Die Ammonolyse von (NH4)2GeF6. Darstellung und Struktur von NH4[Ge(NH3)F5]

Ammonolysis Reaction of (NH₄)₂GeF₆. Synthesis and Structure of NH₄[Ge(NH₃)F₅] (NH₄)₂GeF₆ reacts with ammonia to yield NH₄[Ge(NH₃)F₅] at 280°C. The reaction path was elucidated by in situ time and temperature resolved X-ray powder diffraction. NH₄[Ge(NH₃)F₅] crystallizes isostructurally to NH₄[Si(NH₃)F₅] in the tetragonal space group P4/n (No. 85) with lattice constants a = 619.41(1) pm and c = 724.70(1) pm. The germanium atom is coordinated by five fluorine atoms and the nitrogen atom of the ammonia molecule. The ammonium cation is located on the Wyckoff position (2 a) in P4/n. The crystal structure is stabilized by extensive hydrogen bonding.     

Synthese und Kristallstruktur zweier Formen von Ammoniummonomolybdat (NH4)2MoO4

Synthesis and Structure of Two Forms of Ammonium Monomolybdate (NH₄)₂MoO₄ Ammonium monomolybdate (NH₄)₂MoO₄ exists in two different polymorphic forms which differ in their lattice constants and in the arrangement of the ammonium cations relative to the molybdate anions. The ammonium molybdates (NH₄)₂MoO₄(mS60)¹⁾ and (NH₄)₂MoO₄(mP60)²⁾ are synthesized by the reaction of ammonia and (NH₄)₆[Mo₇O₂₄] · 4 H₂O. (NH₄)₂MoO₄(mS60) crystallizes isostructural to the potassium compound in space group C2/m (Nr. 12) and lattice constants a = 1263.6(3), b = 652.2(1) pm, c = 776.4(2) pm and β = 117.36(1)° (V = 568.3(2) · 10⁶ pm³) containig four formula units per unit cell (R = 0.0250). (NH₄)₂MoO₄(mP60) crystallizes monoclinic in space group P2₁/n (Nr. 14) and lattice constants a = 622.8(2), b = 777.0(1) pm, c = 1118.8(4) pm and β = 98.09(2)° (V = 536.0(3) · 10⁶ pm³) (R = 0.0205). The different arrangements of the polyhedra within the unit cell is caused by hydrogen bridges. A transition point was not yet determined.     

Zeit- und temperaturaufgelöste Röntgenpulverdiffraktometrie: Die Reaktion von (NH4)2SnF6 mit Ammoniak

Time and Temperature Resolved in situ X-Ray Powder Diffractometry. The Reaction of (NH₄)₂SnF₆ with Ammonia The thermal decomposition of (NH₄)₂SnF₆ under an atmosphere of ammonia is reported. The complicated reaction paths were illucidated by time and temperature resolved in situ x-ray powder diffractometry. It is shown that this technique is a powerful tool to observe structural changes during reaction. It offers also a valuable access to thermodynamic and kinetic data for solid state and gas phase reactions. (NH₄)₂SnF₆ decomposes under ammonia below room temperature to NH₄F and amorphous SnF₄ · x NH₃. At a temperature of 80°C an intermediate product, (NH₄)₄SnF₈, is formed, which decomposes at 140°C into (NH₄)₂SnF₆ and NH₄F. At 250°C (NH₄)[Sn(NH₃)F₅] and Sn(NH₃)₂F₄ are formed. The latter crystallises C-centered monoclinic with lattice constants a = 844.1(5) pm, b = 630.5(3) pm, c = 520.2(3) pm and b? = 114.02(7)°. At 330°C a further decomposition yields SnF₂(NH₂)₂ with a C-centered monoclinic cell and lattice constants a = 1 069(7), b = 325.3(2), c = 504.8(3) pm and b? = 105.83(7)°. Finally above 500°C tin metal is formed.     

