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  • Wiley-Blackwell  (3)
  • 1980-1984  (3)
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  • 1
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Kristallstruktur der Diphenyldithiophosphinsäure (C6H5)2P(S)SH wurde röntgenographisch bei tiefer Temperatur und Normaltemperatur aus Einkristalldiffraktometerdaten bestimmt und bis zu R-Werten von 0,037 (140 K, (sin Θ)/λ 〈 0,81 Å-1) und 0,035 (293 K, (sin Θ)/λ 〈 0,64 Å-1) verfeinert. Die Verbindung kristallisiert in der monoklinen Raumgruppe P21/c mit den bei 140 K (in Klammern: 293 K) gemessenen Gitterkonstanten a = 9,824(3) (9,887), b = 10,061(3) (10,175), c = 14,342(4) (14,433) Å, β = 122,08(3) (121,73)° und V = 1201,1 (1234,9) Å3, Z - 4. Im Kristall sind individuelle Moleküle über fast lineare S—H…S-Wasserstoffbrückenbindungen zu schraubenförmig gewundenen Ketten verknüpft. Bei 140 K beträgt der S…S-Abstand innerhalb der Brücke 3,790(1) Å; die weiteren geometrischen Daten der Wasserstoffbrücke sind: d(S—H): 1,25(2), d(S…H): 2,56(2), d(P—S): 2,077(1), d(P=S): 1,954(1) Å, ∢ (S—H…S): 169,5(14), ∢ (P—S…S): 98,87(2), ∢ (P=S…S): 96,65(2)°.Investigations on Compounds Containing S—H…S Hydrogen Bonds. Crystal Structure of Diphenyldithiophosphinic Acid at 140 and 293 KThe crystal structure of diphenyldithiophosphinic acid (C6H5)2P(S)SH was determined from X-ray diffraction data collected at 140 and 293 K and was refined to R factors of 0.037 (140 K, (sin Θ)/λ 〈 0.81 Å-1) and 0.035 (293 K, (sin Θ)/λ 〈 0.64 Å-1) respectively. The compound crystallizes in the monoclinic space group P21/c with unit cell parameters at 140 K (in parentheses: at 293 K): a = 9.824(3) (9.887), b = 10.061(3) (10.175), c = 14.342(4) (14.433) Å, β = 122.08(3) (121.73)° and V = 1201.1 (1234.9) Å3, Z = 4. In the crystalline state individual molecules are linked together by nearly linear S—H…S hydrogen bonds so that endless helical chains are formed. At 140 K the S…S distance within the hydrogen bond is 3.790(1) Å; the other distances and angles associated with the bridge are: d(S—H): 1,25(2), d(S…H): 2,56(2), d(P—S): 2,077(1), d(P=S): 1.954(1) Å, ∢ (S—H…S): 169.5(14), ∢ (P—S…S): 98.87(2), ∢ (P—S…S): 96.65(2)°.
    Additional Material: 3 Ill.
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  • 2
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: CF3SO2N=SCl2 reagiert mit (CH3)2S[NSi(CH3)3]2, (C4H8)S[NSi(CH3)3]2 oder (C5H10)S[NSi(CH3)3]2 unter Trimethylchlorsilanabspaltung zu den achtgliedrigen S4N4-Derivaten S4N4(NSO2CF3)2(CH3)4 3, S4N4(NSO2CF3)2(C4H8)2 4a und S4N4(NSO2CF3)2(C5H1 0)2 4b. In den achtgliedrigen SN-Ringen haben die Schwefelatome die Koordinationszahl 3 und 4. Die Röntgenstrukturanalyse von 4a ergab eine Sessel-Konformation. 4a kristallisiert orthorhombisch in der Raumgruppe Pna21 mit a = 17,641(4), b = 6,406(2), c = 19,130(4) Å, dx = 1,815 g cm-3 und Z = 4. Die mittleren S—N-Abstände betragen an den vierfach koordinierten Schwefelatomen 1,597 Å und an den Schwefelatomen mit der Koordinationszahl 3 1,650 Å.CF3SO2N—SCl2 reagiert mit trimethylzinnhaltigen S—N-Verbindungen zum bekannten CF3SO2N[Sn(CH3)3]S(CH3)NSO2CF3 und Dimethylzinndichlorid.Synthesis and X-Ray Structure Analysis of S4N4-Derivatives with Threefold and Fourfold Coordinated Sulfur AtomsCF3SO2N=SCl2 reacts with (CH3)2S[NSi(CH3)3]2, (C4H8)S[NSi(CH3)3]2 or (C5H10S[NSi(CH3)2]2 under elimination of (CH3)3SiCl to yield the eight-membered S4N4 derivatives S4N4-NSO2CF3)2(CH3)4, 3, S4N4(NSO2CF3)2(C4H8)2 4a und S4N4(NSO2CF3)2(C5H1 0)2 4b. In the eight-membered SN-rings the sulfur atoms have the coordination number 3 and 4. The X-ray structure analysis of 4a revealed a chair conformation. 4a crystallizes in the orthorhombic space group Pna21 with a = 17.641(4), b = 6.406(2), c = 19.130(4) Å, dx = 1.815 g cm-3, and Z = 4. The average S—N distance was found to be 1.597 Å at fourfold coordinated sulfur atoms and 1.650 Å at sulfur with coordination number 3. CF3SO2N=SCl2 reacts with trimethyl tin-containing S—N compounds to the known CF3SO2N[Sn(CH3)3]S(CH3)NSO2CF3 and dimethyl tin dichloride.
