Contribution a l'etude des systemes Ca3(PO4)2-MSO4 (M=Sr,Ba)

In the systems Ca₃(PO₄)₂-MSO₄ (M = Sr, Ba), the series of single phase Ca_21?3xM_2xI(PO₄)_14?2x(SO₄)_2x with 0<x<0.15 forM=Sr and 0<x<0.1 forM = Ba have been prepared. These solid solutions, respectively strontium phosphosulfate and barium phosphosulfate, are isostructural with anhydrous tricalcium orthophosphate. They have been characterized by their infrared spectra and their crystallographic unit cell parameters.     

Zur Struktur von H3Co(CN)6 und Ag3Co(CN)6

The X-ray powder patterns of H₃Co(CN)₆ and Ag₃Co(CN)₆ have been indexed on the basis of a hexagonal unit cell: The length of the N? X? N-bond along the c-axis is 3.29 Å for X ? H and 4.24 Å for X ? Ag. These distances are in agreement with data obtained from infrared spectra and with structural properties of similar compounds.     

Syntheses,crystal structures,and IR spectra of isonicotinamide-isonicotinamidium bis(isonicotinamide)-tetrakis(isothiocyanato)ferrate(III) and isonicotinamidium chloride

Reaction of iron(III) thiocyanate with isonicotinamide (inia) in ethanol leads to formation of a dark red, air stabile crystalline iron(III) compound of composition [iniaH·inia][Fe(inia)₂(NCS-N)₄]. Single-crystal X-ray diffraction analysis shows the triclinic P–1 space group with unit cell parameters: a?=?8.2440(4)?Å, b?=?9.5540(3)?Å, c?=?11.2590(5)?Å, α?=?93.945(4)°, β?=?95.554(4)°, γ?=?96.285(3)°, and Z?=?1. The iron compound contains [iniaH·inia]⁺ cations and [Fe(inia)₂(NCS-N)₄]^– anions, which are held together by ionic interactions and hydrogen bonding. The Fe(III) is octahedrally coordinated by six nitrogens, four from NCS^– in the equatorial plane and two from inia occupying axial positions. The [iniaH]Cl has been formed by reaction of inia with hydrochloric acid. [iniaH]Cl crystallized in the monoclinic C2/c space group with unit cell parameters: a?=?25.156(5)?Å, b?=?5.095(1)?Å, c?=?12.747(3)?Å, and Z?=?8. Both compounds have also been characterized by elemental analyses and infrared spectroscopy. Structural and infrared spectral data are compared with data of similar compounds in the literature.     

The single crystal Raman spectra of Cs2Zn(N3)4

Raman spectra of Cs₂Zn(N₃)₄ are reported for single crystals at 300 K and for powdered material at 80 K, respectively. Above 200 cm⁻¹ the spectral features are dominated by the vibrational aspects of the isolated azide ions (all of which occupy general positions in the unit cell). Site group splittings have a pronounced effect in both the 600 cm⁻¹ and 1200 cm⁻¹ regions whereas in the 2000 cm⁻¹ region factor group splittings play an additional role. Infrared spectra at room temperature of powdered Cs₂Zn(N₃)₄, together with Raman and infrared spectra of K₂Zn(N₃)₄ and Rb₂Zn(N₃)₄ are also discussed.     

Synthesis,Characterization, Crystal Structure,and hybrid DFT Computation of Antimony(III) Chloride Diazide,SbCl(N3)2

SbCl(N₃)₂ was synthesized by the reaction of two equivalents of sodium azide with SbCl₃ in CH₂Cl₂. The structure of the compound was determined by X‐ray structure determination. SbCl(N₃)₂ crystallizes in the monoclinic space group C2/c with a = 11.694(4), b = 7.751(4) and c = 12.241(5) Å, β = 100.45(1)°, with 8 formula units per unit cell. The SbCl(N₃)₂ molecules show interactions to form chains. The frequencies obtained by Raman and infrared spectroscopy were assigned to the normal modes of the SbCl(N₃)₂ molecules in comparison with computational results.     

