Biological Properties of Antimony(III) Fluoride Complexes

Result of a study of how antimony trifluoride and fluoride complexes MSb₂F₇ (M = K, Rb, Cs, Tl, NH₄), MSbF₄ (M = Na, K, Rb, Cs, NH₄), and M₂SbF₅ (M = Na, K, Rb, Cs, Tl, NH₄) affect the growth of associations of marine bacteria and vital activity of marine alga Ulva Fenestrata are presented. The possible ways of using Sb(III) fluoride compounds are discussed.     

Synthesis, crystal structure, and vibrational spectra of MVO(SO4)2 (M = Rb, Cs, or Tl)

A series of MVO(SO₄)₂ vanadium complexes, where M = Rb, Cs, or Tl, were prepared, and their crystal structures and physicochemical properties studied. The rubidium and thallium compounds of this series were found to be isostructural to each other and to crystallize, like KVO(SO₄)₂ and NH₄VO(SO₄)₂, in orthorhombic system (space group P2₁2₁2₁, No. 19, Z = 4) with the unit cell parameters a = 4.9735(2) Å, b=8.7894(4) Å, c = 16.6968(8) Å, V = 729.88 ų (Rb); and a = 4.9636(1) Å, b = 8.7399(2) Å, c = 16.8598(4) Å, V = 731.39 ų (Tl). The cesium compound was found to crystallize in monoclinic system (space group P2₁/a, No. 14-2, Z = 4): a = 10.0968(6) Å, b = 8.9131(4) Å, c = 9.8675(5) Å, β = 114.640(2)°, V = 807.16 ų. The MVO(SO₄)₂ crystal structure is built of VO₆ octahedra, which are linked into layers by bridging SO₄ groups. At the apex of each VO₆ octahedron, there is a short V-O terminal bond having a length of 1.54(1) Å (Rb), 1.57(2) Å (Tl), and 1.52(4) Å (Cs).     

Structural Study of Alkaline 1-Phenyl-1H-1, 2, 3, 4-tetrazole-5-thiolate Salts: An Example of Periodicity in Alkaline Cations

The alkaline 1-phenyl-1H-1, 2, 3, 4-tetrazole-5-thiolate salts, M[C₆H₅N₄CS] (M = Li ( 1 ), Na ( 2 ), K ( 3 ), Rb ( 4 ) and Cs ( 5 )) were obtained and characterized by means of mass spectrometry (FAB⁺) and NMR (¹H; ¹³C) spectroscopy. The structures of Na ( 2 ), K ( 3 ), Rb ( 4 ) and Cs ( 5 ) compounds were determined by X-ray diffraction methods. The ligand shows a rich variety of coordination patterns with the alkaline cations. The formation of a four-membered ring MSCN in the compounds with heavier alkali cations (K, Rb and Cs) is shown. In all the cations the coordination number around it increases with the ionic radius. Compounds with Cs⁺ and Rb⁺ exhibited the formation of Cs-C and Rb-C interactions with the phenyl group.     

Kernresonanzuntersuchungen an zeolithischen Heptagermanaten, 2. Mitt.

Zusammenfassung An zeolithischen Heptagermanaten der FormelMe ₃HGe₇O₁₆·xH₂O, (Me=NH₄, Li, Tl, Cs und Na;x=0–6) wurden Kernresonanzuntersuchungen durchgeführt. Es wurden Messungen an¹H und¹⁴N in Ammoniumzeolith sowie an⁷Li,²⁰⁵Tl,¹³³Cs und²³Na zwischen Zimmertemp. und der Temperatur des flüssigen Stickstoffs ausgeführt. Es zeigt sich, daß die Kationen Diffusionsbewegungen ausführen, die sowohl durch höhere Temperatur als auch durch das Vorhandensein von Wassermolekülen begünstigt werden.

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NMR investigation of zeolitic heptagermanates, II

Zeolitic heptagermanates with compositionMe ₃HGe₇O₁₆·xH₂O, (Me=NH₄, Li, Tl, Cs and Na;x=0–6) have been investigated by NMR. Measurements on¹H and¹⁴N in ammoniumzeolites and on⁷Li,²⁰⁵Tl,¹³³Cs and²³Na have been performed between room temperature and liquid nitrogen temperature. It is observed that the cations execute diffusional motions, which are favoured by higher temperature as well as by the presence of water molecules.