Darstellung und Struktur eines Ammoniumdiamidodioxophosphats(V), NH4PO2(NH2)2

Synthesis and Structure of an Ammonium Diamidodioxophosphate(V), NH₄PO₂(NH₂)₂ The ammonolysis of P₃N₅ under ammonothermal conditions (T = 400°C, p(NH₃) = 6 kbar, 14 d in autoclaves) in the presence of small definite amounts of water leads to the formation of NH₄PO₂(NH₂)₂. The structure was solved by single crystal X-ray methods. NH₄PO₂(NH₂)₂: P2₁/c (Nr. 14), a = 6.886(1) Å, b = 8.366(2) Å, c = 9.151(2) Å, β = 111.78(3)°, Z = 4, R₁/wR₂ = 0.026/0.072, Z(F > 2σ(F)) = 1183, N(variables) = 87. In NH₄PO₂(NH₂)₂ the anions [PO₂(NH₂)₂]^? are linked to chains by N? H …? N and N? H …? O bridge bonds. The ammonium ions are located between these chains and are donors for N? H …? O bridge bonds which connect the chains three-dimensionally.     

Darstellung und Struktur von Tetraethylcyclotetraarsoxan-Komplexen von Kupfer(I)-Halogeniden

Preparation and Structure of Tetraethylcyclotetraarsoxane Complexes of Copper(I) Halides The polymeric complexes [Cu₄Cl₄{cyclo-(C₂H₅AsO)₄}₃]_n ( 1 ), [Cu₃Br₃{cyclo-(C₂H₅AsO)₄}₂]_n ( 2 ) and [Cu₆I₆{cyclo-(C₂H₅AsO)₄}₃]_n ( 3 ) were prepared by the reaction of (C₂H₅AsO)_n and CuX (X = Cl, Br, I) in acetonitrile and characterised by X-ray analysis. All three complexes contain only tetramers (C₂H₅AsO)₄ as ligands, in which the As₄O₄ ring systems coordinate between two and four Cu-atoms. In each case one As₄O₄ ring with a crown-shaped conformation is observed, which coordinates either four (in 1 ) or three (in 2 and 3 ) axially sited Cu-atoms. In addition there are further (C₂H₅AsO)₄ ligands, which display either a boat-chair- (in 1 ) or a twist-chair-conformation (in 1–3 ). The individual building units are connected to one another via Cu? X? Cu bridges (in 2 and 3 ) and/or centrosymmetric As₄O₄ ring systems (in 1–3 ) into chain ( 1 ) or layer structures ( 2 und 3 ).     

Struktur und ausgewählte Reaktionen von ReCl4(PPh3)2

ReCl₄(PPh₃)₂ – Reactions and Structure The compounds ReCl₄(PPh₃)₂ and Re₂OCl₃(C₂H₅COO)₂(PPh₃)₂ resulting from the reaction of ReOCl₃(PPh₃)₂ with PPh₃ in boiling propionic acid and HCl atmosphere were characterized by their VIS-spectra and structural data. Ligand exchange reactions with acetylacetone gave ReCl₂(acac)₂ as well as ReCl₂(acac)(PPh₃)₂. Crystallographic data see “Inhaltsübersicht”.     

Darstellung und spektroskopische Charakterisierung von bindungsisomeren Halogenoselenocyanato-Osmaten(IV) und -Rhenaten(IV)

Preparation and Spectroscopic Characterization of Bond Isomeric Halogenoselenocyanato-Osmates(IV) and -Rhenates(IV) By oxidative ligand exchange of appropriate chloro-iodo complexes of Os^IV or Re^IV with (SeCN)₂ in CH₂Cl₂ or by heterogeneous reaction with Pb(SeCN)₂ or AgSeCN in CH₂Cl₂ the new complexes cis-[OsCl₄(NCSe)(SeCN)]^2?, tr.-[OsCl₄Br(NCSe)]^2?, tr.-[OsCl₄Br(SeCN)]^2?, [ReCl₅(NCSe)]^2?, [ReCl₅(SeCN)]^2?, tr.-[ReCl₄I(NCSe)]^2?, tr.?[ReCl₄(NCSe)(SeCN)]^2? and tr.?[ReCl₄(NCSe)₂]^2? are formed and isolated as pure compounds by ion exchange chromatography on DEAE-cellulose. The bond isomers are significantly distinguished by the frequencies of innerligand vibrations: n?_CN(Se) > n?_CN(N); n?_CSe(N) > n?_CSe(Se); δ_NCSe > δ_SeCN. The electronic spectra (10 K) of the solid salts reveal a bathochromic shift for the charge transfer bands of the Se isomers as compared with the corresponding N isomers. The intra-configurational transitions are observed for the Os^IV complexes at 600 to 2400 and for the Re^IV complexes at 500 to 1600 nm. The ⁷⁷Se nmr signals of the Os^IV bond isomers are registrated for Se binding in the region 970 to 1040 ppm, for N coordination downfield at 1540 to 1640 ppm.     

