Tl3Al7S12 — ein neues Al-reiches Thioaluminat: Darstellung,Kristallstruktur und Eigenschaften

Tl₃Al₇S₁₂ — a Novel Al-rich Thioaluminate: Preparation, Crystal Structure, and Properties The new ternary phase Tl₃Al₇S₁₂ was prepared from the binary compounds Tl₂S and Al₂S₃ at 700 °C under vacuum. The structure of a yellow plateshaped single crystal was determined at room temperature. The compound crystallizes in the monoclinic polar space group P2₁ (No. 4) with a = 9.040(2), b = 12.381(2), c = 9.569(2) Å and β = 95.91(2)°. The polymeric anionic part of the structure can be described as a puckered layer-like arrangement of cornersharing [AlS₄]-tetrahedra parallel to (001). The aluminium-sulfur layers are connected via single sulfur atoms. The voluminous monovalent thallium atoms bridge the layers of the anionic framework. The mean Al? S bond lengths are 2.227 Å for μ₂-S? Al and 2.298 Å for μ₂-S? Al. In the strongly asymmetric coordination sphere of thallium the Tl? S bond lengths vary from 3.009(9) to 3.907(9) Å and contain four short and two or three longer distances. A rather short Tl…?Tl distance of 3.619(3) Å is observed between two of the three crystallographically independent Tl atoms, so that a weak bonding interaction has to be discussed. Vibrational spectroscopic data for the new phase are reported and discussed.     

Bis(phthalocyaninato(2–)rhenium(II)): Synthesis,Properties, and Crystal Structure

Blue, paramagnetic bis(phthalocyaninato(2–)rhenium(II)) (μ_eff = 0,88 μ_B, per Re, at 300 K) is prepared by thermal decomposition of trans-bis(triphenylphosphine)phthalocyaninato(2–)rhenium(II), in boiling triphenylphosphine. It crystallizes in the triclinic space group P 1 with cell parameters as follows: a = 7.799(3) Å, b = 12.563(7) Å, c = 12.69(1) Å, α = 89.97(5)°, β = 94.14(5)°, γ = 106.39(4)°; Z = 1. Two cofacial phthalocyaninates are bonded together by a Re–Re bond with a Re–Re distance of 2.285(2) Å. The Re atoms are located distinctly outside the centre of the (N_iso)₄ planes by 0.426(3) Å. The Re–N_iso distance varies from 1.99(1) to 2.04(1) Å (average 2.02 Å). The pc^2– ligands are in an eclipsed conformation and concavely distorted. In the UV-VIS-NIR spectrum the B region is split into two bands of comparable intensity due to strong excitonic coupling. The Re–Re stretching vibration at 240 cm^–1 is selectively enhanced in the resonance Raman spectrum (λ_exc = 488 nm).     

Synthesis and Crystal Structure of Er_2Si_2O_7

1INTRODUCTIONThecompoundwithcompositionIRE,O,:ZSiO,(RE~rareEarth)exhibitsex-tensivepolymorphismthatarecharacterizedbyboundariesateuropiumandholmiumalongtheseriesoftrivalentrareearths.Asfarasthestructureisconcerned,typeCisofspecialstabilitybecauseitsrangecanbeextendedbeyondthesmallestrareearthLug toScs tl'z}.Notlongago,wereportedstructureofNd,Si,O,withstructureformAt33.SynthesisandstructureofErZSiZO7withstructureformCarehereinre-ported.2EXPERIMENTAL'ThestartingmaterialsEr,O,…     

Structure and vibrational spectra of dicyclopentadienylzinc. A DFT study

The quantum-chemical DFT calculations of the Cp₂Zn structure confirm the conclusion made earlier from the vibrational spectra that the sandwich structure (⁵-C₅H₅)₂Zn (A) is not energetically favorable and more favorable are the close in energy -structure (⁵-C₅H₅)(¹-C₅H₅)Zn (B) and -structure (¹-C₅H₅)₂Zn (C). The vibrational spectra of structures B and C with the DFT-derived force fields were calculated. A comparison of the calculated spectra of the isolated Cp₂Zn molecules with the experimental data gives no way of deciding between the B and C structures. It is most likely that the molecule is nonrigid and experiences a strong influence from the nearest environment in solution or in the crystalline state.     