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Mit 9 Abbildungen     

Über Tetrabromothallate MTlBr4 (M = K,Rb, Cs,NH4)

On the Tetrabromothallates MTlBr₄ (M = K, Rb, Cs, NH₄) The tetrabromothallates MTlBr₄ (M = K, Rb, Cs, NH₄) were obtained by dehydratisation of the appropriate hydrates MTlBr₄ · nH₂O and by the reaction of TlBr, MBr, and Br₂ in closed glass tubes at 400°C. KTlBr₄ and NH₄TlBr₄ crystallize orthorhombic in the Ga[GaCl₄]-type with the following lattice constants a = 795.2(3), b = 1036.0(4), c = 1042.1(5) pm (KTlBr₄), and a = 812.6(3), b = 1070.1(13), c = 1110.6(10) pm (NH₄TlBr₄), respectively.     

The vanadium monophosphates AVOPO4: Synthesis of a second form β-KVOPO4 and structural relationships in the series

A new form of potassium vanadophosphate β-KVOPO₄ has been synthesized using hydrothermal technique which showed the role of the extra adduct, here W or WO₃. The structure of this phase, isotypic to Rb and Cs monophosphates, has been determined from a single crystal X-ray study. Structural relationships between the different monophosphates of the AVOPO₄ series with A = Li, Na, K, Rb, Cs, NH₄ are presented in which K⁺ appears as a boundary cation: with cations smaller than K⁺ the vanadium(IV) is octahedral and pyramidal with larger ones, both coordinations existing with K⁺.     

Univalent metal uranyl carbonates

Optimal procedures were developed for the synthesis of A _4?m ^I B _m ^I [UO₂(CO₃)₃]·nH₂O (A^I = Li, Na, K, Rb, Cs, NH₄, Ag, Tl; B^I = Na; m = 0?1; n = 0?6) compounds. The structure and thermal decomposition of these compounds were studied by X-ray diffraction, precision IR spectroscopy, and thermal analysis. The IR bands were assigned using mathematical simulation based on small-vibration theory. The standard enthalpies of formation of the compounds at 298.15 K were determined for the first time by reaction calorimetry.     

Synthese und Struktur von Hydrogensulfaten des Typs M(HSO4)(H2SO4) (M = Rb,Cs und NH4)

Synthesis and Structure of Hydrogen Sulfates of the Type M(HSO₄)(H₂SO₄) (M = Rb, Cs and NH₄) From the binary systems M₂SO₄/H₂SO₄ (M = Rb, Cs, NH₄), three new hydrogen sulfates of the type M(HSO₄)(H₂SO₄) could be synthesized and structural characterized. The rubidium and caesium compounds are isotypic whereas NH₄(HSO₄)(H₂SO₄) is topologically very similar to both. All three compounds crystallize with nearly identical cell parameters [Rb: a = 7.382(1), b = 12.440(2), c = 7.861(2), β = 93.03(3); Cs: a = 7.604(1), b = 12.689(2), c = 8.092(2), β = 92.44(3); NH₄: a = 7.521(3), b = 12.541(5), c = 7.749(3), β = 92.74(3)], in the monoclinic space group P2₁/c, There exist two kinds of SO₄-tetrahedra: HSO₄^? anions (S1) and H₂SO₄-molecules (S2). The HSO₄^? anions form hydrogen bridged zigzag chains. In the case of the Rb and Cs compounds, the H₂SO₄ molecules connect these chains forming double layers. The metal atoms are coordinated by 9 O-atoms with M? O-distances of 2.97 – 3.39 Å (Rb) and 3.13 – 3.51 Å (Cs). In the ammonium compound additional hydrogen bonds are formed originating from the NH₄⁺ cation. This finally leads to the formation of S2? NH₄⁺ chains (parallel to the S1 chains) as well as to a three-dimensional connection of both kinds of chains.     