Synthese und Struktur von Hexa-t-butyl-1,4-dichloro-1,4-distanna-2,3,5,6,7,8-hexaphosphabicyclo[2.2.2]octan – Eine neue Käfigverbindung mit dem Sn(P2)3Sn-Gerüst

Synthesis and Structure of Hexa-t-butyl-1,4-dichloro-1,4-distanna-2,3,5,6,7,8-hexaphosphabicyclo[2.2.2]octane – a New Cage Compound with the Sn(P₂)₃Sn Skeleton The reaction of the diphosphide K₂[(tBuP)₂] 1 with SnCl₄ leads by a redox process mainly to (tBuP)_3,4 and other sideproducts. However, at the same time a threefold [2 + 1]-cyclocondensation reaction takes place yielding the new cage compound hexa-t-butyl-1,4-dichloro-1,4-distanna-2,3,5,6,7,8-hexaphosphabicyclo[2.2.2]octane, ClSn(tBuP? PtBu)₃SnCl 2 . 2 could be obtained in a pure form and characterized ³¹P and ¹¹⁹Sn NMR spectroscopically; 2 was also characterized by a single crystal structure analysis.     

Darstellung und Kristallstruktur von Rb2Sn3S7 · 2H2O und Rb4Sn2Se6

Preparation and Crystal Structure of Rb₂Sn₃S₇ · 2 H₂O and Rb₄Sn₂Se₆ Rb₂Sn₃S₇ · 2 H₂O has been prepared by hydrothermal reaction of SnS₂ and Rb₂CO₃ in an with H₂S saturated aqueous solution at 190°C. The crystal lattice contains chain anions [Sn₃S₇^2?] which display both SnS₄ tetrahedra and SnS₆ octahedra. Methanolothermal reaction of SnCl₂ with Se and Rb₂CO₃ at 145°C leads to the formation of Rb₄Sn₂Se₆ which contains edge-bridged bitetrahedral [Sn₂Se₆]^4? anions.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von vier bindungsisomeren Tetrachlorodirhodanoosmaten(IV)

Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of Four Linkage Isomeric Tetrachlorodirhodanoosmates(IV) By treatment of cis- or trans-[OsCl₄I₂]^2? with (SCN)₂ in dichloromethane the linkage isomers cis-[OsCl₄(NCS)₂]^2? ( 1 ), trans-[OsCl₄(NCS)(SCN)]^2? ( 2 ), cis-[OsCl₄(NCS)(SCN)]^2? ( 3 ) and trans-[OsCl₄(SCN)₂]^2? ( 4 ) are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-Ray structure determinations on single crystals of cis-(Ph₄As)₂[OsCl₄(NCS)₂] (triclinic, space group P1 , a = 10.019(5), b = 11.702(5), c = 21.922(5) Å, α = 83.602(5)°, β = 85.718(5)°, γ = 73.300(5)°, Z = 2), trans-(Ph₄As)₂[OsCl₄ · (NCS)(SCN)] (monoclinic, space group P2₁/c, a = 18.025(5), b = 11.445(5), c = 23.437(5) Å, β = 94.208(5)°, Z = 4), cis-(Ph₄As)₂[OsCl₄(NCS)(SCN)] (triclinic, space group P1 , a = 10.579(5), b = 11.682(5), c = 22.557(5) Å, α = 81.073(5)°, β = 85.807(5)°, γ = 87.677(5)°, Z = 2) and trans-(Ph₄As)₂ · [OsCl₄(SCN)₂] (triclinic, space group P1 , a = 10.615(5), b = 11.691(5), c = 11.907(5) Å, α = 111.314(5)°, β = 96.718(5)°, γ = 91.446(5)°, Z = 1) reveal the complete ordering of the complex anions. The via N or S coordinated thiocyanate groups are located nearly direct above one of the cis-positioned Cl ligands with Os? N? C angles of 171.2° and 174.3° ( 1 ), 162.3° ( 2 ), 172° ( 3 ) and Os? S? C angles of 108.3° ( 2 ), 105.7° ( 3 ) and 105.5° ( 4 ). Using the molecular parameters of the X-Ray determinations the low temperature (10 K) IR and Raman spectra of the (n-Bu₄N) salts of all four linkage isomers are assigned by normal coordinate analyses based on a modified valence force field. The valence force constants are f_d(OsN) = 1.59 ( 1 ), 1.67 ( 2 ), 1.60 ( 3 ) and f_d(OsS) = 1.27 ( 2 ), 1.31 ( 3 ) and 1.32 mdyn Å^?1 ( 4 ). Taking into account increments of the trans influence a good agreement between observed and calculated frequencies is achieved.     