Vibrational spectra and IR dichroism of poly(tetramethyl-p-silphenylene-siloxane) and its chain structure

Raman spectra of poly(tetramethyl-p-silphenylene-siloxane) were investigated in solution with depolarization ratios and in the solid state. Polarized infrared (IR) spectra were studied on oriented polymer samples. Assignments of the vibrational bands are given and IR dichroic and Raman data are in agreement with tetragonal P4₁ space group symmetry. These data provide information on the arrangement of the Si? C₆H₄? Si groups in the unit cell. On the basis of vibrational spectra the dynamic interaction between adjacent benzene rings is negligibly small and the rings preserve their local D_2h Pseudosymmetry.     

Die Kristallstruktur von Magnesiumhexaaqua-bis(hexamethylen-tetramin-1-ium)-hexacyanoferrat(II)

The Crystal Structure of Magnesiumhexaaqua-bis(hexamethylenetetramine-1-ium)-hexacyanoferrate(II) Single crystals of [Mg(H₂O)₆](C₆H₁₃N₄)₂[Fe(CN)₆] were obtained from diffusion of a methanolic solution of hexamethylenetetramine into an aqueous solution of a mixture of MgCl₂ and H₄[Fe(CN)₆] were obtained from diffusion of a methanolic solution of hexamethylenetetramine into an aqueous solution of a mixture of MgCl₂ and H₄[Fe(CN)₆]. Characterization of the product was performed by CHN-analysis, electron microscopy, infrared spectra, and X-ray methods. The compound is orthorhombic, a = 1386.3(4), b = 1386.3(4), c = 1385.6(4) pm, space group Pbca, the structure wa refined to an unweighted R = 6.7% (1255 intensities). According to the infrared spectra and the X-ray refinement intensive hydrogen bonds are present.     

Thermal decomposition of Np(IV) and Pu(III, IV) oxalates

Thermal decomposition of Pu(C₂O₄)₂·6H₂O, Pu₂(C₂O₄)₃·10H₂O and Np(C₂O₄)₂ ·6H₂O has been studied by using combination of gas chromatography, infrared spectroscopy, spectrophotometry and complex thermal analysis. We also investigated the decomposition of Pu oxalate under its -radiation. The reduction of Pu(IV) to Pu(III) has been confirmed. We found Np(V), which is formed from Np(IV), on the basis of infrared and absorption spectra of the intermediate compounds.     

[Ge2S5(S2)]4−, A NLO-Active Unit Leading to an Asymmetric Structure Discovered in Li2Cs4Ge2S5(S2)Cl2: An Experimental and Theoretical study

Metal-centered MS₄ tetrahedra are fundamentally important building blocks for the structural construction of infrared (IR) nonlinear optical (NLO) mateirals, because they have a large effect on properties like second-harmonic generation, birefringence, band gap, etc. Therefore, rational design and selection of these tetrahedra could effectively help synthesize new materials and give satisfactory properties. In this work, we reported a new NLO-active [Ge₂S₅(S₂)]⁴⁻ unit composed of two corner-shared GeS₄ tetrahedra with a nonpolar covalent S−S bond, discovered in a new compound of Li₂Cs₄Ge₂S₅(S₂)Cl₂. To the best of our knowledge, this [Ge₂S₅(S₂)]⁴⁻ unit has never been discovered. [Ge₂S₅(S₂)]⁴⁻ units have intrinsic asymmetric features and lead to the whole structure being noncentrosymmetric (NCS). Further, real-space atom-cutting methods reveal that they make almost all the contribution to the second-harmonic generation response (SHG) for Li₂Cs₄Ge₂S₅(S₂)Cl₂. All of the above indicate that the [Ge₂S₅(S₂)]⁴⁻ unit is a new functional unit and a good choice for designing new IR NLO materials.     