Structure and vibrational spectra of mononitroalkanes

Structures and force fields for several mononitroalkane molecules were determined by ab initio quantum-chemical methods. The data obtained were used for calculation of the frequencies and modes of normal vibrations. Potentialities of different methods (RHF, MP2, and B3LYP) and basis sets for estimation of the structures and spectra were studied.     

Synthesis and Structure of a New Polymorph Ba_2CuSi_2O_7

1INTRODUCTIONTheuniqueelectronicpropertiesofcopperoxidesandoxyhalideshaveattractedmuchattentionduetotheirpotentialapplicationsassupercon-ductors,catalysts,luminescentmaterialsandp-typetransparentconductors[1].Inanefforttoexplorenewframeworkstructuresofmixed-metaloxyha-lidessuchasCuAgOCl,wehaveobtainedanewpolymorphofthebariumdicopperdisilicate,b-Ba2CuSi2O7.Inthispaper,wewillreportthesolid-statesynthesisandcrystalstructureofthisnewphaseanddiscussthedifferencesbetweenthestructuresofb-Ba2C…     

Na2B2Se7, K2B2S7 und K2B2Se7: Drei Perchalkogenoborate mit neuem polymeren Anionengerüst

Na₂B₂Se₇, K₂B₂S₇, and K₂B₂Se₇: Three Perchalcogenoborates with a Novel Polymeric Anion Network Na₂B₂Se₇ (I 2/a; a = 11.863(4) Å, b = 6.703(2) Å, c = 13.811(6) Å, β = 109.41(2)°; Z = 4), K₂B₂S₇ (I 2/a; a = 11.660(2) Å, β = 6.827(1) Å, c = 12.992(3) Å, β = 106.78(3)°; Z = 4), and K₂B₂Se₇ (I 2/a; a = 12.092(4) Å, b = 7.054(2) Å, c = 13.991(5) Å, β = 107.79(3)°; Z = 4) were prepared by reaction of stoichiometric amounts of sodium selenide (potassium sulfide) with boron and sulfur or of potassium selenide and boron diselenide, respectively, at 600°C with subsequent annealing. The crystal structures consist of polymeric anion chains of composition ([B₂S₇]^2?)_n or ([B₂Se₇]^2?)_n formed by spirocyclically connected five-membered B₂S₃ (B₂Se₃) rings and six-membered B₂S₄ (B₂Se₄) rings. The nine-coordinate alkaline metal cations are situated in between.     

Synthesis and Crystal Structure of 9-Pyridyl-1,8-dioxo-2,3,4,5,6,7-hexahydroxanthene

1 INTRODUCTION The Koevenagel condensation catalyzed by bases or Lewis acid has been the subject of many synthetic applications since its discovery[1] although the pre- sence of catalyst is not always indispensable[2]. Mo- reover, the reaction of aromatic aldehyde with 1,3- cyclohexanedione under different conditions afforded different products[3～6]. In continuing efforts for the application of 1,3-cyclohexanedione derivatives to construct new heterocycles with biological activi- ties[7…     

Darstellung,spektroskopische Charakterisierung und Kristallstruktur von (CF3)2C(F)OH2+Sb2F11–

Preparation, Spectroscopic Characterization, and Crystal Structure of (CF₃)₂C(F)OH₂⁺Sb₂F₁₁^– Hexafluoroacetone, (CF₃)₂CO, reacts at –78 °C with the superacid HF/SbF₅ under formation of the primary oxonium salt, (CF₃)₂C(F)OH₂⁺Sb₂F₁₁^–, which is characterized by vibrational spectroscopy and NMR spectra. The salt crystallizes in the triclinic space group P1 with a = 817.9(1), b = 989.0(1), c = 1003.8(1) pm and 2 formula units per unit cell.     

Synthesis and Crystal Structure of Nd_2Si_2O_7 in Low Temperature Form

1INTRoDUCTIONAmongthesilicates,rareearthdisilicatesarespecialbecausetheyshowexten-sivepolymorphism"~".Theconfigurationof(Si,O,)doubletetrahedraisrelativelyrelatedtoperiodicityoftherareearthelectronicstructures,suchasvariationinionicsizeordiscontinuityinchemicalbondingproperties,andalsousefulfordiscussingthedegreeofd-pffbondinginsilicates.SmolinandShepelevhavesynthesizedhightem-peratureformofNd,Si,O,crystallizedinorthorhombicsystem"'.Werecent1yob-tainedlowtemperatureformofNd,Si,O,,which…     

