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  • 1
    ISSN: 0044-2313
    Keywords: Rare Earths ; Bromides ; Copper ; Synthesis ; Crystal Structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Crystal Structure of (NH4)3Cu4Ho2Br13. Further Bromides of the (NH4)3Cu4M2Br13 Type (M = Dy—Lu, Y) and on Rb3Cu4Ho2Br13Single crystals of (NH4)3Cu4Ho2Br13 were obtained for the first time from the reaction of CuBr with HoBr3 which was contaminated with NH4Br: cubic, space group Pn3, Z = 2, a = 1101.71(5) pm. The crystal structure may be considered as a variant of the fluorite type according to [(HoBr6)4][(NH4)6(Cu4Br)2] ≡ Ca4F8. Pure products can be prepared from the binary halides in glass ampoules at 350°C. The bromides (NH4)3Cu4M2Br13 (M = Dy—Lu, Y) and Rb3Cu4Ho2Br13 are isotypic with (NH4)3Cu4Ho2Br13.
    Notes: Einkristalle von (NH4)3Cu4Ho2Br13 wurden erstmals bei der Reaktion von CuBr mit HoBr3, das mit NH4Br „verunreinigt“ war, erhalten: kubisch, Raumgruppe Pn3, Z = 2, a = 1101,71(5) pm. Die Kristallstruktur ist gemäß [(HoBr6)4][(NH4)6(Cu4Br)2] ≡ Ca4F8 als eine Variante des Flußspat-Typs aufzufassen. Reine Produkte können aus den binären Halogeniden bei 350°C in Glasampullen dargestellt werden. Die Bromide (NH4)3Cu4M2Br13 (M = Dy—Lu, Y) und Rb3Cu4Ho2Br13 sind mit (NH4)3Cu4Ho2Br13 isotyp.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0044-2313
    Keywords: Lithium ; Rare Earth Halides ; Crystal Structure ; Ionic Conductivity ; NMR Spectroscopy ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ternary Halides of the A3MX6Type. VII. The Bromides Li3MBr6 (M=Sm—Lu, Y): Synthesis, Crystal Structure, and Ionic MobilityThe bromides Li3MBr6 (M=Sm—Lu, Y) are obtained from the binary components LiBr and MBr3. They crystallize with a substitution/addition variant of the AlCl3- type of structure as was established from single crystal X-ray diffraction data for Li3ErBr6 (monoclinic, C2/m, Z = 2, a = 689.0(3), b = 1191.6(9), c = 684.2(6) pm, β = 109.77(6)°) and by powder X-ray diffraction for the remaining bromides. They are isotypic with Na3GdI6 and Li3ScCl6, respectively. Impedance spectroscopy and 7Li-NMR spectroscopy show that the lithium ions are highly mobile.
    Notes: Die Bromide Li3MBr6 (M=Sm—Lu, Y) erhält man durch Umsetzung der binären Komponenten LiBr und MBr3. Sie kristallisieren in einer Substitutions-Additions-Varianten des AlCl3-Typs, was anhand von röntgenographischen Untersuchungen an einem Einkristall von Li3ErBr6 (monoklin, C2/m, Z = 2, a = 689,0(3); b = 1191,6(9); c = 684,2(6) pm, β = 109,77(6)°) sowie an Pulverproben der übrigen Bromide nachgewiesen wurde. Sie sind isotyp mit Na3GdI6 bzw. Li3ScCl6. Impedanzmessungen und 7Li-NMR-Messungen an Pulverproben zeigen eine hohe Mobilität der Li+-Ionen.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0044-2313
