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  • 1
    ISSN: 0044-2313
    Keywords: Potassium hydroxide dihydrate ; tetrahydrate ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Hydrates of Weak and Strong Bases. V. Crystal Structures of KOH · 2H2O (Substructure) and KOH · 4H2OIn the context of studies on formation and structure of base hydrates the crystal structures of KOH · 2H2O and KOH · 4H2O have been determined. For both structures, Mokα diffractometer data were used, obtained at -150°C, which allowed also the complete set of H atoms to be localized and refined. The dihydrate, melting incongruently at 33°C, crystallizes with a superstructure. The substructure, which is reported here, is tetragonal with space group I41/amd and Z = 8 formula units per unit cell of dimensions a = 7.154 and c = 13.415 Å. With 462 independent observed reflections an R value of 0.026 was obtained. K(H2O)8+ cubes via common faces form rods and these in a tetragonal four-layer packing pattern are further linked into a three-dimensional framework. The OH-ions, hydrogen-bonded by the H2O molecules, are located with a twofold disorder in additional cubes of this frame-work, not occupied by K+ ions. The tetrahydrate, melting congruently at -33.7°C, is monoclinic with space group P21/c and Z = 4. The unit cell dimensions are a = 6.951, b = 11.530, c = 7.080 Å and β = 99.19°. With 2198 independent observed reflections the final R value is 0.025. Trigonal K(H2O)6+ prisms across common edges form layers, which are linked with each other via OH- ions and only loosely cation-bonded H2O molecules.
    Notes: Im Rahmen von Untersuchungen zu Bildung und Struktur von Basehydraten wurden die Kristallstrukturen von KOH · 2H2O und KOH · 4H2O bestimmt. Benutzt wurden hierzu bei -150°C mit Mokα-Strahlung erhaltene Diffraktometerdaten, mit denen auch sämtliche H-Atome lokalisiert und verfeinert werden konnten. Das bei 33°C inkongruent schmelzende Dihydrat kristallisiert mit einer Überstruktur. Die Substruktur, über die hier berichtet wird, ist tetragonal mit der Raumgruppe 141/amd und Z = 8 Formeleinheiten pro Elementarzelle sowie den Gitterkonstanten a = 7,154 und c = 13,415 Å. Mit 462 unabhängigen beobachteten Reflexen wurde ein R-Wert von 0,026 erreicht. K(H2O)8+ -Würfel bilden über gemeinsame Flächen Stäbe und durch weitere Verknüpfung ein nach dem Muster einer tetragonalen Vierschichtpackung aufgebautes dreidimensionales Gerüst. Die OH- -Ionen befinden sich, durch Wasserstoffbrücken von den H2O-Molekülen gebunden, mit zweifacher Fehlordnung in weiteren, nicht mit K+ -Ionen besetzten Würfeln dieses Gerüsts. Das bei -33,7°C kongruent schmelzende Tetrahydrat ist monoklin mit der Raumgruppe P21/c und Z = 4. Die Gitterkonstanten betragen a = 6,951, b = 11,530, c = 7,080 Å und β = 99,19°. Mit 2198 unabhängigen beobachteten Reflexen liegt der abschließende R-Wert bei 0,025. Trigonale K(H2O)6+ -Prismen bilden über gemeinsame Kanten Schichten, die durch Wasserstoffbrücken über OH- -Ionen und nur locker an die Kationen gebundene H2O-Moleküle miteinander verbunden sind.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 620 (1994), S. 509-513 
    ISSN: 0044-2313
    Keywords: (difluoro)methylphosphine ; (difluoro)methylphosphonium salts ; preparation ; single crystall X-ray structure ; vibrational and NMR spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Crystal Structures of CH3PF2H+AsF6- and CH3PF2H+SbF6- and a simple Method for Preparation of CH3PF2A simple method for preparation of CH3PF2 from CH3PCl2 is reported. The phosphonium salts CH3PF2H+MF6- are obtained by the reaction of CH3PCl2 with superacidic systems HF/MF5 (M = As, Sb). CH3PF2H+SbF6- crystallizes in the space group P1 with a = 548.4(4) pm, b = 695.5(8) pm, c = 960.2(9) pm, α = 94.68(5)°, β = 97.19(6)°, γ = 94.41(6)° and Z = 2. CH3PF2H+SbF6- crystallizes in P1 with a = 554.3(3), b = 724.2(4), c = 970.4(5), α = 94.73(4)°, β = 96.14(5)°, γ = 95.30(4)°.
