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  • 1995-1999  (1)
  • 1985-1989  (1)
  • 1
    ISSN: 0044-2313
    Keywords: TlEu[PS4] ; Tetrathiophosphate(V) ; Crystal Structure ; Vibrational Spectrum ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Kristallstruktur und Schwingungsspektrum von Thallium(I)-Europium(II)-tetrathiophosphat(V), TlEu[PS4]TlEu[PS4] wurde aus den Elementen bei 1 150 K in einer evakuierten Quarzampulle dargestellt. Die Verbindung bildet transparente, orangefarbene, luft- und feuchtigkeitsbeständige Nadeln, die orthorhombisch, Pnma (Nr. 62) mit a = 12,157(2), b = 6,581(1), c = 8,802(2) Å, Z = 4 kristallisieren. Charakteristisch sind diskrete [PS4]3--Anionen, die durch Tl+ und Eu2+ verbunden sind. Sie sind verzerrt tetraedrisch mit P—S-Abständen zwischen 2,028 und 2,043 Å und so angeordnet, daß Liganden benachbarter Gruppen trigonale S6-Prismen bilden, entlang [0 0 1] zu Säulen verknüpft, die parallel (1 0 0) über gemeinsame Kanten zu gewellten Schichten kondensiert sind. Dazwischen sind leere, verzerrte Halbwürfel und zur Hälfte mit P-Atomen besetzte Tetraederlücken Durch die alternierende Besetzung mit Tl+ und Eu2+ sind diese Prismen leicht verzerrt. Man kann daher diese Struktur als eine geordnete, teilweise aufgefüllte Überstruktur des InNi2-Typs auffassen (InInNi4□2tet ≙ TlEuS4P□1tet), aber auch als zentrosymmetrische Variante der TlSn[PS4]-Struktur (Raumgruppe Pna21). Das Schwingungsspektrum entspricht der Strukturbestimmung, die beobachteten Raman- und Infrarotbanden lassen sich zwanglos auf der Basis von [PS4]3- -Einheiten mit C2v-Symmetrie zuordnen.
    Notes: TlEu[PS4] was synthesized from the elements in a sealed quartz ampoule at 1 150 K. The compound forms transparent orange needles, stable in air and moisture. It crystallizes in the orthorhombic system, space group Pnma (No. 62), with cell dimensions a = 12.157(2), b = 6.581(1), c = 8.802(2) Å, Z = 4. The crystal structure consists of discrete [PS4]3- anions interconnected by Tl+ and Eu2+. The tetrahedral [PS4]3- groups are slightly distorted with P—S bond lengths in the range 2.028 to 2.043 Å. These tetrahedral anions are arranged in such a way that the sulfur atoms form columns of distorted trigonal S6 prisms along [0 0 1]. The columns are condensed via common edges to puckered layers parallel to (1 0 0). The interlayer region consists of empty distorted half-cubes and tetrahedral holes, half of them filled by P atoms. The trigonal prisms in the columns are centered alternately by Tl+ and Eu2+. In this way, the structure can be regarded as an ordered superstructure of the InNi2 type, where half of the tetrahedral holes are filled by phosphorus atoms: InInNi4□2tet ≙ TlEuS4P□1tet. TlEu[PS4] is a centrosymmetric variant of the TlSn[PS4] structure type (space group Pna21). The vibrational spectrum is in accordance with the X-ray crystal structure, the Raman and infrared vibrations are assigned on the basis of [PS4]3- units with C2v symmetry.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0377-0486
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: AuPS4 has been prepared and characterized by vibrational spectroscopy, differential thermal analysis and chemical analysis. The frequencies are tentatively assigned. A polymer chain structure is proposed. Normal coordinate analyses have been carried out for different fragments of the AuPS4 chain. PED calculations show strong v(Au—S) and δ(SPS) couplings and remarkably high Au—S frequencies.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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