    Keywords: Rare-Earth Halides ; Crystal Structure ; Ionic Conductivity ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ternary Halides of the A3MX6 Type. V. Synthesis, Crystal Structures, and Sodium Ionic Conductivity of the Ternary Iodides Na3MI6 (M = Sm, Gd-Dy) and of the Solid Solution Halides Na3GdBr6-xIxThe system Na3GdBr6-xIx exhibits a complete solid solution. The influence of the successive substitution of iodide for bromide on structure and ionic conductivity has been investigated systematically. X-ray structure determination from single crystal and powder data shows that the cryolite-type of structure is observed for x 〈 1 [Na3GdBr5.1I0.9, monoclinic, P21/n, Z = 2, a = 734.6(10), b = 779.5(9), c = 1101(2) pm, β = 90.8(2)°]. For x 〉 3 the new Na3GdI6 type is observed [monoclinic, C2/m, Z = 2, a = 787.5(1), b = 1353.4(2), c = 778.3(1) pm, β = 110.14(1)°; for Na3GdBr2.4I3.6: a = 772.7(4), b = 1323.3(7), c = 765.8(4) pm, β = 110.14(3)°]. In between, an ordered variant of the Na3GdI6 structure type is found with a doubled c axis [for Na3GdBr4.8I1.2: monoclinic, C2/c, Z = 4, a = 751.5(4), b = 1285.7(6), c = 1413.7(7) pm, β = 99,65(2)°]. Ionic conductivity measurements by impedance spectroscopy exhibit a decline of the activation energies for Na+ conductivity for halides with unchanged crystal structures with increasing substitution by iodide.
    Notes: Das System Na3GdBr6-XIX zeigt vollständige Mischkristallbildung. Der Einfluß des sukzessiven Austausches von Bromid gegen Iodid auf Struktur und Ionenleitfähigkeit wurde systematisch untersucht. Röntgenographische Untersuchungen an Einkristallen und Pulverproben ergaben, daß der Kryolith-Typ für x 〈 1 auftritt [Na3GdBr5,1I0,9 monoklin, P21/n, Z = 2, a = 734,6(10), b = 779,5(9), c = 1101(2) pm, β = 90,8(2)°]. Für x 〉 3 tritt der neue Na3GdI6-Typ auf [monoklin, C2/m, Z = 2, a = 787,5(1), b = 1353,4(2), c = 778,3(1) pm, β = 110,14(1)°; für Na3GdBr2,4I3,6: a = 772,7(4), b = 1323,3(7), c = 765,8(4) pm, β = 110,34(3)°]. Dazwischen beobachtet man eine ebenfalls bisher nicht bekannte Ordnungsvariante zum Na3GdI6-Typ, die eine verdoppelte c-Achse aufweist [für Na3GdBr4,8I1,2: monoklin, C2/c, Z = 4, a = 751,5(4), b = 1285,7(6), c = 1413,7(7) pm, β = 99,65(2)°]. Leitfähigkeitsmessungen mittels Impedanzspektroskopie zeigen in Bereichen mit unveränderter Kristallstruktur eine schrittweise Abnahme der Aktivierungsenergie mit zunehmendem Iodidgehalt.
    Additional Material: 5 Ill.
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  • 4
    ISSN: 0044-2313
    Keywords: Scandium ; Halides ; Crystal Structures ; Ionic Conductivity ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ternary Halides of the A3MX6 Type. IV. Ternary Halides of Scandium with Sodium, Na3ScX6 (X = F, Cl, Br): Synthesis, Structures, Ionic ConductivityX-ray studies on single crystals of Na3ScF6 and Na3ScBr6 show, that Na3ScF6 crystallizes with the cryolite type (monoclinic, P21/n, Z = 2, a = 560.16(9), b = 580.31(8), c = 812.1(2)pm, β = 90.720(14)°) and Na3ScBr6, as the only ternary bromide of the rare earth elements with sodium, in the Na3CrCl6 type (trigonal, P31c, Z = 2, a = 728.95(7), c = 1309.29(17)pm). The ionic conductivity of powder samples of Na3ScF6, Na3ScBr6 and of Na3ScCl6 was studied by impedance spectroscopy. Activation energies were determined as 1.22 eV, 0.80 eV and 0.71 eV for the fluoride, chloride and bromide, respectively. The differences are explained from the crystal structures and the sizes and polarizabilities of the anions.
