/2 Nb₂O₅, with x = 0.95 and 0.90. A niobium concentration limit in the liquid phase is established in order to grow BTO:Nb with good crystalline quality. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

(C2N2H10)2Mg(HP2O7)2·2H2O synthesis and crystal structure

(C₂N₂H₁₀)₂Mg(HP₂O₇)₂·2H₂O, is a new inorganic organic hybrid structure. It has been synthetized using wet chemistry. Its crystal structure consists of cis- and trans-edge sharing [MgO₄(H₂O)₂] octahedra resulting in chains, which are linked via [HP₂O₇] units to form [Mg(HP₂O₇)₂(H₂O)₂]⁴⁻ layers. The Mg²⁺ cations and the ethylendiammonium cations are located on centers of inversion. The ethylendiammonium cations are alternately located in the interlayer space. The cohesion of the crystal is well ensured by coulombic interactions between anions and cations and by several hydrogen bonds. The diphosphate anion shows an eclipsed conformation.     

Selective etching of ZnTe in HF:H2O2:H2O solution: Interpretation of extended defect‐related etch figures

HF:H₂O₂:H₂O solution (40%wt.HF: 30wt.%H₂O₂: H₂O, 3:2:1 by volume) was used to reveal extended defects (line, face and volume defects) in bulk ZnTe crystals grown from Te solution. The etch patterns were analyzed based on their size, shape and distribution. The etch figures, both in the shape of pits and hillocks with high resolution, show forms controlled by the symmetries of the respective faces were produced. Two different sizes of pits were observed, the larger‐size pits correspond to dislocations penetrating the surface, however, the smaller‐size texture pits are produced on the defect‐free region, which serve as standard pits on respect faces. The face defects, such as grain boundaries, sub‐grain boundaries, dislocation walls, twins and stacking faults, can be all displayed clearly. Another essential feature of the etchant is that, it can effectively dissolve Te‐rich phase (Te inclusion/precipitates), which makes it promising to reveal the shape of this volume defect.     

Reactivity of SiCl and SiF groups in SiO2 glass with mobile interstitial O2 and H2O molecules

Reactions of common network-bound halogens in synthetic SiO₂ glass, SiCl and SiF groups, with interstitial O₂ and H₂O molecules incorporated by thermally annealing were studied. It was found that the chemical properties are distinctly different between SiCl and SiF groups. SiCl groups react with interstitial O₂ and H₂O to form interstitial Cl₂ and HCl, respectively. In contrast, formation of interstitial F₂ and HF due to the reaction of SiF groups with interstitial O₂ and H₂O is not observed. The reactivity of SiCl and SiF groups is in accord with the properties and thermodynamic data of their respective analogous compounds, SiCl₄ and SiF₄.     

Effect of composition on ionic transport in SiO2–B2O3–Na2O glasses

Ionic diffusion was investigated in the SiO₂–B₂O₃–Na₂O glass system over a wide composition range by impedance spectroscopy measurements. The Na⁺ cation transport mechanism was described by an interstitial pair migration model based on Frenkel defects in ionic crystals. The activation energy of the static electrical conductivity is shown to be correlated with the boron coordination number in these glasses. Published ¹¹B NMR results were used to calculate the activation energies of sodium cations acting as charge compensators for the [BO_4/2]⁻ tetrahedron and of sodium cations bonded to non-bridging oxygen atoms. These values are in agreement with the activation energies of the Na₂O–B₂O₃ and Na₂O–SiO₂ binary systems, respectively.     

Synthesis and physicochemical characterization of a porous coordination polymer of Sn-Cu xylarate: The structure of [Sn4Cu8.5(HL)2(L)4O2(OH)(H2O)12.5] · 17.2H2O

A porous coordination polymer of Sn-Cu xylarate [Sn₄Cu_8.5(HL)₂(L)₄O₂(OH)(H₂O)_12.5] · 17.2H₂O (H₅ L is xylaric acid) is synthesized for the first time and characterized by chemical analysis, IR spectroscopy, and X-ray diffraction. Centrosymmetric heterometallic fragments [Sn₄Cu₆(HL)₂(L)₄O₂(H₂O)₆] (A) including copper Cu1–3 and tin Sn1,2 atoms are distinguished in the structure. The Cu4(OH)_0.5(H₂O)_2.5 bridges connect A units into chains running along the c axis, and the Cu5(OH)(H₂O) bridges connect A fragments into layers perpendicular to the c axis. The Cu4,5 atoms form a framework whose voids accommodate the crystallization water molecules.     

A Novel Coordination Structure of Dichromates Bonding to Copper (II): [Cu(bipy)2(Cr2O7)] · 2 H2O

Dark-green multimetal compound crystal [Cu(bipy)₂(Cr₂O₇)]· 2 H₂O was obtained from aqueous solution of Cu(NO₃)₂, K₂Cr₂O₇ and bipyridine. The crystal structure was determined by X-ray crystallography: triclinic P1 , a = 7.716(3) Å, b = 9.656(3) Å, c = 15.517(5)Å, α = 77.41(3)°, β = 81.04(3)°, γ = 82.33(3)°, Z = 2. In this compound, two chromium atoms and a copper atom are linked by two oxo bridges (Cu(II) O Cr(VI) O Cr(VI)). The copper coordination polyhedron corresponds to a five-coordinated distorted trigonal bipyramid.     