[Ag(NH3)2]ClO4: Kristallstrukturen,Phasenumwandlung, Schwingungsspektren

[Ag(NH₃)₂]ClO₄: Crystal Structures, Phase Transition, and Vibrational Spectra [Ag(NH₃)₂](ClO₄) is obtained from a solution of AgClO₄ in conc. ammonia as colourless single crystals (orthorhombic, Pnmn, Z = 4, a = 795.2(1) pm, b = 617.7(1) pm, c = 1298.2(2) pm, R_all = 0.0494). The structure consists of linearly coordinated cations, [Ag(NH₃)₂]⁺, stacked in a staggered conformation and of tetrahedral (ClO₄)^‐ anions. A first order phase transition was observed between 210 and 200 K and the crystal structure of the low‐temperature modification (monoclinic, P2/m, Z = 4, a = 789.9(5) pm, b = 604.1(5) pm, c = 1290.4(5) pm, β = 97.436(5)°, at 170 K, R_all = 0.0636) has also been solved. Spectroscopic investigations (IR/Raman) have been carried out and the assignment of the spectra is discussed.     

Neue ternäre Alkalimetallhydroxide,MLi2(OH)3mit M ≙ K,Rb, Cs sowie ein Caesiumdilithiumamid,CsLi2(NH2)3 – Strukturverwandtschaft zum BaNiO3-Typ und zu LiOH

New Ternary Alkalimetalhydroxides, MLi₂(OH)₃with M ? K, Rb, Cs and a Cesiumdilithiumamide, CsLi₂(NH₂)₃- Structural Relations to the BaNiO₃-type and to LiOH The systems LiOH/MOH with M ? K, Rb, Cs have been investigated. Several synthetic routes were chosen. Phase analysis was done by x-ray methods. In addition to the binary hydroxides only one ternary compound was found in each of the corresponding systems. The reaction of Cs and Li metal with NH₃ in high-pressure autoclaves leads to CsLi₂(NH₂)₃ and further ternary amides. X-ray structure determinations of the four compounds were performed. The isotypic hydroxides crystallize in the space group P2₁/m with two formula units in the unit cell. CsLi₂(NH₂)₃shows orthorhombic symmetry (Cmcm, Z = 4) and its structure is closely related to that of the hydroxides. (For lattice parameters see ?Inhaltsübersicht”?). The atomic arrangements for the hydroxides and for tho amide can be dorived from the BaNiO₃-type of structure as well as from that of LiOH. The structural influence of the charge asymmetry of the anions is discussed.     

Untersuchungen über Alkalimetall-1,2-ethandithiolate

Studies on 1,2-Ethanedithiolates of Alkali Metals The 1,2-ethanedithiolates M₂[SCH₂CH₂S], where M = Li, Na, K, Rb, Cs, Tl, NH₄, have been prepared by different procedures. The compounds have been characterized by means of chemical and physical methods.     

Ammonium-Alkali-Hexafluorometallate(lll) vom Elpasolith-Typ

Inhaltsübersicht. Durch Festkörperreaktion in Gold- oder Platinampullen unter Druck wurde die Darstellung von Ammonium-Alkali-Hexafluorometallaten(III) vom Typ (NH₄)₂AMF₆ (A = Li, Na, K, Rb) und A₂NH₄MF₆ (A = Eb, Cs) mit M = Al, Ga, Cr, Fe und V versucht. Die Verbindungen (NH₄)₂NaMF₆, (NH₄)₂KMF₆ und Cs₂NH₄MF₆ kristallisieren kubisch flächenzentriert im Elpasolith-Typ, wie aus Röntgenpulveraufnahmen, z. T. auch durch Intensitätsrechnung, belegt wird. Die Ammoniumionen liegen hier entweder in reiner 12facher (Na- und K-Verbindung) oder in reiner 6facher Koordination (Cs-Verbindung) vor. Ammonium Alkali Hexafluorometallates(III) of Elpasolite Type The preparation of ammonium alkali hexafluorometallates(III) of type (NH₄)₂AMF₆ (A = Li, Na, K, Rb) and A₂NH₄MF₆ (A = Rb, Cs), where M means Al, Ga, Cr, Fe and V, was attempted (by solid state reaction in sealed gold or platinum tubes under pressure. The compounds (NH₄)₂NaMF₆, (NH₄)₂KMF₆ and Cs₂NH₄MF₆ crystallize cubic face centered in the elpasolite structure as could be showed by X-ray powder patterns, in part by calculations of intensities. The ammonium ion have the coordination number 12 (Na and K compounds) or 6 respectively (Cs compounds).     

