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  • 1
    Electronic Resource
    Electronic Resource
    Ternäre Halogenide vom Typ A3MX6. VII [1]. Die Bromide Li3MBr6 (M=Sm—Lu, Y): Synthese, Kristallstruktur, Ionenbeweglichkeit (1997)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 623 (1997), S. 1352-1356 
    Details
    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
    URL: http://dx.doi.org/10.1002/zaac.19976230905
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  • 2
    Electronic Resource
    Electronic Resource
    Über ein Oxidchlorid des Calciums: Ca4OCl6 (1991)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 596 (1991), S. 89-92 
    Details
    ISSN: 0044-2313
    Keywords: Calcium oxychloride ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: An Oxychloride of Calcium: Ca4OCl6Ca4OCl6 (hexagonal, P63mc, Z = 2), a = 905.8(3), c = 686.3(4) pm, (R = 0.031) crystallizes as colourless needles from reducing melts (CaCl2, Ca) that contain small amounts of „oxygen“. It contains „isolated“ tetrahedral units [Ca4O] and is isotypic with e.g., Ba4OCl6, Yb4OCl6 and K6HgS4. Ca4OCl6 does not form in the dehydration process of, for example, CaCl2 · 6 H2O.
    Notes: Ca4OCl6 (hexagonal, P63mc, Z = 2, a = 905.8(3)); c = 686.3(4) pm, (R = 0,031) kristallisiert in Form farbloser Nadeln aus „reduzierenden Schmelzen“ (CaCl2, Ca), die wenig „Sauerstoff“ enthalten. Es enthält „isolierte“ tetraedrische [Ca4O]-Einheiten und ist isotyp mit z. B. Ba4OCl6, Yb4OCl6 oder K6HgS4. Ca4OCl6 entsteht nicht beim Entwässern von z. B. CaCl2 · 6 H2O.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19915960112
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  • 3
    Electronic Resource
    Electronic Resource
    [Rb2(H2O)2][Re3(μ-Cl)3Br7(H2O)2]2 · H2O, ein gemischtes Halogenid-Hydrat mit anionischen Dimeren {[Re3(μ-Cl)3Br7(H2O)2]2 · H2O}2-Professor Kurt Dehnicke zum 60. Geburtstage gewidmet (1991)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 595 (1991), S. 131-137 
    Details
    ISSN: 0044-2313
    Keywords: Rhenium ; rubidium rhenium halide hydrates ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: [Rb2(H2O)2][Re3(μ-Cl)3Br7(H2O)2]2 · H2O, a Mixed Halide-Hydrate with the Anionic Dimer {[Re3(μ-Cl)3Br7(H2O)2]2 · H2O}2-[Rb2(H2O)2][Re3(μ-Cl)3Br7(H2O)2]2 · H2O crystallizes as dark redbrown single crystals from an hydrobromic-acid solution of ReCl3 and RbBr at 0°C. An important feature of the crystal structure (monoclinic, C2/c; a = 1494.61(8); b = 835.71(4); c = 3079.96(19) pm; β = 97.801(4)°; Vm = 573.9(4) cm3mol-1; R = 0.060; Rw = 0.038) is the connection of two anions [Re3(μ-Cl)3Br7(H2O)2]- via a water molecule to dimers, {[Re3(μ-Cl)3Br7(H2O)2]2 · H2O}2-. These dimeric units are contained in slabs that are stacked in the [001] direction and held together by Rb+ cations and crystal water.
    Notes: [Rb2(H2O)2][Re3(μ-Cl)3Br7(H2O)2]2 · H2O kristallisiert in dunklen, rotbraunen Einkristallen aus bromwasserstoffsaurer Lösung von Rheniumtrichlorid und Rubidiumbromid bei 0°C. Ein wichtiges Merkmal der Kristallstruktur (monoklin; C2/c; a = 1494,61(8); b = 835,71(4); c = 3079,96(19) pm; β = 97,801(4)°; Vm = 573,9(4) cm3mol-1; R = 0,060; Rw = 0,038) ist die Verknüpfung zweier Anionen [Re3(μ-Cl)3Br7(H2O)2]- über ein Wassermolekül zu Dimeren {[Re3(μ-Cl)3Br7(H2O)2]2 · H2O}2-. Diese dimeren Baugruppen sind zu Schichtpaketen zusammengefaßt, die längs [001] gestapelt und über die Rb+-Ionen in Gemeinsamkeit mit Kristallwasser verbunden sind.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19915950113
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  • 4
    Electronic Resource
    Electronic Resource
    Synthese und Kristallstrukturen der Alkali-Tetraiodoindate(III), Alnl4 (A = Li, K, Rb, Cs)Professor Klaus Brodersen zum 65. Geburtstage am 12. August 1991 gewidmet (1991)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 602 (1991), S. 31-37 
    Details
    ISSN: 0044-2313
    Keywords: Alkali-iodoindates(III) ; indium ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Crystal Structures of the Alkali-tetraiodoindates(III), AInI4 (A = Li, K, Rb, Cs)Single crystals of the yellow alkaliiodoindates(III), AInI4 (A = Li, K, Rb, Cs), are obtained from mixtures of the binary components by slow cooling of the melts. LiInI4 is isotypic with LiAlCl4: monoclinic, P21/c, Z = 4; a = 838.9(4); b = 751.2(3); c = 1526,7(8) pm; β = 92.67(4)°. KInI4 belongs to the ATIX4 type of structure (A = NH4, K, Rb; X = Br, I): cubic, F4 3c, Z = 24; a = 1990.8(1) pm. RbInI4 crystallizes with the β-GaBr2 type: trigonal, R3c, Z = 18; a = 2452.6(6); c = 978.6(4) pm. CsInI4 is isostructural with CsTII4: monoclinic, P21/c, Z = 4; a = 738.4(1); b = 1875.7(3); c = 853.6(2) pm; β = 105.75(2)°. In all structures almost regular tetrahedral polyhedra [InI4]- occur. The coordination numbers of the alkali cations cover the wide range from 6 (Li+) via 9 (Rb+) and 11 (Cs+) to 12 (K1+).