Synthesis,infrared and 121Sb Mössbauer spectra of some Antimony(III) Thiocyanate Complexes

The first isolation of an antimony(III) thiocyanate complex salt, [(CH₃)₄N][Sb(CNS)₄] ( I ), and of two adducts of the Sb(CNS)₃ formal unit with potentially tridentate nitrogen donors, Sb(CNS)₃tpta ( II ) and [Sb(CNS)₃]₃(dqp)₂ ( III ), is described. In these derivatives, infrared and Mössbauer spectral data are essentially indicating the predominant presence of N-bonded thiocyanate. For complex I , the occurrence also of groups bridging through the nitrogen atom is advanced.     

Darstellung,spektroskopische Charakterisierung und Kristallstrukturen von Quecksilber(II)‐bis(tetracyanoborat) Hg[B(CN)4]2 und Diquecksilber(I)‐bis(tetracyanoborat) Hg2[B(CN)4]2

Preparation, Spectroscopic Characterization and Crystal Structures of Mercury(II)‐bis(tetracyanoborate) Hg[B(CN)₄]₂ and Dimercury(I)‐bis(tetracyanoborate) Hg₂[B(CN)₄]₂ Hg[B(CN)₄]₂ ( 1 ) is synthesised by the reaction between Hg(NO₃)₂ and K[B(CN)₄]₂. In a comproportionation reaction of 1 with elemental mercury the corresponding mercury(I) salt Hg₂[B(CN)₄]₂ ( 2 ) is obtained. The compounds were characterised by vibrational‐ and NMR‐spectroscopy, and their crystal structures were determined. Hg[B(CN)₄]₂ crystallizes in the trigonal system in the space group P3¯m1 with a = 781.75(3) pm, c = 601.68(2) pm, V = 318.44(2)ų, and one formula unit per unit cell. For Hg₂[B(CN)₄]₂ an orthorhombic unit cell with a = 568.9(1) pm, b = 3280.9(7) pm, c = 601.68(2) pm, V = 1389.6(5)Å, and Z = 4 is observed.     

Etherate,pyridine, and aniline compounds of the complex tri- and tetra-iodoacids of Zn(II) and Cd(II)

The preparation, for the first time, and the properties of the title compounds are described. Analytical conductometric, spectral (infrared and ultraviolet) and data from X-ray powder spectra yield information about the probable structure of the complexes in the solid state. The existence of metal-nitrogen bond for all pyridine and aniline complexes, except H₂CdI₄·4An (An=aniline), is adduced from infrared and far infrared spectral studies.

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Etherate, Pyridin- und Anilin-Verbindungen der komplexen Tri- und Tetra-Jodsäuren vonZn(II) undCd(II)

Zusammenfassung Die Darstellung und die Eigenschaften der Titelverbindungen werden erstmalig beschrieben. Analytische und konduktometrische Daten, sowie IR, UV und Röntgenpulveraufnahmen ergaben Informationen, aus denen die wahrscheinliche Struktur der Komplexe im festen Zustand abgeleitet wurde. Die Existenz von Metall—Stickstoff-Bindungen für alle Pyridin- und Anilin-Komplexe, mit Ausnahme von H₂CdI₄·4An (An=Anilin), ergibt sich aus den Daten von IR und fernem IR.

     

Multiple morphological micelles formed from the self-assembly of poly(styrene)-b-poly(4-vinylpyridine) containing cobalt dodecyl benzene sulfonate