Structure of a Manganese (II) Complex Containing Saccharin and 1,10-Phenanthroline: [Mn(Sacch)2(o-Phen)2(H2O)2] · H2O

The X-ray crystal structure of the mononuclear manganese(II) complex containing saccharin and 1,10-phenanthroline, [Mn(Sacch)₂(o-Phen)₂(H₂O)₂] · H₂O, is reported. The manganese atom has a geometrical structure of hexa-coordinated distorted octahedron, saccharins interact with the central atom through water molecules.     

XAFS study of six-coordinated silicon in R2O–SiO2–P2O5 (R = Li,Na, K) glasses

The local structures around silicon and phosphorous atoms in R₂O–SiO₂–P₂O₅ (R = Li, Na and K) glasses have been investigated using Si and P K-edge XAFS spectroscopy by transmission mode at BL-4 and BL-3 at the synchrotron facility in Ritsumeikan University. As a result of XANES and EXAFS analyzes, six-coordinated silicon atoms were observed in the glasses. The fraction of six-coordinated silicon atom changed with increasing of the concentration of alkali oxide and P₂O₅. For the change of concentration of alkali oxide, it takes maximum values which are 60% in Li₂O, 90% in Na₂O and 85% in K₂O system at 20 mol% alkali oxide. It gradually increased up for the increase of the concentration of P₂O₅ to 55% in Li₂O, 80% in Na₂O and 90% in K₂O system. The Si–O inter-atomic distance in the glasses changes from 1.63 to 1.79 Å with increasing the fraction of six-coordinated silicon atom. On the other hand, it was not observed the local structural change around the phosphorous atom.     

Simulation of ion transport in layered cuprate La2SrCu2O6

Oxygen diffusion in layered cuprate La₂SrCu₂O₆ has been simulated by the molecular dynamics method in the temperature range of 300–2500 K. The lattice is found to transform at temperatures above 1550 K; this transformation is accompanied by a change in the pair correlation functions. The abrupt change in the oxygen diffusion coefficient in the range of 1500–1550 K may indicate the presence of a phase transition to the superionic state. The motion of oxygen anions could be traced at the microscopic level. It has been proven for the first time that the La₂SrCu₂O₆ crystal lattice allows, along with displacements of O1 ions within the CuO₂ layer, their migration from the crystallographic positions to the intermediate unoccupied O3 positions. The motion of O2 anions is also fairly complicated: they move not only in their layer over the O2 positions but they also jump to the neighboring layer to occupy the O1 positions. The oxygen diffusion coefficient in layered cuprate La₂SrCu₂O₆ exceeds that in cuprates with perovskite structure and structure of the K₂NiF₄ type (at the same temperatures), which indicates that this material has good prospects for electrodes with mixed ionic-electronic conductivity.     

Properties and structure of (1 − x)Li2O–xNa2O–Al2O3–4SiO2 glass systems

(1 − x)Li₂O–xNa₂O–Al₂O₃–4SiO₂ glasses were studied for the progressive percentage substitution of Na₂O for Li₂O at the constant mole of Al₂O₃ and SiO₂. The crystallization temperature at the exothermic peak increased from 898 to 939 °C when the Na₂O content increases from 0 to 0.6 mol. The coefficient of thermal expansion and density of these as-quenched glasses increase from 6.54 × 10⁻⁶ °C⁻¹ to 10.1 × 10⁻⁶ °C⁻¹ and 2.378 g cm⁻³ to 2.533 g cm⁻³ when the Na₂O content increases from 0 to 0.4 mol, respectively. The electrical resistivity has a maximum value at Na₂O · (Li₂O + Na₂O)⁻¹ = 0.4. The activation energy of crystallization decreases from 444 to 284 kJ mol⁻¹ when the Na₂O content increased from 0 to 0.4 mol. Moreover, the activation energy increases from 284 kJ mol⁻¹ to 446 kJ mol⁻¹ when the Na₂O content increased from 0.4 to 0.6 mol. The FT-IR spectra show that the symmetric stretching mode of the SiO₄ tetrahedra (1035–1054 cm⁻¹) and AlO₄ octahedra (713–763 cm⁻¹) exhibiting that the network structure is built by SiO₄ tetrahedra and AlO₄.     

Crystal Structure of RbD2PO4.D2O: A new Hydrate Phase of KDP‐type Compounds

The mono‐hydrate phase as well as the water‐free RbD₂PO₄ (DRDP) is obtained by crystal growth from fully deuterated aqueous solution. Its crystal structure was determined by combined neutron and X‐ray single crystal diffraction. It consists of double layers of PO₄ tetrahedra with D₂O planes in between. The PO₄ groups are linked by fully ordered deuterium bonds O‐D‐O. RbD₂PO₄.D₂O dehydrates below 329(5)K and undergoes a phase transition to RbD₂PO₄ (DRDP).