    Notes: Es wird über eine einfache Darstellung von CH3PF2 aus CH3PCl2 berichtet, welches in den supersauren Systemen HF/MF5 (M = As, Sb) zu den Phosphoniumsalzen CH3PF2H+MF6- protoniert wird. CH3PF2H+AsF6- kristallisiert in der Raumgruppe P1 mit a = 548,4(4) pm, b = 695,5(8) pm, c = 960,2(9) pm, α = 94,68(5)°, β = 97,19(6)°, γ = 94,41(6)° und Z = 2, das isostrukturelle CH3PF2H+SbF6- mit a = 554,3(3), b = 724,2(4), c = 970,4(5), α = 94,73(4)°, β = 96,14(5)°, γ = 95,30(4)°.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 596 (1991), S. 35-46 
    ISSN: 0044-2313
    Keywords: Cyclosilazanes ; Si3N4 ceramics ; preparation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cyclosilazanes as Precursors of Si3N4-CeramicsThe products obtained in the reaction of 1-trimethylsilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane 1 with butyllithium and fluorosilanes depend on the reaction conditions.Lithiated 1 reacts with SiF3N(SiMe3)2 at low temperatures to give the mono- and disubstituted compounds (2, 3) and the 1,3,5,7-tetraaza-2,4,6,8-tetrasilabicyclo-[4.2.0] octane 4. The permethylated bicyclus 5 is formed in the analogous reaction with MeSiF2N(SiMe3)2. At room temperature the monolithium salt of 1 reacts with SiF3N(SiMe3)2 to give the cyclodisilazane 6. 6 forms with butyllithium the lithium derivate 7. 7 reacts with SiF3N(SiMe3)2 to give 8, an isomeric cyclodisilazane of 3. In the reaction of lithiated 1 with Me2SiF2 the silylcoupled cyclodisilazane 9 is obtained, which is a suitable precursor of Si3N4 ceramics.The results of the crystal structure determination of 7 and the results of the pyrolysis of 9 are reported.
    Notes: Die Produktbildung in der Reaktion von 1-Trimethylsilyl-2,2,4,4,6,6-hexamethylcyclotrisilazan 1 mit Butyllithium und Fluorsilanen ist durch die Reaktionsbedingungen steuerbar.Lithiiertes 1 reagiert mit F3SiN(SiMe3)2 bei tiefen Temperaturen unter Bildung der Mono- und Disubstitutionsverbindungen 2, 3 sowie des 1,3,5,7-Tetraaza-2,4,6,8-tetrasilabicyclo [4.2.0] octans 4. Ein permethylierter Bicyclus (5) entsteht in analoger Reaktion mit MeSiF2N(SiMe3)2. Bei Raumtemperatur reagiert das Monolithiumsalz von 1 mit F3SiN(SiMe3)2 unter Kontraktion zum Cyclodisilazan 6. 6 bildet mit Butyllithium das Lithiumderivat 7. 7 reagiert mit F3SiN(SiMe3)2 zu 8, dem zu 3 isomeren Cyclodisilazan. In der Reaktion von lithiiertem 1 mit Me2SiF2 wird das silylverbrückte Cyclodisilazan 9 erhalten, das in Pyrolysereaktionen ein geeignetes Ausgangsmaterial für Si3N4-Keramiken darstellt. Die Resultate der Röntgenstrukturanalyse von 7 und der Pyrolyse von 9 werden mitgeteilt.