Über die Systeme AJ/CoJ2 und die kristallchemischen Beziehungen in der Gruppe der Doppelhalogenide AnCoX(n+2) mit X = Cl,Br, J [1]

The Systems AI/CoI₂ (A = Alkali Metal, Tl, Ag) and the Crystal Chemistry of the Double Halides A_nCoX_(n+2) with X = Cl, Br, I The systems AI/CoI₂ (A = Cs, Rb, K, Tl, Na, Ag) were investigated by differencethermal analysis. The systems of NaI and AgI are found to be eutectical. A compound A₂CoI₄ always exists in the other systems. Cs₂CoI₄ crystallizes in the β-K₂SO₄ type with a coordination number (C.N.) for Cs equal to 9/10. Results obtained with single crystal technique reveal for the first time that among the double halides Rb₂CoI₄ is of the monoclinic Sr₂GeS₄ type (C. N. for Rb = 6(+2)). The compounds K₂CoJ₄, Tl₂CoJ₄, T-K₂CoBr₄, and T-Tl₂CoBr₄ are isotypic. Both structure groups are characterized by isolated CoX₄^2? tetrahedra. Reflectance spectra and magnetic susceptibilities can be explained on the basis of crystal field theory. – Our results close presently existing gaps in the knowledge on systems of CoBr₂ and CoCl₂ too.     

Syntheses and characterization of ANi(AsF6)3 (A = H3O, O2, NO, NH4, K, Rb, and Cs) compounds

ANi(AsF₆)₃ (A = O₂⁺, NO⁺, NH₄⁺) compounds could be prepared by reaction between corresponding AAsF₆ salts and Ni(AsF₆)₂. When mixtures of AF (A = Li, Na, K, Rb, Cs) and NiF₂ are dissolved in aHF acidified with an excess of AsF₅ the corresponding AAsF₆ and Ni(AsF₆)₂ were formed in situ. For A = Li and Na only mixtures of AAsF₆ and Ni(AsF₆)₂ were obtained, while for A = K, Rb and Cs, the final products were ANi(AsF₆)₃ (A = K-Cs) compounds contaminated with AAsF₆ (A = K-Cs) and Ni(AsF₆)₂.ANi(AsF₆)₃ (A = H₃O⁺, O₂⁺, NO⁺, NH₄⁺ and K⁺) compounds are structurally related to previously known H₃OCo(AsF₆)₃. The main features of the structure of these compounds are rings of NiF₆ octahedra sharing apexes with AsF₆ octahedra connected into infinite tri-dimensional network. In this arrangement cavities are formed where single charged cations are placed.In O₂Ni(AsF₆)₃ the vibrational band belonging to O₂⁺ vibration is found at 1866 cm⁻¹, which is according to the literature data one of the highest known values, and it is only 10 cm⁻¹ lower than the value for free O₂⁺.     

Darstellung und Kristallstruktur von (NH4)2[V(NH3)Cl5]. Die Kristallchemie der Salze (NH4)2[V(NH3)Cl5], [Rh(NH3)5Cl]Cl2 und M2VXCl5 mit M = K,NH4, Rb,Cs und X = Cl,O

Preparation and Crystal Structure of (NH₄)₂[V(NH₃)Cl₅]. The Crystal Chemistry of the Compounds (NH₄)₂[V(NH₃)Cl₅], [Rh(NH₃)₅Cl]Cl₂, and M₂VXCl₅ with M = K, NH₄, Rb, Cs and X ? Cl, O (NH₄)₂[V(NH₃)Cl₅] crystallizes like [Rh(NH₃)₅Cl]Cl₂ in the orthorhombic space group Pnma with Z = 4. The compounds are built up by isolated NH₄⁺ or Cl^? and complex MX₅Y ions. The following distances have been observed: V? N: 213.8, V? Cl: 235.8–239.1, Rh? N: 207.1–208.5, Rh? Cl: 235.5 pm. Both structures differ from the K₂PtCl₆ type mainly in the ordering of the MX₅Y polyhedra. The compounds M₂VCl₆ and M₂VOCl₅ with M = K, NH₄, Rb, and Cs crystallize with exception of the orthorhombic K₂VOCl₅ in the K₂PtCl₆ type. The ordering of the MX₅Y polyhedra in the compounds (NH₄)₂[V(NH₃)Cl₅], [Rh(NH₃)₅Cl]Cl₂ and K₂VOCl₅ enables a closer packing.     

