Peroxofluorokomplexe der Übergangsmetalle. IX. Kristallstruktur von Ba3[Ti(O2)F5]2 · 2 H2O

Transition Metal Peroxofluoro Complexes. IX. Crystal Structure of Ba₃[Ti(O₂)F₅]₂ · 2 H₂O The pale yellow hydrat Ba₃[Ti(O₂)F₅]₂ · 2 H₂O crystallizes tetragonal (space group P4₂/mbc, a = 1 248.5(3), c = 812.2(2) pm; Z = 4; R = 0.026 for 404 independent reflections). It contains isolated [Ti(O₂)F₅]^3? anions. Thermal decomposition leads directly to α-Ba₃Ti₂O₂F₁₀, which is isotypic to α-Ba₃Al₂F₁₂.     

Peroxofluorokomplexe der Übergangsmetalle. VII. Peroxofluorokryolithe A3Ti(O2)F5 (A = K,Na) und K2NaTi(O2)F5 Kristallstruktur von K3Ti(O2)F5

Transition Metal Peroxofluoro Complexes. VII. Peroxofluorokryolithes A₃Ti(O₂)F₅ (A = K, Na) and K₂NaTi(O₂)F₅. Crystal Structure of K₃Ti(O₂)F₅ Peroxofluorokryolithes A₃Ti(O₂)F₅ (A = K, Na) and K₂NaTi(O₂)F₅ were prepared at pH 4.5–6 by adding H₂O₂ and AOH/AF to solutions of TiO₂ in hydrofluoric acid or aqueous solutions of TiF₄. In the range of pH 3–4.5 exist phases of peroxofluoro-kryolithes with variations in stoichiometrie. A single crystall X-ray structure analysis of K₃Ti(O₂)F₅ (Fm3m, a = 883.6(1) pm) yielded a disordered kryolithstructure (R = 0.020, R_W = 0.017). Na₃Ti(O₂)F₅ was found to crystallize in two monoclinic low-temperature – and one cubic high-temperature modifications. K₂NaTi(O₂)F₅ crystallizes cubic (Fm3m) with a = 847.8(1) pm. Vibrational spectra have been measured and thermal behavior was studied by DTA/DTG and high-temperature guinier. At pH 9.5 K₃Ti(O₂)₂F₃ has been synthesized     

Peroxofluorokomplexe der Übergangsmetalle. III,Darstellung, Kristallstruktur und Schwingungsspektren von K6Ta3(O2)3OF13 · H2O mit einem μ-Oxo-diperoxo-octafluoroditantalat(V)-Anion

Transition Metal Peroxofluoro Complexes. III. Preparation, Crystal Structure, and Vibrational Spectra of K₆Ta₃(O₂)₃OF₁₃ · H₂O Containing a m?-Oxo-diperoxo-octafluoroditantalate(V) Anion K₆Ta₃(O₂)₃OF₁₃ · H₂O has been prepared from solution and his crystal structure was determined by X-ray single crystal investigation: Space group Pnma, lattice constants a = 1 653.6 pm, b = 883.5 pm, c = 1 365.8 pm, Z = 4, R = 0.033. The compound yields [Ta(O₂)F₅]^2? groups as well as m?-oxo-bridged [Ta₂O(O₂)₂F₈]^4? anions with very diffrent O? O distances within the peroxo groups (139 pm vs. 164 and 175 pm) correlating well with the i.r. and Raman spectra. The different bonding in connection with an oxo-bridge is discussed.     

Peroxofluorokomplexe der Übergangsmetalle. IV. Zur Strukturchemie von Diperoxo-tetrafluorotantalaten(V): K3Ta(O2)2F4 und verwandte Phasen sowie (NH4)3Ta(O2)2F4

Transition Metal Peroxofluoro Complexes. IV. Structural Chemistry of Diperoxo-tetrafluorotantalates (V): K₃Ta(O₂)₂F₄ and Related Phases and (NH₄)₃Ta(O₂)₂F₄ Dependent on the preparative conditions K₃Ta(O₂)₂F₄ crystallizes in a monoclinic (a = 908.2(1), b = 899.2(1), c = 910.0(2) pm, β = 90.37(1)°) or — with variations in stoichiometry – in cubic phases (a = 905 to 909 pm) of the elpasolite type. The i.r. data as well as the thermal decomposition to tetragonal K₃TaO₂F₄ (a = 621.0(2), c = 884.3(4) pm, with superstructure) with cis-standing O atoms indicate the cis-position also for the O₂ groups. A single crystal X-ray structure analysis of (NH₄)₃Ta(O₂)₂F₄ (space group Fm3m, a = 941.4(7) pm, Z = 4, R_w = 0.032) yielded disordered elpasolite structure. The [Ta(O₂)₂F₄] octahedra have cis-configuration. No phase transition has been observed by X-rays when cooling down to 120 K.     