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  • 4
    ISSN: 0044-2313
    Keywords: Ruthenium ; boranes ; organoruthenaboranes ; preparation ; mass, n.m.r. spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Organoruthenaboran-Chemie. IX. Die Reaktion von [{(η6-C6Me6)RuCl2}2] und [{(η6-MeC6H4-4-iPr)RuCl2}2] mit dem [nido-B9H12]--AnionDie Reaktion zwischen [NnBu4][nido-B9H12] und [{(η6-C6Me6)RuCl2}2] in CH2Cl2-Lösung ergibt [5-Cl-6-(η6-C6Me6)-nido-6-RuB9H12] (12%), [6-(η6-C6Me6)-nido-6-RuB9H13] (1%) und [1-(η6-C6Me6)-isocloso-1-RuB9H9] (2%). Die entsprechende Reaktion mit dem p-Cymol-Analogon [{(η6-MeC6H4-iPr)RuCl2}2] ergibt [5-Cl-6-(η6-MeC6H4-4-iPr)-nido-6-RuB9H12] (15%), [6-(η6-MeC6H4-4-iPr)-nido-6-RuB9H13] (1%) und [1-(η6-MeC6H4-4-iPr)-isocloso-1-RuB9H9] (3%). Die Produkte sind gelbe, luftstabile Festkörper; sie wurden chromatographisch getrennt und massenspektroskopisch und NMR-spektroskopisch charakterisiert.
    Notes: Reaction between [NnBu4][nido-B9H12] and [{(η6-C6Me6)RuCl2}2] in CH2Cl2 solution yields [5-Cl-6-(η6-C6Me6)-nido-6-RuB9H12] (12%), [6-(η6-C6Me6)-nido-6-RuB9H13] (1%), and [1-(η6-C6Me6)-isocloso-1-RuB9H9] (2%). The corresponding reaction with the p-cymene analogue [{(η6-MeC6H4-4-iPr)RuCl2}2] yields [5-Cl-6-(η6-MeC6H4-4-iPr)-nido-6-RuB9H12] (15%), [6-(η6-MeC6H4-4-iPr)-nido-6-RuB9H13] (1%), and [1-(η6-MeC6H4-4-iPr)-isocloso-1-RuB9H9] (3%). The products were all yellow, air-stable solids; they were separated by chromatography and characterized by mass spectrometry and n.m.r. spectroscopy.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 618 (1992), S. 60-63 
    ISSN: 0044-2313
    Keywords: Litho-Manganate(V), Cs2{Li[MnO4]} ; preparation ; single crystal structure ; MAPLE calculation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The First “Litho-Manganate(V)” with Layer-Structure: Cs2{Li[MnO4]}By heating intimate mixtures of the oxides [CsO1,2, Li2MnO3; Cs: Mn = 2,3 : 1; Ag-Zylinder, 580°C, 62 d] blue-green single crystals of Cs2{Li[VO4]} were obtained for the first time. The new “Litho-Manganate(V)” crystallices orthorhombic (SG: Cmc21) with a = 596.08(7), b = 1202.6(1), c = 816.8(1) pm (Guinier-Simon data), Z = 4. It is isotypic with Cs2{Li[VO4]} [1].The structure was determined by four-circle-diffractometer data [Mo—Kα, for 496Io(hkl) R = 3.1%, R, = 2.4%], parameters see text.The Madelung Part of Lattice Energie, MAPLE and Effective Coordination Numbers, ECoN, these calculated via Mean Fictive Ionic Radii, MEFIR, are calculated and disscussed.
