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  • Lanthanides  (8)
  • preparation  (4)
  • Ionic Conductivity  (3)
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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 602 (1991), S. 31-37 
    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+).
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 513-516 
    ISSN: 0044-2313
    Keywords: Synthesis ; Crystal Structure ; Lanthanides ; Ternary Lithium Nitrates ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Structure of the First Anhydrous Ternary Lithium Nitrates of the Lanthanides, Li2[M(NO3)5] (M = La, Pr—Eu).Single crystals of the ternary lithium nitrates of the lanthanides, Li2[M(NO3)5] (M = La, Pr—Eu), are obtained by dissolving the respective anhydrous nitrate, previously obtained by dehydration of M(NO3)3 · 6 H2O at 180°C under vacuum, in a melt of LiNO3. In the crystal structure of Li2[Pr(NO3)5] (orthorhombic, Pnnm, Z = 4, a = 899.6(2), b = 1 052.7(2), c = 1 178.6(2)pm; R = 0.072, Rw = 0.034) there are two crystallographically different Pr3+ ions, each surrounded by six bidentate nitrate ligands. One nitrate group is bridging between Pr1 and Pr2 resulting in a winded chain, ∞1[(O2/2NO2/1)Pr1(NO3)4(O2/2NO2/1)Pr2(O2/2NO2/1)(NO3)4]5-, running along [010]. The chains are packed hexagonally and held together by lithium ions. The coordination polyhydron of Li+ may be described as a bicapped trigonal prism.
    Notes: Einkristalle der ternären Nitrate der Lanthanide vom Typ Li2[M(NO3)5] (M = La, Pr—Eu) erhält man durch Auflösen der zuvor bei 180°C unter Vakuum entwässerten Hydrate M(NO3)3 · 6 H2O in einer Lithiumnitrat-Schmelze. Die Röntgenstrukturanalyse am Beispiel von Li2[Pr(NO3)5] (orthorhombisch, Pnnm, Z = 4; a = 899,6(2); b = 1 052,7(2); c = 1 178,6(2)pm; R = 0,072; Rw = 0,034) zeigt, daß zwei kristallographisch verschiedene Pr3+ vorliegen, die von jeweils sechs zweizähnigen Nitratliganden umgeben sind. Eine Nitratgruppe verbrückt zwischen Pr1 und Pr2, so daß sich eine gewundene Kette gemäß ∞1[(O2/2NO2/1)Pr1(NO3)4(O2/2NO2/1)Pr2(O2/2NO2/1)(NO3)4]5- ergibt, die längs [010] verläuft. Die Kettenstränge sind gemäß einer hexagonalen Stabpackung angeordnet und werden durch Li+-Ionen zusammengehalten. Die Koordination um Li+ kann als zweifach bekapptes trigonales Prisma beschrieben werden.
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  • 3
    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.
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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.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 623 (1997), S. 1493-1495 
    ISSN: 0044-2313
    Keywords: Synthesis ; Crystal structure ; Crown ether ; Lanthanides ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: [La2I2(OH)2(dibenzo-18-crown-6)2]I(I3), a Cationic Dimeric in-cavity Complex with Iodide and Triiodide as AnionsSingle crystals of [La2I2(OH)2(dibenzo-18-crown-6)2]I(I3) are obtained from the reaction of LaI3 and dibenzo-18-crown-6 in acetonitrile. The crystal structure monoclinic, C2/m, Z = 4, T = 293 [100] K, a = 2179(3) [2162.3(3)], b = 1070.3(3) [1069.6(1)], c = 1118.2(3) [1110.6(1)] pm, β = 93.1(1) [92.83(1)]°, R1 = 0.0601 [0.0411], wR2 = 0.1449 [0.1014] contains hydroxide-bridged cationic dimers and iodide as well as triiodide as anions.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 596 (1991), S. 89-92 
    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.
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  • 7
    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.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 622 (1996), S. 759-765 
    ISSN: 0044-2313
    Keywords: Metallothermic Reduction ; Lanthanides ; Alkaline Earth Metals ; Crystal Structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ternary Bromides and Iodides of Divalent Lanthanides and Their Alkaline-Earth Analoga of the Type AMX3 and AM2X5Metallothermic reduction of the tribromides and -iodides MX3 (M = Sm, Dy, Tm, Yb) with alkali metals as well as with indium and thallium (A = Cs, Rb, K, In, Tl) results in most cases in ternary compounds with the composition AMX3 and AM2X5, respectively. Analogous compounds with M = Ba, Sr, Ca were synthesized from the binary components. The AMX3 compounds crystallize with the following types of structure: the perovskite-type and its distorted variants, the NaNbO3-II- and the GdFeO3-type, the NH4CdCl3- and the stuffed PuBr3-type. These structure types differ by a gain of condensation of the [MX6] octahedra (three-dimensional connection via corners within the variants of the perovskite-type, double chains of edge- and face-connected octahedra within the NH4CdCl3-type, and layers of corner- and edge-connected octahedra within the stuffed PuBr3-type of structure). This comes along with a reduction of the coordination number of A+ from 12 (“ideal” perovskite) to 8 + 2 (GdFeO3-type), 9 (NH4CdCl3-type), and 8 (stuffed PuBr3-type). Thus, the A/[MX6] size ratio determines which AMX3 type of structure is adopted. If the M2+ ion is large enough, ternary compounds with the composition AM2X5 occur either in addition to the AMX3 compounds or exclusively. They crystallize with the TlPb2Cl5 type of structure (C.N.(M2+) = 7 and 8). All of the AMX3 and AM2X5 compounds are summarized in a structure field diagram.