Darstellung und Kristallstruktur der Hexaselenodiphosphate(IV) von Antimon und Bismut

Preparation and Crystal Structure of the Hexaselenodiphosphates(IV) of Antimony and Bismuth Sb₄(P₂Se₆)₃ and Bi₄(P₂Se₆)₃ are synthesized from the elements via chemical transport reactions with iodine. The isotypic compounds crystallize in the monoclinic space group P2₁/n (No. 14) with lattice parameters a = 2 077.7(4) pm, b = 749.35(5) pm, c = 949.49(8) pm, β = 91.25(1)° for Sb₄(P₂Se₆)₃ and a = 2 086.9(3) pm, b = 747.45(6) pm, c = 959.23(6) pm, β = 91.73(1)° for Bi₄(P₂Se₆)₃, respectively. This new structure type is closely related to the structure of Pb₂P₂Se₆ showing an ordered cation distribution combined with a reorientation of the ethane like [P₂Se₆]^4? units. From the interatomic distances in the coordination spheres a smaller lone pair effect of Bi^III compared to Sb^III may be deduced. For both compounds UV/VIS spectra and temperature dependence of the electrical resistivity are reported.     

Struktur von Bis[salicylaldehyd-2-hydroxyanilato(2—)]vanadium(IV)

Molecular Structure of Bis[salicylaldehyde-2-hydroxyanilato(2—)]vanadium(IV) By the reaction of tris(acetylacetonato)vanadium(III) with salicylaldehyde-2-hydroxyanil the non-oxo vanadium(IV) complex of this ligand was prepared. Bis[salicylaldehyde-2-hydroxyanilato(2—)]vanadium(IV) has a distorted octahedral structure. Crystallographic data see “Inhaltsübersicht”.     

Darstellung und Kristallstrukturen von (Ph3PNPPh3)2[Re2Br10] und (Ph4P)[Re2Br9]

Synthesis and Crystal Structures of (Ph₃PNPPh₃)₂[Re₂Br₁₀] and (Ph₄P)[Re₂Br₉] Depending on the molar ratio by reaction of [n-Bu₄N]₂[ReBr₆] with the Lewis acid BBr₃ in dichloromethane the bioctahedral complexes [n-Bu₄N]₂[Re₂Br₁₀] and [n-Bu₄N][Re₂Br₉] are formed. The X-ray structure determination on (Ph₃PNPPh₃)₂[Re₂Br₁₀] (monoclinic, space group C 2/c, a = 20.007(4), b = 15.456(5), c = 24.695(4) Å, β = 107.53(2)°, Z = 4) reveals a centrosymmetric edge-sharing complex anion with approximate D_2h symmetry and mean terminal and bridging Re–Br bond lengths of 2.453 (equatorial), 2.482 (axial) and 2.591 Å, respectively, and a Re–Re distance of 3.880 Å. (Ph₄P)[Re₂Br₉] (triclinic, space group P 1, a = 11.062(2), b = 12.430(3), c = 13.163(5) Å, α = 72.94(2), β = 68.47(2), γ = 82.09(2)°, Z = 2) contains a confacial bioctahedral anion with nearly D_3h symmetry and mean terminal and bridging Re–Br distances of 2.460 and 2.536 Å, respectively, and a Re–Re distance of 2.780 Å.     