A series of supramolecular block copolymers were prepared using poly(styrene)-b-poly(4-vinylpyridine)(PS-b-P4VP) which coordinated with cobalt dodecyl benzene sulfonate (Co(DBS)₂) in tetrahydrofuran (THF). Fourier transformation infrared spectroscopy (FTIR), UV-vis absorption spectroscopy (UV) and differential scanning calorimetry (DSC) showed that Co(DBS)₂ coordinated to the lone electron pairs of the pyridine nitrogens in the P4VP block and leaded to complexes. The supramolecular block copolymers could self-assemble into nanosized micelles with different shapes and dimensions in THF, depending on the number of Co(DBS)₂ groups per 4-vinylpyridine (repeat unit was denoted by n) and the ratio between PS block length and P4VP block length. Transmission electron microscopy (TEM) results showed that when the number of repeat units of P4VP was more than that of PS, micelles with different interesting shapes such as spheres, rods, vesicles, large compound vesicles (LCVs) and the large compound micelles (LCMs) were observed if increasing the content of the Co(DBS)₂ in PS-b-P4VP copolymer/THF solution; When the number of repeat units of P4VP was less than that of PS, the micelle morphologies changed from spheres to rods, bi-layer, and LCMs if the Co(DBS)₂ content was increased progressively.     

Binary and Ternary Complexes of Copper(II) Involving N,N,N′,N′-Tetramethylethylenediamine (Me4en) and Various Biologically Relevant Ligands

Binary and ternary complexes of copper(II) involving N,N,N′,N′-tetramethylethylene-diamine (Me₄en) and various biologically relevant ligands containing different functional groups are investigated. The ligands (L) used are dicarboxylic acids, amino acids, peptides and DNA unit constituents. The ternary complexes of amino acids, dicarboxylic acids or peptides are formed by simultaneous reactions. The results showed the formation of Cu(Me₄en)(L) complexes with amino acids and dicarboxylic acids. The effect of chelate ring size of the dicarboxylic acid complexes on their stability constants was examined. Peptides form both Cu(Me₄en)(L) complexes and the corresponding deprotonated amide species Cu(Me₄en)(LH₋₁). The ternary complexes of copper(II) with (Me₄en) and DNA are formed in a stepwise process, whereby binding of copper(II) to (Me₄en) is followed by ligation of the DNA components. DNA constituents form both 1:1 and 1:2 complexes with Cu(Me₄en)²⁺. The concentration distribution of the complexes in solution was evaluated. [Cu(Me₄en)(CBDCA)] and [Cu(Me₄en)(malonate)] are isolated and characterized by elemental analysis and infrared measurements.     

An infrared and raman spectroscopic study of metal(II) Di(2-methylpyridine) tetracyanonickelate complexes: Ni(C6H7N)2Ni(CN)4 and Cd(C6H7N)2Ni(CN)4

The results of an infrared and Raman spectroscopic study are reported for two new metal 2-methylpyridine tetracyanonickelate complexes, M(C₆H₇N)₂Ni(CN)₄, M=Ni or Cd. Their structure consists of corrugated polymeric layers of {M-Ni(CN)₄} with 2-methylpyridine molecules bound directly to the metal (M). These complexes can act as host lattices in the formation of inclusion compounds with dioxane guest molecules.     

Die Synthese und einige Eigenschaften von Hydraziniumfluoroscandaten(III)

The synthesis of N₂H₅ScF₄·0.5 HF·0.5 H₂O, N₂H₅ScF₄, and N₂H₆ScF₅ is described. The thermal properties and infrared spectra of the compounds obtained are discussed. The assignation of the bands in infrared spectra (4000 to 250 cm^?1) of the first two compounds is consistent with the presence of hydrazinium⁺¹ ion and for the third one with the presence of hydrazinium⁺² ion.     

Synthesis and Thermal Decomposition of Cobalt(II) bis (Tartrato) Cobaltate(II) Trihydrate

The paper describes the synthesis and characterization of cobalt(II) bis (tartrato) cobaltate(II) trihydrate Co[Co[C₄O₆H₄)₂]·3H₂O. The complex was characterized on the basis of elemental analysis, infrared, electronic, e.s.r. spectra and X-ray powder diffraction studies. The thermal decomposition of the complex led to a mixture of Co₂O₃and Co₃O₄in air at about 400°C, whereas in nitrogen it was decomposed to a mixture of CoO and C at about 384°C. A tentative reaction mechanism is suggested for the thermal decomposition of the complex in air and nitrogen. This revised version was published online in July 2006 with corrections to the Cover Date.     