    Notes: Die metallothermische Reduktion der Tribromide und -iodide MX3 (M = Sm, Dy, Tm, Yb) mit Alkalimetallen sowie mit Indium und Thallium (A = Cs, Rb, K, In, Tl) liefert überwiegend ternäre Verbindungen der Zusammensetzungen AMX3 bzw. AM2X5. Analoge Erdalkaliverbindungen (M = Ba, Sr, Ca) wurden aus den jeweiligen binären Komponenten dargestellt. Die Halogenide AMX3 kristallisieren im Perowskit-Typ und seinen Verzerrungsvarianten, dem NaNbO3-II-bzw. dem GdFeO3-Typ, sowie im NH4CdCl3- oder im aufgefüllten PuBr3-Typ. Diese Strukturtypen unterscheiden sich durch eine zunehmende Verknüpfung der [MX6]-Oktaeder (allseitige Eckenverknüpfung in den Perowskitvarianten, Doppelstränge aus kanten- und flächenverknüpften Oktaedern im NH4CdCl3-Typ und kanten- und eckenverknüpfte Oktaederschichten im aufgefüllten PuBr3-Typ). Sie geht mit einer Verkleinerung der Koordinationszahl des A+-Ions von 12 im idealen Perowskit über 8 + 2 (GdFeO3-Typ) und 9 (NH4CdCl3-Typ) auf 8 (aufgefüllter PuBr3-Typ) einher, so daß das A/[MX6]-Größenverhältnis ausschlaggebend dafür ist, welcher Strukturtyp für die Zusammensetzung AMX3 auftritt. Sind die M2+-Ionen groß genug, treten (zusätzlich oder ausschließlich) Verbindungen vom Typ AM2X5 auf, die im TlPb2Cl5-Typ kristallisieren (C.N.(M2+) = 7 und 8). Alle erhaltenen Verbindungen wurden in einem Strukturfelddiagramm zusammengefaßt.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 1466-1470 
    ISSN: 0044-2313
    Keywords: Synthesis ; Crystal structure ; Halides ; Clusters ; Lanthanides ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The First Bromide with Trigonal-Bipyramidal [M5(C2)] Clusters: [Pr5(C2)]Br9The bromide [Pr5(C2)]Br9 is obtained via metallothermic reduction of PrBr3 with rubidium in the presence of praseodymium and carbon in a sealed niobium container at 730°C as dark red single crystals. [Pr5(C2)]Br9 crystallizes in the monoclinic crystal system [P21/n; Z = 4; a = 1 006.9(1); b = 1 886.1(1); c = 1 045.9(1) pm; β = 108.130(1)°; Rint = 0.059; R1 = 0.038; wR2 = 0.077]. One edge in the base of the trigonal bipyramid in [Pr5(C2)]Br9 is usually long (440 pm). It is not brigded by a Bri ligand. In addition to the eight Bri, the cluster is coordinated by 12 terminal ligands (Bra). Except for the known Bra-a-a and Bri-a connections, Bri-a-a brigdes are observed for the first time for trigonal-bipyramidal clusters.
    Notes: Das Bromid [Pr5(C2)]Br9 erhält man durch metallothermische Reduktion von PrBr3 mit Rubidium in Gegenwart von Praseodym und Kohlenstoff in einer verschweißten Niobampulle bei 730°C in Form dunkelroter Kristalle. [Pr5(C2)]Br9 kristallisiert im monoklinen Kristallsystem [P21/n; Z = 4; a = 1 006,9(1); b = 1 886,1(1); c = 1 045,9(1) pm; β = 108,130(1)°; Rint = 0,059; R1 = 0,038; wR2 = 0,077]. Eine Kante in der Basis der trigonalen Bipyramide in [Pr5(C2)]Br9 ist mit 440 pm ungewöhnlich lang und wird nicht von einem Bri-Liganden überbrückt. Zusätzlich zu den acht Bri werden die Cluster von 12 terminalen Liganden koordiniert (Bra). Neben den bekannten Bra-a-a- und Bri-a-Brücken treten hier erstmals bei trigonal-bipyramidalen Clustern Bri-a-a-Brücken auf.
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  • 10
    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.
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