Synthese,Struktur und Phasenumwandlung von Se4(MoOCl4)2

Synthesis, Crystal Structure, and Phase Transition of Se₄(MoOCl₄)₂ Dark green, very air sensitive crystals of Se₄(MoOCl₄)₂ are formed from selenium and MoOCl₄ at 190°C in a sealed, evacuated glass ampoule in quantitative yield. The structure is built of nearly square planar Se₄²⁺ ions and centrosymmetric dimeric MoOCl₄^? ions which are linked by bridging Cl atoms. At ?21°C Se₄(MoOCl₄)₂ undergoes a reversible solid state phase transition of first order. Structure determinations at ?70°C and 23°C show that during the phase transition the structures of the ions remain unchanged, while the orientations of the ions with respect to each other change in such a way that in the low temperature form the Se₄²⁺ ions obtain a higher coordination number by Cl and O atoms of neighboring MoOCl₄^? ions.     

Simultaneous spectrophotometric determination of Sn(II) and Sn(IV) by mean centering of ratio kinetic profiles and partial least squares methods

Two spectrophotometric methods are described for the simultaneous determination of binary mixtures of Sn(II) and Sn(IV) in water samples and fruit juice samples, without prior separation steps, using the mean centering of ratio kinetic profiles and partial least squares (PLS) methods. The methods are based on the difference in the rate of the reactions of Sn(II) and Sn(IV) with pyrocatechol violet at pH 4.0. The methods allow rapid and accurate determination of Sn(II) and Sn(IV). The analytical characteristics of the methods for the simultaneous determination of binary mixtures of Sn(II) and Sn(IV) were calculated. The results showed that the methods were capable to simultaneous determination of 0.1–1.80 mg L⁻¹ each of cations. The proposed methods were successfully applied to the simultaneous determination of Sn(II) and Sn(IV)in an orange juice sample.     

Bariumstannat‐Pulver durch hydrothermale Synthese und durch Thermolyse von Bariumzinn(IV)‐glykolaten. Synthese und Struktur von [Ba(C2H6O2)4][Sn(C2H4O2)3] und [Ba(C2H6O2)2][Sn(C2H4O2)3]·CH3OH

Barium Stannate Powders from Hydrothermal Synthesis and by Thermolysis of Barium‐Tin(IV)‐Glycolates. Synthesis and Structure of [Ba(C₂H₆O₂)₄][Sn(C₂H₄O₂)₃] and [Ba(C₂H₆O₂)₂][Sn(C₂H₄O₂)₃]·CH₃OH The hydrothermal reaction as well as the microwave assisted hydrothermal reaction of SnO₂·aq with barium hydroxide gives Ba[Sn(OH)₆] ( 1 ) as powder with bar like particles. Compound 1 of the same morphology can also be isolated from a hydrothermal reaction of [Ba(C₂H₆O₂)₄][Sn(C₂H₄O₂)₃] ( 3 ). The reaction of SnO₂·aq with Ba(OH)₂·8H₂O in ethylene glycol yields the glycolate [Ba(C₂H₆O₂)₄][Sn(C₂H₄O₂)₃] ( 3 ), which forms in methanol the solvate [Ba(C₂H₆O₂)₂][Sn(C₂H₄O₂)₃]·CH₃OH ( 4 ). Compounds 1 , 3 and 4 react at different temperatures to BaSnO₃ ( 2 ) consisting of powders with different morphologies; because of the grain size of the resulting powders compounds 3 and 4 are suitable as precursor for the fabrication of corresponding ceramics.     