    Notes: Erstmals wurde Cs2{Li[MnO4]} beim Tempern inniger Gemenge der Oxide [CsO1,2, Li2MnO3; Cs: Mn = 2,3 : 1; Ag-Zylinder, 580°C, 62d] in Form blaugrüner Einkristalle erhalten. Das neue “Litho-Manganat(V)” kristallisiert orthorhombisch (RG: Cmc21) mit a = 596,08(7), b = 1202,6(1), c = 816,8(1) pm (Guinier-Simon-Daten), Z = 4. Es ist isotyp zu Cs2{Li[VO4]} [1].Die Strukturaufklärung erfolgte mittels Vierkreisdiffraktometerdaten [Mo—Kα, für 496 Io(hkl) R = 3,1%, Rw = 2,4%], Parameter siehe Text.Der Madelunganteil der Gitterenergie, MAPLE und die Effektiven Koordinationszahlen, ECoN, diese über Mittlere Fiktive Ionenradien, MEFIR, werden berechnet und diskutiert.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 618 (1992), S. 74-76 
    ISSN: 0044-2313
    Keywords: Tris(fluoraryl)boranes ; preparation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Properties of New Tris(fluoroaryl)boranesB(2-FC6H4)3, B(4-FC6H4)3, B(2,6-F2C6H3)3 and B(C5F4N)3 are prepared from the reactions of RMgX with boron trifluoride, B(OC6F5)3 and B(SC6F5)3 from C6F5XH (X = O, S) and boron trichloride. The synthetic routes and the properties of these mainly new compounds are described.
    Notes: B(2-FC6H4)3, B(4-FC6H4)3, B(2,6-F2C6H3)3 und B(C5F4N)3 werden durch Reaktionen von RMgX mit Bortrifluorid, B(OC6F5)3 und B(SC6F5)3 aus C6F5XH (X = O, S) mit Bortrichlorid dargestellt. Die Syntheseverfahren und die Eigenschaften der meist neuen Verbindungen werden beschrieben.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 849-852 
    ISSN: 0044-2313
    Keywords: Bis(pyridin)bis(trifluoromethyl)zinc ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal and Molecular Structure of Bis(pyridine)bis(trifluoromethyl)zincBis(pyridin)bis(trifluoromethyl)zinc 1 has been isolated and characterized by means of single-crystal X-ray diffraction techniques. The title compound represents the first structure determination of a fully fluorinated alkylzinc compound (monoclinic, space group P21/c, Z = 4, a = 8.856(3), b = 18.158(3), c = 8.979(3) Å, β = 98.14(2)°, R = 0.054, Rw = 0.035). The zinc atom is in a distorted tetrahedral environment. The molecular structure of [ClZn(CCl2CF3) η2O]2 2 was solved, but is not included in a structural comparison due to crystallographic disorder.
    Notes: Der Pyridin-Komplex 1 von Bis(trifluoromethyl)zink wurde durch Einkristall-Röntgenstrukturanalyse charakterisiert. Die Titelverbindung repräsentiert die erste Struktur eines vollfluorierten Zinkalkyls (monoklin, Raumgruppe P21/c, Z = 4, a = 8,856(3), b = 18,158(3), c = 8,979(3) Å, β = 98,14(2)°, R = 0,054, Rw = 0,035). Das Zinkatom ist verzerrt tetraedrisch koordiniert. Die Kristall- und Molekülstruktur der zweikernigen Zinkverbindung [ClZn(CCl2CF3) η2O]2 2 wurde bestimmt, kann aber wegen kristallographischer Fehlordnung nicht einem Strukturvergleich unterzogen werden.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1419-1425 
    ISSN: 0044-2313
    Keywords: Lithium permanganate, Li[MnO4] ; preparation ; crystal structure ; neutron powder data ; MAPLE calculation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Coordination Number 4 or 6 for Lithium?: The Crystal Structure of Lithium Permanganate, Li[MnO4]Waterless 7Li[MnO4] was obtained by dehydration of 7Li[MnO4] · 3 D2O at 60°C above P4O10 in vacuum as violet powder.The structure determination by neutron diffraction measurements via pulsed polychromatic neutron source [time-of-flight powder diffractometer; profile-R-value = 2.1%, Bragg-R-value = 7.4%] confirms the space group Cmcm with a = 551.402(8), b = 839.754(15), c = 635.911(10) pm (Z = 4); parameters see text. The crystal structure of Li[MnO4] corresponds to the CrVO4-type with coordination number 6 for lithium and 4 for manganese.The Madelung Part of Lattice Energie, MAPLE, the Effective Coordination Numbers, ECoN and the charge distribution were calculated and discussed.