Synthesis and Crystal Structure of Borate Oxide Co_3BO_5

1　ＩＮＴＲＯＤＵＣＴＩＯＮＳｏｌｉｄ ｓｔａｔｅｂｏｒａｔｅｓｅｘｈｉｂｉｔａｖａｒｉｅｔｙｏｆｐｈｙｓｉｃａｌａｎｄｃｈｅｍｉｃａｌｆｅａｔｕｒｅｓ,ｒａｎｇｉｎｇｆｒｏｍｎｏｎｌｉｎｅａｒｏｐｔｉｃａｌｐｒｏｐｅｒｔｉｅｓｏｆ β ＢａＢ2 Ｏ4(β ＢＢＯ) [1 ] ｔｏｔｈｅｃａｔａｌｙｔｉｃａｃｔｉｖｉｔｙｏｆＣｕ2 Ａｌ6Ｂ4Ｏ1 7[2 ] ,ｗｈｉｃｈｈａｖｅａｔｔｒａｃｔｅｄｇｒｅａｔａｔｔｅｎｔｉｏｎｏｆｍａｎｙｓｃｉｅｎｔｉｆｉｃｒｅｓｅａｒｃｈｅｒｓ.Ａｓｐａｒｔｏｆｏｕｒｅｆｆｏｒｔｔｏｓｙｎｔ…     

Synthesen und Schwingungsspektren der homoleptischen Acetonitrilkomplex-Kationen [Au(NCCH3)2]+, [Pd(NCCH3)4]2+, [Pt(NCCH3)4]2+ und des Adduktes CH3CN · SbF5. Kristallstrukturen der Salze [M(NCCH3)4][SbF6]2 · CH3CN,M = Pd,Pt

The Syntheses and Vibrational Spectra of the Homoleptic Metal Acetonitrile Cations [Au(NCCH₃)₂]⁺, [Pd(NCCH₃)₄]²⁺, [Pt(NCCH₃)₄]²⁺, and the Adduct CH₃CN · SbF₅. The Crystal and Molecular Structures of [M(NCCH₃)₄][SbF₆]₂ · CH₃CN, M = Pd or Pt Solvolyses of the homoleptic metal carbonyl salts [M(CO)₄][Sb₂F₁₁]₂, M = Pd or Pt, in acetonitrile leads at 50 °C both to complete ligand exchange for the cations as well as to a conversion of the di-octahedral anion [Sb₂F₁₁]^– into [SbF₆]^– and the molecular adduct CH₃CN · SbF₅ according to: [M(CO)₄][Sb₂F₁₁]₂ + 7 CH₃CN → [M(NCCH₃)₄][SbF₆]₂ · CH₃CN + 2 CH₃CN · SbF₅ + 4 CO M = Pd, Pt The monosolvated [M(NCCH₃)₄][SbF₆]₂ · CH₃CN are obtained as single crystals from solution and are structurally characterized by single crystal x-ray diffraction. Both salts are isostructural. The cations are square planar but the N–C–C-sceletial groups of the ligands depart slightly from linearity. The new acetonitrile complexes as well as [Au(NCCH₃)₂][SbF₆] and the adduct CH₃CN · SbF₅ are completely characterized by vibrational spectroscopy.     

Darstellung und Eigenschaften von Diphthalocyaninaten des Bismuts, [Bi(Pc)2]k (k = 1−, 0, 1+); Kristallstruktur von gemischtvalentem [Bi(Pc)2] · CH2Cl2

Synthesis and Properties of Diphthalocyaninates of Bismuth, [Bi(Pc)₂]^k (k = 1?, 0, 1+); Crystal Structure of mixed-valent [Bi(Pc)₂] · CH₂Cl₂ Blue di(phthalocyaninato(2-))bismuthate(III), [Bi(Pc^2?)₂]^?, is obtained by the reaction of BiO(NO₃) with molten 1,2-dicyanobenzene in the presence of potassium methylate and isolated as tetra-n-butylammonium (ⁿBu₄N)⁺ and bis(triphenylphosphine)iminium (PNP)⁺ salt. Green mixed-valent [Bi(Pc)₂] · CH₂Cl₂ is prepared by anodic oxidation of [Bi(Pc^2?)₂]^?. It crystallizes in the orthorhombic γ modification (Pnma; a = 28.176(5), b = 22.913(3), c = 7.925(1) Å, Z = 4). The Bi^III ion is eightfold coordinated by the N_iso atoms of the slightly distorted Pc ligands in a square antiprismatic manner. The average Bi? N_iso bond distance is 2.467 Å. The complex is paramagnetic (μ_eff = 1.84 μ_B). Oxidation of [Bi(Pc^2?)₂]^? with bromine yields purple, diamagnetic [Bi(Pc^?)₂]Br_x (1.5 ≤ x ≤ 2.5). The redox properties are investigated electrochemically. UV-Vis-NIR, MIR/FIR and resonance Raman spectra of the new bismuth(III) complexes are discussed and compared with those of diphthalocyaninates of the lanthanides.     