Peroxofluorokomplexe der Übergangsmetalle. VI. Darstellung,Schwingungsspektren und Kristallstruktur von (NH4)3Zr(O2)F5. Ein neues Fehlordnungsmodell für Ammonium-peroxopentafluorometallate(IV) mit Elpasolith-Struktur

Transition Metal Peroxofluoro Complexes. VI. Preparation, Vibrational Spectra, and Crystal Structure of (NH₄)₃Zr(O₂)F₅. A New Disorder Model for Ammonium Peroxopentafluoro Metallates(IV) with Elpasolite Structure (NH₄)₃Zr(O₂)F₅ has been prepared from solution and characterized by the i.r. and raman spectra. The disordered crystal structure was determined: space group Fm3 m, Z = 4, a = 944.01(8) pm, R_w = 0.014 for 162 reflections. A new disorder model – revised with respect to former proposals made for the isotypic Ti compound – allows now to derive unambiguously the geometry of the complex anions: d(O? O) = 157(1), d(Zr? O) = 206.3(9), d(Zr? F), average 203.8 pm. An analogous treatment of the disorder for (NH₄)₃Ti(O₂)F₅ also led to a significant improvement of the results (R_w = 0.019, d(O? O) = 151(2), d(Ti? O) = 197(1), d(Ti? F), average 191.6 pm).     

Kristallstruktur und spektroskopische Daten von Rb2[VOF4(H2O)]

Crystal Structure and Spectroscopic Data of Rb₂[VOF₄(H₂O)] Blue crystals of Rb₂[VOF₄(H₂O)] have been obtained from hydrofluoric acid. The crystal structure (space group Cmcm, a = 969.6(4), b = 780.6(2), c = 835.4(4) pm, Z = 4, d_c = 3.486 gcm^?3, d_m = 3.41 gcm^?3, R_w = 0.032 for 411 independent reflections) shows isolated [VOF₄(H₂O)]^2? anions — with H₂O in trans-position to the relatively long V? O bond (d(V? O) = 166.8(7) pm) — which are connected with each other by hydrogen bonds forming infinite chains. The blue colour of the compound despite of the isotypism to the “green” modification of Cs₂[VOF₄(H₂O)] is discussed on the basis of the structural data, i.r./Raman and u.v./vis reflection spectra. The magnetic moment is 1.72 B.M. at 295 K.     

Zur Existenz der Verbindung K2TiOF4: Pyrohydrolytischer Abbau von K2TiF6 und thermochemisches Verhalten von K2Ti(O2)F4 · H2O

On the Existence of the Compound K₂TiOF₄: Pyrohydrolytic Degradation of K₂TiF₆ and Thermochemical Behaviour of K₂Ti(O₂)F₄ · H₂O In an attempt to prepare K₂TiOF₄ we used the following three ways; solid-state reaction of K₂TiF₆, TiO₂, and KF, pyrohydrolysis of K₂TiF₆ at 450 and 550°C, and thermal decomposition of K₂Ti(O₂)F₄ · H₂O. In each case the reaction products were mixtures of several compounds, always containing the kryolith-phase K_2+xTiO_xF_6?x and TiO₂. At 130°C K₂Ti(O₂)F₄ · H₂O forms K₂Ti(O₂)F₄ by loss of H₂O, and at 230°C the peroxogroup decomposes, yielding K₂TiOF₄ as main product. K₂TiOF₄ crystallizes tetragonally with the following lattice parameters: a = 769.7(1) and c = 1153.9(2)pm. The i.r. spectrum shows an absorption band at 810 cm^?1, pointing to infinite chains of ? Ti? O? Ti? O? .     

Kristallstruktur und schwingungsspektrometrische Daten von cis-Na2[Pd(SO3)2en] · 4 H2O

Crystal Structure and Data from Vibrational Spectra of cis-Na₂[Pd(SO₃)₂en] · 4 H₂O The compound cis-Na₂[Pd(SO₃)₂en] · 4 H₂O (en = 1,2-diaminoethane) crystallizes in the orthorhombic space group Pnma with a = 623.7(2), = 1070.9(10), c = 1989.5(30) pm and Z = 4. In the [Pd(SO₃)₂en]^2? anions the trans-influence of the sulfite ligands manifests itself in long Pd? N bonds with short Pd? S distances. A set of Na⁺ ions is present in face-sharing octahedra Na(OH₂)₆⁺, forming rods [Na(OH₂)_6/2]⁺ parallel to [100]. A second set of Na⁺ ions is surrounded by two H₂O molecules and four O atoms from SO₃ ligands of two anions to form likewise octahedra with face-sharing, yielding rods [Na(OH₂)_2/2{(OSO₂)₂Pd en}_2/2]^? parallel to [100]. Comparatively low v(Pd? N)-frequencies reveal the trans-influence of the sulfite ligands also in the vibrational spectra.     