Kristalline Chrome(III)-phosphat-Hexahydrate

Cristalline Chromium(III) Phosphate Hexahydrate On precipitation of chromium (III) phosphate from a cold water solution, two further crystalline modifications of the previously described CrPO₄ · 6 H₂O with the same composition are obtainable. The three phases can be characterized by means of their X-ray diffraction patterns. The least stable of the three forms (γ-CrPO₄ · 6H₂O) is isomorphous with the corresponding hydrate of the chromium(III) arsenate and forms cubic crystals with a₀ = 9.42 Å and 4 molecules in the unit cell. A structural explanation can be given for the most stable of the phases (α-CrPO₄ · 6 H₂O) which forms monoclinic crystals for the space group C_c with eight molecules in the unit cell and the dimensions a₀ = 9.87, b₀ 6.89, c₀ = 23.49 Å and β = 99.4·     

Photochemical studies of M(CO)6 (M = Cr,Mo, W) at low temperature in solution. Infrared spectra of M(CO)5 (solvent) (solvent = methylcyclohexane,methylene chloride) and W(CO)5L (L = aromatic hydrocarbon)

The infrared spectra of M(CO)₅(MCH) (MCH = methylcyclohexane; M = Cr, Mo, W), formed by 366 nm irradiation of M(CO)₆ at ?78°C in rigorously purified methylcyclohexane, are reported. The previously reported spectrum of “W(CO)₅” at low temperature in methylcyclohexane/isopentane solution is attributed to W(CO)₅(impurity), where the impurity is probably an aromatic or olefinic hydrocarbon. Spectra in methylene chloride solution are also discussed. The photochemical reactions of W(CO)₆ with aromatic hydrocarbon ligands in methylcyclohexane solution were also studied at ?78°C in a low temperature infrared cell. Irradiation (366 nm) of W(CO)₆ at ?78°C in rigorously purified methylcyclohexane solution containing approximately 5% (v/v) toluene, benzene, mesitylene, biphenyl, or p-xylene initially produces the complex W(CO)_5? (MCH). In the presence of the aromatic hydrocarbon, this complex is unstable and it decomposes in a dark reaction to give a complex which has an infrared spectrum typical for a C_4v M(CO)₅X molecule. It is proposed that the product of the dark reaction is W(CO)₅(aromatic), formed by reaction of W(CO)₅(MCH) with the aromatic ligand in solution. The infrared spectra of the W(CO)_5? (aromatic) complexes are different from the spectra previously reported for these complexes. It is shown that the spectra previously reported for W(CO)_5? (aromatic) are actually attributable to W(CO)₅(hexane) (hexane was the solvent used in the previous study); these spectra were probably obtained before W(CO)₅(hexane) had time to react with the aromatic hydrocarbon.     

Über metall-alkyl-verbindungen: XIV. Die kristallstrukturen von K[In(CH3)4], Rb[In(CH3)4] und Cs[In(CH3)4]

The crystal structure of KInMe₄ and CsInMe₄ have been determined from single crystal diffractometer data. Lattice parameters of RbInMe₄ obtained by powder methods are given. KInMe₄ and RbInMe₄ are isostructural (space group I4₁/amd), containing four formula units in the unit cell. CsInMe₄ belongs to space group P4? 2m with one formula unit per unit cell. Lattice parameters in Å: KInMe₄:a=9.904(2), c=8.132(2); RbInMe₄:a=10.208(2), c=8.146(2); CsInMe₄:a=7.459(1), c=4.163(1). All compounds consist of isolated alkali cations and tetrahedral InMe₄-anions. InC distances are 2.239(3) in KInMe₄ and 2.26(2) in CsInMe₄. The appearance of three different structure types of alkali metal tetramethyl indates is explained by the increasing alkali ion radii.