    Notes: Einkristalle der gelben Iodoindate(III) der Alkalimetalle, AInI4 (A = Li, K, Rb, Cs), erhält man aus Gemengen der binären Komponenten durch langsames Abkühlen der Schmelzen. LiInI4 ist isotyp mit LiAlCl4: monoklin, P21/c, Z = 4; a = 838,9(4); b = 751,2(3); c = 1526,7(8) pm; β = 92,67(4)°. KInI4 gehört zum ATIX4-Typ (A= NH4, K, Rb; X= Br, I): kubisch, F4 3c, Z = 24; a = 1990,8(1) pm. RbInI4 kristallisiert im β-Ga[GaBr4]-Typ: trigonal, R3c, Z = 18; a = 2452,6(6); c = 978,6(4) pm. CsInI4 ist isotyp mit CsTII4: monoklin, P21/c, Z = 4; a = 738,4(1); b = 1875,7(3); c = 853,6(2) pm; β = 105,75(2)°. Stets liegen annähernd tetraedrische Baugruppen [InI4]- vor. Die Koordinationszahlen der Alkali-Kationen überstreichen das Spektrum von 6 (Li+) über 9 Rb+, 11 (Cs+) bis 12 (K1+).
    Additional Material: 6 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19916020104
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  • 5
    Electronic Resource
    Electronic Resource
    Synthesis, crystal structure, magnetism, and absorption spectra of A2UX5 Type Halides (A = K, Rb; X = Cl, Br, I)Dedicated to Professor Hugo F. Franzen on his 60th Birthday (1994)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 620 (1994), S. 1339-1345 
    Details
    ISSN: 0044-2313
    Keywords: Alkali uranium halides, A2UX5 (A = K, Rb; X = Cl, Br, I) ; preparation ; crystal structure ; magnetic susceptibility ; UV-Vis spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese, Kristallstruktur, Magnetismus und Absorptionsspektren von Halogeniden des Typs A2UX5 (A = K, Rb; X = Cl, Br, I)Die ternären Uran(III)-halogenide A2UX5 (A = K, Rb; X = Cl, Br, I) wurden aus den binären Komponenten AX und UX3 in verschweißten Tantalampullen gewonnen. Nach Guinier-Aufnahmen (Raumtemperatur) kristallisieren sie sämtlich im K2PrCl5/Y2HfS5-Typ. Einkristall-Strukturverfeinerungen wurden für K2UI5 und Rb2UCl5 unternommen. Magnetische Suszeptibilitätsmessungen erfolgten mit einem SQUID-Magnetometer von Raumtemperatur bis zur Temperatur des flüssigen Heliums: Eindimensionale (innerhalb einer Kette) und dreidimensionale antiferromagnetische Ordnung wird bei tiefen Temperaturen, abhängig vom Abstand U3+—U3+, beobachtet. Absorptionsspektren wurden zwischen 4000 und 28000 cm-1 aufgenommen. Sie zeigen die für U3+ charakteristischen Übergänge und, abhängig vom Halogenid, sehr starke f - d Übergänge oberhalb 14000 bzw. 15000 cm-1.
    Notes: The ternary uranium(III) halides A2UX5 (A = K, Rb; X = Cl, Br, I) have been prepared from the binary components AX and UX3 in sealed tantalum containers. According to their Guinier X-ray powder patterns, they all crystallize with the K2PrCl5/Y2HfS5 type of structure. Lattice constants for ambient temperature are reported. Single-crystal structure refinemens were undertaken for K2UI5 and Rb2UCl5. Magnetic susceptibility data were recorded with a SQUID magnetometer from liquid helium to room temperature. One-dimensional (intrachain) and three-dimensional antiferromagnetic ordering occur at low temperatures dependent upon the U3+—U3+ distance. Absorption spectra were recorded between 4 000 and 28 000 cm-1. They show f - f transitions typical for U3+ and, depending on the halide, very strong f - d transitions above 14 000 to 15 000 cm-1, respectively.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19946200802
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  • 6
    Electronic Resource
    Electronic Resource
    Ternäre Halogenide vom Typ A3MX6. V. Synthese, Kristallstrukturen und Natrium-Ionenleitfähigkeit der ternären Iodide Na3MI6 (M = Sm, Gd-Dy) sowie der Mischkristalle Na3GdBr6-xIxProfessor Joachim Strähle zum 60. Geburtstage gewidmet (1997)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 623 (1997), S. 837-843 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.199762301132
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  • 7
    Electronic Resource
    Electronic Resource
    Ternäre Halogenide vom Typ A3MX6. IV. [1]. Ternäre Halogenide des Scandiums mit Natrium, Na3ScX6 (X = F, Cl, Br): Synthese, Strukturen, IonenleitfähigkeitIn memoriam Wilhelm Klemm (1996)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 622 (1996), S. 173-178 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19966220125
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