    Notes: Durch Trocknung von 7Li[MnO4] · 3 D2O bei 60°C über P4O10 im Vakuum wurde wasserfreies 7Li[MnO4] als violettes Pulver erhalten.Die Strukturaufklärung mittels Neutronenbeugungsmessungen im gepulsten polychromatischen Neutronenstrahl [Flugzeitdiffraktometer; Profil-R-Wert = 2,1%, Bragg-R-Wert = 7,4%] belegt die Raumgruppe Cmcm mit a = 551,402(8), b = 839,754(15), c = 635,911(10)pm (Z = 4); Parameter siehe Text. Die Kristallstruktur von Li[MnO4] entspricht dem CrVO4-Typ mit der Koordinationszahl 6 für Lithium und 4 für Mangan.Der Madelunganteil der Gitterenergie, MAPLE, Effektive Koordinationszahlen, ECoN und die Ladungsverteilung wurden berechnet und diskutiert.
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  • 9
    ISSN: 0044-2313
    Keywords: Methoxy(oxy)sulfonium hexafluoroarsenate ; preparation ; IR spectra ; force field calculation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal Structure, Vibrational Spectra, and Valence Force Field of Methoxy(oxy)-sulfonium Hexafluoroarsenate CH3OSO+ AsF6-Methoxy(oxy)sulfonium hexafluoroarsenate CH3OSO+ AsF6- crystallizes in the monoclinic space group P21/n with a = 547,0(4) pm, b = 1 728.1(5) pm, c = 767.8(4) pm, β = 106.69(4)°, Z = 4. The cation is planar with bond distances d(CO) = 150.2(9) pm, d(SO) = 150.5(5) pm, d(SO) = 139.7(5) pm and angles ∢ (COS) = 125.8(4)°, ∢ (OSO) = 114.9(3)°.The vibrational frequencies of the cation are discussed with correspondence to the values of 34S and 18O labelled substituted species. A force field calculation equates f(CO) = 3.75 Ncm-1, f(SO) = 6.91 Ncm-1, f(SO) = 10.81 Ncm-1.
    Notes: Methoxy(oxy)sulfonium-hexafluoroarsenat CH3OSO+ AsF6- kristallisiert in der monoklinen Raumgruppe P21/n mit a = 547,0(4) pm, b = 1 728,1(5) pm, c = 767,8(4) pm, β = 106,69(4)°, Z = 4. Das Kation ist planar mit Bindungsabständen von d(CO) = 150,2(9) pm, d(SO) = 150,5(5) pm, d(SO) = 139,7(5) pm und Winkeln ∢ (COS) = 125,8(4)°, ∢ (OSO) = 114,9(3)°.Die Schwingungsfrequenzen des Kations werden unter Einbeziehung der 34S und 18O markierten Spezies diskutiert. Eine Kraftfeldberechnung ergibt f(CO) = 3,75 Ncm-1, f(SO) = 6,91 Ncm-1, f(SO) = 10,81 Ncm-1.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 620 (1994), S. 514-518 
    ISSN: 0044-2313
    Keywords: N-Trifluormethyl-difluormethyleneiminium salts ; preparation ; n.m.r., i.r. spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation of the Iminium Salts CF3—NX=CF2+MF6- (X = CH3, F and M = As, Sb) and CF3—NCl=CF2+ AsF6-The preparation of the iminiumsalts CF3—NX=CF2+ MF6- (X = CH3, F and M = As, Sb) and CF3—NCl=CF2+ AsF6- is reported. The salts were characterized by NMR and infrared spectroscopy. CF3—NCH3=CF2+MF6- decompose into MF5 and (CF3)2NCH3.
    Notes: Es wird über die Darstellung der Iminiumsalze CF3—NX=CF2+ MF6- (X = CH3, F und M = As, Sb) und CF3—NCl=CF2+AsF6- berichtet. Die Salze werden durch NMR- und IR-Spektroskopie charakterisiert. CF3—NCH3=CF2+MF6- zerfällt in MF5 und (CF3)2NCH3.
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