Zur Kristallstruktur von SrZn(OH)4 · H2O

Crystal Structure of SrZn(OH)₄ · H₂O Colorless crystals of SrZn(OH)₄ · H₂O are obtained by electrochemical oxidation of Zn in a zinc/iron pair in an aqueous ammonia solution saturated with strontium hydroxide. The X-ray crystal structure determination was now successful including all hydrogen positions: P1 , Z = 2, a = 6.244(1) Å, b = 6.3000(8) Å, c = 7.701(1) Å, α = 90.59(1)°, β = 112.56(2)°, γ = 108.66(2)°, N(F ≥ 3σF) = 1967, N(Var.) = 84, R/R_w = 0.020/0.024. In SrZn(OH)₄ · H₂O Zn²⁺ is tetrahedrally coordinated by four OH^? -ions while Sr²⁺ has 6 OH^? and one H₂O as neighbours. The polyhedra around Sr²⁺ are connected to chains which are linked three-dimensionally by isolated tetrahedra [Zn(OH)₄]. Hydrogen bonds between H₂O as donor and OH^? are characterized by raman spectroscopy.     

Die Kristallstruktur von MgHg(SCN)4 · 2 H2O

Crystal Structure of MgHg(SCN)₄ · 2 H₂O The crystal structure of the monoclinic MgHg(SCN)₄ · 2 H₂O (a ? 1 335.1(6) pm, b ? 531.6(5) pm, c ? 1 867.0(14) pm, β ? 92.3(1)°, Z ? 4, space group C2/c) contains nearly tetrahedral Hg(SCN)₄ and octahedral Mg(OH₂)₂(NCS)₄ groups. These groups are joined together with Hg? SCN? Mg bridges and are forming a network of layers.     

Über die Alkaliselenoarsenate(III) KAsSe3 · H2O,RbAsSe3 · 1/2 H2O und CsAsSe3 · 1/2 H2O

On the Alkali Selenoarsenates(III) KAsSe₃ · H₂O, RbAsSe₃ · 1/2 H₂O, and CsAsSe₃ · 1/2 H₂O The alkali selenoarsenates(III) KAsSe₃ · H₂O, RbAsSe₃ · 1/2 H₂O, and CsAsSe₃ · 1/2 H₂O have been prepared by hydrothermal reaction of the respective alkali carbonate with As₂Se₃ at a temperature of 135°C. Their X-ray structural analyses demonstrated that the compounds contain polyselenoarsenate(III) anions (AsSe₃^?)_n, in wich the basic units are ψ-AsSe₃ tetrahedra, which are linked together through Se? Se bonds into infinite zweier single chains. The Rb and Cs salts are isotypic.     

Die Kristallstruktur des SrHg(SCN)4 · 3 H2O

Crystal Structure of SrHg(SCN)₄ · 3 H₂O SrHg(SCN)₄ · 3 H₂O is orthorhombic, space group Pcca, with a = 19.476(7), b = 8.150(1), c = 8.991(3) Å, V = 1427.1 ų, Z = 4, d_c = 2.67 g · cm^?3, μ(AgKα) = 77.95 cm^?1. The salt consists of nearly tetrahedral Hg(SCN)₄ groups, Sr has a tricapped trigonal prismatic coordination: four N and five O atoms. The thiocyanate groups form end-to-end bridges and connect the Hg and Sr coordination polyhedra.     

Darstellung und Eigenschaften von Heteropolykationenverbindungen. I. Über das Dodekaaluminogermaniumsulfat [GeO4Al12(OH)24(H2O)12](SO4)4 · xH2O

Preparation and Properties of Compounds with Heteropolycations. I. Dodecaaluminogermaniumsulfate [GeO₄Al₁₂(OH)₂₄(H₂O)₁₂](SO₄)₄ · xH₂O By reaction of aqueous solutions of aluminum chloride and sodium germanate and subsequent precipitation as sulfate a cristalline product is obtained, which is the title compound according to chemical analysis and ²⁷Al-NMR in analogy to the wellknown tridecameric basic aluminum cation. From thermal analysis and kinetic measurements is concluded that the title compound has a higher stability than the tridecameric basic aluminum cation.     

Salze von Halogenophosphorsäuren. XIV. Darstellung und Kristallstruktur von Kalium-dikupferhydroxid-bis(monofluorophosphat)-Monohydrat Cu2K(OH)(PO3F)2 · H2O

Salts of Halogenophosphoric Acids. XIV. Preparation and Crystal Structure of Dicopper-potassium-hydroxide-bis(monofluorophosphate) Monohydrate Cu₂K(OH)(PO₃F)₂ · H₂O By the reaction of potassium monofluorophosphate and copper(II) salts in aqueous medium a crystalline, insoluble basic copper potassium monofluorophosphate Cu₂K(OH)(PO₃F)₂ · H₂O 1 is formed. The thermal decomposition of 1 has been studied. 1 crystallizes in the monoclinic space group B2/m with a = 9.094 Å, b = 7.755 Å, c = 6.333 Å, α = β = 90°; γ = 117.55°, and Z = 2.     