    Additional Material: 2 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 474 (1981), S. 149-156 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal Structure of Ti7Cl16 and Ti7Br16: Compounds with Trigonal Ti3 ClustersThe mixed-valence titanium halides Ti7Cl16 and Ti7Br16 are isotypic and have orthorhombic unit cells (space group Pnnm) with a = 14.421(4), b = 9.987(3), c = 6.890(2) Å and a = 5.228(4), b = 10.577(3), c = 7.276(2) Å, Z = 2. The crystal structures were determined from single-crystal X-ray diffraction data (R = 0.029 and 0.063). The structures consist of trimeric Ti3Cl13 and Ti3Br13 cluster units which are linked three-dimensionally to each other and to isolated TiCl6 (TiBr6) octahedra. The Ti—Ti bond lengths in the equilateral Ti3 triangles of the clusters are strongly dependent from the halogen, being 2.953 - 2.955(2) Å for Ti7Cl16 and 3.073 - 3.097(6) Å for Ti7Br16. By the Ti—Ti bonds the Ti atoms of the Ti3Cl13 (Ti3Br13) groups are displaced from the centres of their octahedral coordination towards the Ti3 centre. This leads to the Ti—Cli (Ti—Bri) bond lengths of 2.359 - 2.424(2) Å (2.509 - 2.574(4) Å) being much shorter than the rest of the Ti—Cl (Ti—Br) bonds of 2.508 - 2.642(2) Å (2.659 - 2.826(7) Å).
    Notes: Die gemischt-valenten Titanhalogenide Ti7Cl16 und Ti7Br16 sind isotyp und kristallisieren orthorhombisch in der Raumgruppe Pnnm mit a = 14,421(4), b = 9,987(3), c = 6,890(2) Å bzw. a = 15,228(4), b = 10,577(3), c = 7,276(2) Å, Z = 2. Die Kristallstrukturen wurden aus Einkristall-Röntgenbeugungsdaten bestimmt (R = 0,029 bzw. 0,063). Sie bestehen aus trimeren Ti3Cl13- bzw. Ti3Br13-Clustereinheiten mit formal zweiwertigem Titan (d2), die untereinander und über isolierte TiCl6- (TiBr6-) Oktaeder (formal Ti(IV) (d°)) zu einem dreidimensional vernetzten Gerüst verknüpft sind. Die Ti—Ti-Bindungslängen in den gleichseitigen Ti3-Dreiecken der Clustereinheiten sind stark abhängig vom Halogen und betragen 2,953 - 2,955(2) Å für Ti7Cl16 und 3,073 bis 3,097(6) Å für Ti7Br16. Die Ti-Atome der Ti3Cl13- (Ti3Br13-) Gruppen sind durch die Ti—Ti-Bindungen aus den Zentren ihrer oktaedrischen Koordination stark in Richtung auf das Ti3-Zentrum verschoben. Dies führt zu einer erheblichen Verkürzung der Ti—Cli- (Ti—Bri-) Bindungslängen mit 2,359 bis 2,424(2) Å (2,509 - 2,574(4) Å) gegenüber den übrigen Ti—Cl- (Ti—Br-) Bindungen mit 2,508 bis 2,642(2) Å (2,659 - 2,826(7) Å).
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