    Notes: Röntgenographische Untersuchungen an Einkristallen von Na3ScF6 und Na3ScBr6 ergaben, daß Na3ScF6 im Kryolith-Typ (monoklin, P21/n, Z = 2, a = 560,16(9), b = 580,31(8), c = 812,1(2)pm, β = 90,720(14)°) und Na3ScBr6 als bisher einziges ternäres Bromid der Selten-Erd-Elemente mit Natrium im Na3CrCl6-Typ (trigonal, P31c, Z = 2, a = 728,95(7), c = 1309,29(17)pm) kristallisieren. An Pulverproben von Na3ScF6 und Na3ScBr6 sowie an Na3ScCl6 wurden Leitfähigkeitsuntersuchungen mittels Impedanzspektroskopie vorgenommen und aus den Ergebnissen die Aktivierungsenergien für den Leitungsprozeß zu 1,22 eV, 0,80 eV und 0,71 eV für das Fluorid, Chlorid bzw. Bromid bestimmt. Die Unterschiede werden aus den Kristallstrukturen sowie durch die Größen und Polarisierbarkeiten der Anionen erklärt.
    Additional Material: 4 Ill.
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  • 5
    ISSN: 0044-2313
    Keywords: Lithium ; Rare Earth Halides ; Crystal Structures ; Ionic Motion ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ternary Halides of the A3MX6 Type. VI. Ternary Chlorides of the Rare-Earth Elements with Lithium, Li3MCl6 (M = Tb—Lu, Y, Sc): Synthesis, Crystal Structures, and Ionic MotionSingle crystal X-ray studies on the ternary chlorides Li3ErCl6, Li3YbCl6 and Li3ScCl6 show that they crystallize in three different structure types. Li3ErCl6 (trigonal, P3ml, Z = 3, a = 1117.7(2); c = 603.6(2) pm; the chlorides with M = Tb—Tm, Y are isotypic) and Li3YbCl6 (orthorhombic, Pnma, Z = 4, a = 1286.6(1); b = 1113.2(1); c = 602.95(8) pm; Li3LuCl6 is isotypic) have very similar structures that may be derived from hexagonal closest packings of chloride ions with the cations occupying octahedral holes in part statistically. Li3ScCl6 (monoclinic, C2/m, Z = 2, a = 639.8(1); b = 1104.0(2); c = 639,1(1) pm; β = 109.89(1)°) crystallizes isotypic with Na3GdI6 and Li3ErBr6, structures that may be derived from a cubic closes packings of anions. The ionic movement in Li3YCl6 and Li3YbCl6 has been investigated by impedance and 7Li-NMR spectroscopy.
    Notes: Die ternären Chloride Li3ErCl6, Li3YbCl6 und Li3ScCl6 kristallisieren nach röntgenographischen Untersuchungen an Einkristallen in drei verschiedenen Strukturtypen. Li3ErCl6 (trigonal, P3ml, Z = 3, a = 1117,7(2); c = 603,6(2) pm; isotyp mit M = Tb—Tm, Y) und Li3YbCl6 (orthorhombisch, Pnma, Z = 4, a = 1286,6(1); b = 1113,2(1); c = 602,95(8) pm; Li3LuCl6 ist isotyp) haben sehr ähnliche Strukturen, die sich als hexagonal-dichteste Kugelpackungen von Chlorid-Ionen mit zum Teil statistischer Auffüllung der Oktaederlücken mit Kationen beschreiben lassen. Li3ScCl6 (monoklin, C2/m, Z = 2, a = 639,8(1); b = 1104,0(2); c = 639,1(1) pm; β = 109,89(1)°) kristallisiert isotyp mit Na3GdI6 und Li3ErBr6; die Anionen bilden hier eine kubisch-dichteste Kugelpackung. Die Ionenbewegung in Li3YCl6 und Li3YbCl6 wurde mittels Impedanzspektroskopie und 7Li-NMR-Spektroskopie untersucht.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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