Über Chalkogenolate. 159. Umsetzung von 1,2-Ethandithiolaten mit Kohlenstoffdisulfid 1. Darstellung und Eigenschaften von 1,2-Ethan-bis(trithiocarbonaten)

On Chalcogenolates. 159. Reaction of 1,2-Ethanedithiolates with Carbon Disulfide. 1. Synthesis and Characterization of 1,2-Ethane-bis(trithiocarbonates) The reaction of 1,2-ethanedithiolates with carbon disulfide forms the corresponding 1,2-ethane-bis(trithiocarbonates). The compounds M₂[S₂C? SCH₂CH₂S? CS₂] with M = Li, Na, K, Rb, Cs, NH₄, Tl have been characterized with chemical methods as well as by means of electron absorption, infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra.     

Syntheses and Characterization of 1,4‐Phenylenebisphosphonates,A[HO3PC6H4PO3H2] (A = Li,K, Rb,Cs, Tl,Ag and NH4) and Crystal Structure of 1,4‐Phenylenebisphosphonic Acid

Seven 1,4‐phenylenebisphosphonates of monovalent ions, A(HO₃PC₆H₄PO₃H₂) (A = Li, K, Rb, Cs, Tl, Ag and NH₄), were synthesized and characterized by single‐crystal X‐ray diffraction, spectroscopic and thermal methods. These compounds and the reported sodium analogue have four structure types. The sodium compound, one‐dimensional lithium compound and pillared‐layered cesium compounds have different structure types, whereas the potassium, rubidium, thallium, ammonium and silver compounds have a pillared ladder‐like structure. They undergo initial thermal decomposition in the range of 120–270 °C. Moreover, the single crystal X‐ray structure of 1,4‐phenylenebisphosphonic acid was determined.     

Solid electrolytes with predominant chloride conductivity

The ionic transport features were studied in PbCl₂ and SnCl₂ single crystals and in KPb₂Cl₅, K₂PbCl₄, PbCl₂-Al₂O₃, CsSnCl₃, and SnCl₂ - 6 mol % MCl (M = Li, Na, Ag, K, Tl, Rb, Cs) ceramic materials. A reference data review on electroconductivity of chloride-conducting solid electrolytes was made. A conclusion was made on application prospects of ionic conductors with predominant chloride conductivity as sensitive membranes in solid state electrochemical devices.     

Synthesis and physicochemical properties of new hafnium fluoro complexes (NH4)6MHf4F23 (M = K, Rb, Cs)

Ammonium-containing hafnium fluoro complexes (NH₄)₆MHf₄F₂₃ (M = K, Rb, Cs), which crystallize in orthorhombic symmetry, were synthesized and studied. Their unit cell parameters were determined. The IR absorption spectra of the synthesized complexes were studied in the region of 350?C4000 cm^?1.     

Additive prediction of thermodynamic functions of hydrofluorides

Summary The experimental data available on the thermodynamic functions ⁰ forMF·nHF hydrofluorides [M=Li, Na, K, Rb, Cs, NH₄, Ag(I) and Tl(I);n=1–3] have been evaluated additively. The unknown values of ⁰ forn=0÷7 are predicted.

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Additive Voraussagen der thermodynamischen Funktionen von Hydrogenfluoriden (Kurze Mitt.)

Zusammenfassung Die vorhandenen experimentellen Daten über die thermodynamischen Funktionen ⁰ von HydrogenfluoridenMF·nHF [M=Li, Na, K, Rb, Cs, NH₄, Ag(I) und Tl(I);n=1–3] werden linear ausgeglichen und die fehlendenden Werte für ⁰ mitn=0÷7 vorausgesagt.