Analysis of atomic displacement parameters and molecular motion in crystals. Part 2. X-ray crystal structure of K2Ru(SO4)2 * 6H2O at 160 K and 295 K

Atomic displacement parameters determined from a single-crystal X-ray-diffraction study on K₂Ru(SO₄)₂ * 6H₂O are analyzed in the molecular mean field approximation. The motion of SO₂ ^2– can be described with a rigid-body model, whereas for [Ru(H₂O)₆]²⁺ internal stretching motion and coupling between stretching motion and overall translation are found to be necessary for explaining the observed atomic displacement parameters. Frequencies and force constants of internal motion are not significantly affected by such couplings. K₂Ru(SO₄)₂ * 6H₂O crystallizes in the monoclinic space groupP2₁/c (No. 14), witha = 6.1211(7)Å,b = 12.226(2) Å,c = 8.916(2)Å, = 105.11(1)°,Z = 2 at 160 K anda = 6.1402(7)Å,b = 12.274(2)Å,c = 8.957(1)Å, = 105.25(1)°,Z = 2 at 295 K. The structure was refined to a finalR(F) of 0.017 at 160 K and of 0.019 at 295 K for 1438 and 1299 observed reflections withF ₀ > 6(F₀) and sin / > 0.617 Å^1–.     

双核三螺旋铁配合物的合成和结构

本文选择了2-羟基-1-萘醛与水合肼形成的席夫碱,[(HO)(C₁₀H₆)CH=N-N=CH(C₁₀H₆)(OH)],作为配体,设计组装了双核三螺旋的三价铁配合物。配合物中每一个铁离子以准八面体的配位方式分别与三个NO双齿单元配位, 三个配体分别桥联两个金属形成特定的三螺旋构型。分子内和分子间的π-π堆积作用对螺旋体的形成和堆积方式起着十分重要的作用。作为对照,本文还报道了配体的晶体结构。     

Darstellung und Eigenschaften von trans-Di(fluoro)phthalocyaninato(2–)-rhenat(III); Kristallstruktur des linear-Bis(triphenylphosphin)iminium-Doppelsalzes l(PNP)trans[Re(F)2pc2–] · 0,33l(PNP)F · 2 H2O

Synthesis and Properties of trans -Di(fluoro)phthalocyaninatorhenate(III); Crystal Structure of the linear -Bis(triphenylphosphine)iminium Double Salt ^l (PNP) ^trans[Re(F)₂pc^2–] · 0.33^l (PNP)F · 2 H₂O trans-Bis(triphenylphosphine)phthalocyaninato(2–)rhenium(II) reacts with (ⁿBu₄N)F · 3 H₂O in acetone on air yielding trans-di(fluoro)phthalocyaninato(2–)rhenate(III), ^trans[Re(F)₂pc^2–]^–. The complex anion is precipitated as tetra(n-butyl)ammonium (ⁿBu₄N), or after addition of (PNP)HSO₄ as linear-bis(triphenylphosphine)iminium (^l(PNP)) salt. The latter crystallizes as a double salt of formula ^l(PNP)^trans[Re(F)₂pc^2–] · 0.33^l(PNP)F · 2 H₂O in the cubic space group I23 (no. 197) with the cell parameter a = 21.836(2) Å; V = 10412(2) ų; Z = 6. The Re atom is located in the centre of the (N_iso)₄ plane (N_iso: isoindole-N atom) and coordinates axially two fluorine atoms in a mutual trans position. The Re–N and Re–F distance is 2.035(6) and 1.798(7) Å, respectively. According to the short Re–F distance the asymmetric Re–F stretching vibration is observed in the MIR spectrum at 746 cm^–1. Obviously due to a large spin-orbit coupling, the complex salt with an electronic low-spin d⁴ ground state of Re^III (S = 1) is diamagnetic. Hence a sharp signal is observed at –126.1 ppm in the ¹⁹F NMR spectrum. The UV-VIS-NIR spectrum shows the typical π-π* transitions at 15000 (B), 29500 (Q) and 36900 cm^–1 (N) and trip-multiplet transitions at 9500/10500 cm^–1 and 13200/14100 cm^–1.     