Darstellung und Kristallstruktur von Kupfer(II)-monofluorophosphat-Dihydrat CuPO3F · 2H2O

Salts of Halogenophosphoric Acids. XVII. Preparation and Crystal Structure of Copper(II) Monofluorophosphate Dihydrate CuPO₃F · 2H₂O Copper(II) monofluorophosphate dihydrate, CuPO₃F · 2H₂O 1 was obtained by the reaction of aqueous NH₄HPO₃F and acid (NH₄)₂PO₃F solutions, respectively, using acetone or ethanol as precipitating agents. The thermal dehydration of 1 gives the water-free copper monofluorophosphate CuPO₃F ( 2 ). 1 crystallizes in the monoclinic space group P2₁/c with a = 761,44, b = 780,97, c = 921,02 pm, β = 112,94° and Z = 4.     

Synthese und Kristallstruktur der Rhenium(VII)‐Nitridchloride ReNCl4 und ReNCl4·H2O

Syntheses and Crystal Structures of the Rhenium(VII) Nitride Chlorides ReNCl₄ and ReNCl₄·H₂O Rhenium(VII) nitride chloride, ReNCl₄ ( 1 ) is obtained in form of brown needles with metallic luster by the reaction of ReCl₅ with Cl₃VNCl at 140 °C under vacuum in a sealed glass ampoule. It crystallizes in the tetragonal space group I4 with the lattice parameters a = 826.7(4), c = 405.1(2) pm, and Z = 2. The square pyramidal molecules are connected by asymmetric nitrido bridges to form chains along the crystallographic c axis. The shorter Re‐N distance of 163.0(5) pm corresponds to a triple bond, while the pronounced longer distance of 242.0(5) pm can be interpreted with a weak donor bond. The reaction of ReCl₅ with VN at 170 °C under vacuum in a sealed glass ampoule yields red needles of ReNCl₄·H₂O ( 2 ). It crystallizes in the orthorhombic space group Pnma with a = 1075.4(2), b = 1108.5(2), c = 547.7(5) pm and Z = 4. The Re atoms exhibit a distorted octahedral coordination with the aqua ligand in trans position to the nitrido ligand. The Re‐N triple bond has a bond distance of 166.1(11) pm. The complexes are connected by hydrogen bridges O‐H···N to form chains.     

Über die Pentachlorothallate(III) K2TlCl5 · 2 H2O und M2TlCl5 · H2O (M = Rb,NH4)

On the Pentachlorothallates(III) K₂TlCl₅ · 2 H₂O and M₂TlCl₅ · H₂O (M = Rb, NH₄) The pentachlorothallates(III) K₂TlCl₅ · 2 H₂O and M₂TlCl₅ · H₂O (M = Rb, NH₄) were obtained by crystallization from aqueous solutions of TlCl₃ and MCl. The crystal structure of the monoclinic K₂TlCl₅ · 2 H₂O contains dimeric Tl₂Cl₁₀ anions formed by two edge sharing octahedra. The orthorhombic monohydrates are isotypic with Cs₂[TlCl₅(OH₂)].     

Zur Darstellung und Kristallstruktur der Thiotellurite BaTeS3 · 2 H2O und (NH4)2TeS3

Preparation and Crystal Structure of the Thiotellurites BaTeS₃·2H₂O and (NH₄)₂TeS₃ The new compounds BaTeS₃ · 2 H₂O and (NH₄)₂TeS₃ have been prepared and their structures determined. According to these the anion of the trithiotelluric acid in these compounds represents a distorted trigonal TeS?pyramid. The Te? S-distances are 2.34–2.36 Å. Crystallographic data see ?Inhaltsübersicht”?.     

Triäthanolaminkomplexe. II. Die Kristallstruktur von 2 ZnCl2 · C6H15O3N · H2O

The crystal structure of 2 ZnCl₂ · C₆H₁₅O₃N · H₂O has been determined by direct methods. The triethanolamine complex crystallizes in space group P 2₁/c with a₀ = 10.86, b₀ = 10.08, c₀ = 14.09 Å, β = 93.5° und Z = 4. The structure has been refined by least squares methods. Final R₁ index is 4.4% for 579 reflexions. One half of the zinc atoms are octahedrally coordinated by a chlorine atom, a water molecule and by the nitrogen and the three oxygen of the triethanolamine molecule. The other half is tetrahedrally surrounded by chlorine. The two zinc complexes are connected via a common chlorine atom.