Isotype Strukturen einiger Hexaamminmetall(II)-halogenide von 3d-Metallen: [V(NH3)6]I2, [Cr(NH3)6]I2, [Mn(NH3)6]Cl2, [Fe(NH3)6]Cl2, [Fe(NH3)6]Br2, [Co(NH3)6]Br2 und [Ni(NH3)6]Cl2

The Structures of some Hexaammine Metal(II) Halides of 3 d Metals: [V(NH₃)₆]I₂, [Cr(NH₃)₆]I₂, [Mn(NH₃)₆]Cl₂, [Fe(NH₃)₆]Cl₂, [Fe(NH₃)₆]Br₂, [Co(NH₃)₆]Br₂ and [Ni(NH₃)₆]Cl₂ Crystals of yellow [V(NH₃)₆]I₂ and green [Cr(NH₃)₆]I₂ were obtained by the reaction of VI₂ and CrI₂ with liquid ammonia at room temperature. Colourless crystals of [Mn(NH₃)₆]Cl₂ were obtained from Mn and NH₄Cl in supercritical ammonia. Colourless transparent crystals of [Fe(NH₃)₆]Cl₂ and [Fe(NH₃)₆]Br₂ were obtained by the reaction of FeCl₂ and FeBr₂ with supercritical ammonia at 400°C. Under the same conditions orange crystals of [Co(NH₃)₆]Br₂ were obtained from [Co₂(NH₂)₃(NH₃)₆]Br₃. Purple crystals of [Ni(NH₃)₆]Cl₂ were obtained by the reaction of NiCl₂ · 6H₂O and NH₄Cl with aqueous NH₃ solution. The structures of the isotypic compounds (Fm3 m, Z = 4) were determined from single crystal diffractometer data (see “Inhaltsübersicht”). All compounds crystallize in the K₂[PtCl₆] structure type. In these compounds the metal ions have high-spin configuration. The orientation of the dynamically disordered hydrogen atoms of the ammonia ligands is discussed.     

用2D NMR研究锡配合物配体的交换反应

Two-dimensional 1H exchange spectroscopy was applied to study of the ligand exchange kinetics of the complex [Sn2(μ-OH)2Cl6(DMF)2]•4DMF in DMF-d7 solution. The exchange rate constants for the ligand H2O and DMF between free and coordination states were evaluated.     

Darstellung und Eigenschaften von Vanadyl(IV)-Saccharinat

Summary The synthesis of a new vanadyl(IV)/saccharin complex is reported. Its bonding characteristics differ considerably from all known divalent metal-saccharinates. In this complex a VO(OH)⁺ moiety is coordinated to a saccharin molecule through its carbonyl oxygen and to a saccharinate ion through its deprotonated nitrogen. Two water molecules complete the coordination sphere. X-ray powder diagrams, infrared- and electronic absorption-spectra were recorded and analyzed for the characterization of the compound and its coordination properties. Besides, the magnetic susceptibility and the thermal behaviour were also investigated.

     

Darstellung,Kristallstruktur und Normalkoordinatenanalyse der bindungsisomeren Pentachlororhodanoosmate(IV)

Preparation, Crystal Structure and Normal Coordinate Analysis of Linkage Isomeric Pentachlororhodanoosmates(IV) By treatment of [OsCl₅I]^2? with (SCN)₂ in dichloromethane the linkage isomers [OsCl₅(NCS)]^2? and [OsCl₅(SCN)]^2? are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-ray structure determination on single crystals of (Ph₄As)₂[OsCl₅(NCS)] (monoclinic, space group P2₁/a, a = 18.872(2), b = 11.6024(2), c = 22.786(1), β = 109.057(1)°, Z = 4) and (Ph₄As)₂[OsCl₅(SCN)] (monoclinic, space group P2₁/a, a = 19.057(2), b = 11.306(2), c = 22.612(1), β = 106.64(2)°, Z = 4) reveals the complete ordering of the complex anions. The thiocyanate group is located above one of the Cl ligands of the equatorial plane with the Os? N? C angle of 166.1° for N bonding and the Os? S? C angle of 109.9° for S bonding. The IR and Raman spectra of both linkage isomers known from literature are assigned by normal coordinate analysis based on the general valence force field using the molecular parameters of the X-ray determination. The valence force constants are f_d(OsN) = 1,81 and f_d(OsS) = 1,32 mdyn/Å. Taking into account increments of the trans influence a good adjustment between observed and calculated frequencies is achieved.