Darstellung und Eigenschaften von Phthalocyaninato(2–)indaten(III) mit einzähnigen Acido-Liganden; Kristallstruktur von Tetra(n-butyl)ammonium-cis-difluoro-Phthalocyaninato(2–)indat(III)-Hydrat

Preparation and Properties of Phthalocyaninato(2–)indates(III) with Monodentate Acido Ligands; Crystal Structure of Tetra(n-butyl)ammonium cis -Difluorophthalocyaninato(2–)indate(III) Hydrate Tetra(n-butyl)ammonium cis-diacidophthalocyaninato(2–)indates(III) with the monodentate acido ligands fluoride, chloride, cyanide and formiate are synthezised by the reaction of chlorophthalocyaninatoindium(III) or cis-dihydroxophthalocyaninatoindate(III) with the respective tetra(n-butyl)ammonium salt or ammonium formiate and are characterized by their UV/VIS spectra and their vibrational spectra. The difluoro-complex salt crystallizes as a hydrate ((ⁿBu₄N)^cis[In(F)₂pc^2–] · H₂O) in the monoclinic space group P2₁/n (no. 14) with cell parameters: a = 13.081(3) Å, b = 13.936(2) Å, c = 23.972(2) Å; β = 97.79(1)°, Z = 4. Hexa-coordinated indium is surrounded by four isoindole nitrogen atoms (N_iso) and two cis-positioned fluorine atoms. The average In–F and In–N_iso distance are 2.0685(4) and 2.2033(5) Å, respectively, and the F–In–F angle is 81.5(1)°. The In atom is displaced outside the centre (Ct) of the N_iso plane towards the fluoride ligands: d(In–Ct) = 0.953(1) Å. The phthalocyaninato(2–) core is nonplanar (unsymmetrical concave distortion).     

Synthesis and Crystal Structure of Ho_4S_3Si_2O_7

1 INTRODUCTION Halide fluxes are excellent media for growing single crystals of chalcogenides[1~5]. On our research in the Ln-Cu-Zn-Se system to find new phases and to search for potential infrared ceramic materials, two new compounds, KHo2CuSe4 and KEr2CuSe4, were synthesized from the reaction of the precursor with KCl flux[6]. In an attempt to synthesize the homologous sulfide by the same method using KBr as flux in a sealed evacuated quartz tube, single crystals of Ho4S3Si2O7 w…     

[NH3(CH2)5NH3][Fe2{O3PC(CH3)(OH)(PO3H)}2]·2H2O:一个新的二膦酸亚铁化合物的合成、结构与性质研究

通过水热合成得到一个新的有机二膦酸亚铁化合物[NH₃(CH₂)₅NH₃][Fe₂^Ⅱ{O₃PC(CH₃)(OH)(PO₃H)}₂]·2H₂O,该化合物包含阴离子型共价双链[Fe₂^Ⅱ{O₃PC(CH相似文献   

Methyloxoniumhexafluorometallate – Synthese,spektroskopische Charakterisierung sowie die Kristallstruktur von H3COH2+AsF6–

Methyloxoniumhexafluorometallates – Synthesis, Spectroscopic Characterization and Crystal Structure of H₃COH₂⁺AsF₆^– Up to now the protonation of methanol as a hydrogen bridged dimethanolium ion [H(CH₃OH)₂]⁺ was observed by different X-ray crystal structure studies. Now the preparation of H₃COH₂⁺MF₆^– in super acid media HF/MF₅ (M = As, Sb) is reported. The thermolabile and moisture sensitive salts are characterized by vibrational and NMR spectroscopy. H₃COH₂⁺AsF₆^– crystallizes in the monoclinic space group P2₁/m (No. 11) with a = 487.8(1), b = 714.0(2), c = 848.2(2) pm, β = 98.03°(2) with 2 formula units per unit cell.