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  • 1
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Drei Bromide des Lanthans: LaBr2, La2Br5 und LaBr3Farbloses LaBr3 wurde durch Umsetzung von La2O3 mit NH4Br bzw. in einkristalliner Form durch chemischen Transport mit AlBr3 erhalten. Schwarze Einkristalle von LaBr2 und La2Br5 wachsen aus der Schmelze, die man bei der metallothermischen Reduktion von LaBr3 mit Lithium erhält (verschweißte Tantalampulle, 850°C). Die Kristallstrukturen der drei Lanthanbromide wurden verfeinert: LaBr2. 2H2-Typ, hexagonal (P63/mmc); a = 409,88(4) pm; c = 1 390,0(1) pm; R = Rw = 0,092; La2Br5. Pr2I5-Typ, monoklin (P21/m); a = 789,09(6) pm; b = 424,89(4) pm; c = 1342,3(1) pm β = 91,60(1)º; R = 0,067; Rw = 0,055; LaBr3. UCl3-Typ, hexagonal (P63/m) a = 797,13(4) pm; c = 452,16(4) pm; R = 0,036; Rw = 0,032.
    Notes: Colourless LaBr3 was obtained via the ammonium-bromide route and in singlecrystalline form by chemical vapour-phase transport with aluminium tribromide. Black single crystals of LaBr2 and La2Br5 have been grown from the melts that are obtained by lithium reduction of lanthanum tribromide in sealed tantalum ampoules at 850°C. The crystal structures of the three bromides of lanthanum were refined: LaBr2. 2H2-MoS2 type, hexagonal (P63/mmc), a = 409.88(4) pm, c = 1390.0(1) pm, R = Rw = 0.092; La2Br5. Pr2I5 type, monoclinic (P21/m), a = 789.09(6) pm, b = 424.89(4) pm, c = 1342.3(1) pm, β = 91.60(1)º, R = 0.067, Rw = 0.055; LaBr3. UCl3 type, hexagonal (P63/m), a = 797.13(4) pm, c = 452.16(4) pm, R = 0.036, Rw = 0.032.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 533 (1986), S. 181-185 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Oxychlorides under Reducing Conditions: Single Crystals of NdOCl and GdOClSingle crystals of NdOCl and GdOCl are obtained in metallothermic reduction reactions of NdCl3 and GdCl3, respectively, with sodium due to ubiquitous oxidic impurities by crystallization from the melt. The crystal structures of NdOCl [a = 402.49(2), c = 678.37(5) pm] and GdOCl [a = 394.95(3), c = 667.08(7) pm], both PbFCl structure type (P4/nmm, Z = 2) were refined.
    Notes: Bei der metallothermischen Reduktion von NdCl3 bzw. GdCl3 mit Natrium werden, durch kaum vermeidbare oxydische Verunreinigungen bedingt, Einkristalle von NdOCl bzw. GdOCl durch Kristallisation aus der Schmelze erhalten. Die Kristallstrukturen (PbFCl-Typ, P4/nmm, Z = 2) wurden verfeinert. Es ist: a = 402,49(2); c = 678,37(5) pm (NdOCl) und a = 394,95(3); c = 667,08(7) pm (GdOCl).
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  • 3
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Crystal Structure of Praseodymium(III)-monoacetatohexaaquo-dichloridemonohydrate, [Pr(CH3COO)(H2O)6]Cl2 · H2OSingle crystals of [Pr(CH3COO)(H2O)6]Cl2 · H2O (pale green) may be obtained from a solution of PrCl3 · 7 H2O in aqueous acetic acid by isothermic evaporation at room temperature. [Pr(CH3COO)(H2O)6]Cl2 · H2O crystallizes with the triclinic system, space group P1 (No. 2); a = 872.27(9) pm, b = 933.02(8) pm, c = 961.75(9) pm; α = 105.238(9)°, β = 107.913(9)°, γ = 110.568(8)°; R = 0.023, Rw = 0.022 (Z = 2). Pr3+ is nine-coordinated by O2- of six water molecules, one bidentate acetate group, and the bridging oxygen from another (formally monodentate) acetate anion. Centrosymmetric dimers {[Pr(CH3COO)(H2O)6]2}4+ are thus formed, held together by four “lone-some” Cl- anions and two “zeolithic” water molecules per dimer. The chloride ions are surrounded by five (Cl1) and six (Cl2) aquo ligands, respectively. The “zeolithic” water molecule (O9z) has four aquo ligands and two chloride ions (Cl1 and Cl2) as nearest neighbours.
    Notes: [Pr(CH3COO)(H2O)6]Cl2 · H2O wird in Form von blaßgrünen Einkristallen durch Eindunsten wäßriger, essigsaurer Lösungen von PrCl3 · 7 H2O erhalten. Die Verbindung kristallisiert triklin (Z = 2), Raumgruppe P1 (Nr. 2); a = 872,27(9) pm; b = 933,02(8) pm; c = 961,75(9) pm; α = 105,238(9)°; β = 107,913(9)°; γ = 110,568(8)°; R = 0,023; Rw = 0,022. Pr3+ ist von insgesamt neun Sauerstoffatomen umgeben: Sechs gehören zu „Hydratwasser“-Molekülen, zwei zu einer chelatartig angreifenden, das neunte zu einer einzähnig koordinierenden Acetatgruppe. Durch Verbrückung über Acetationen entstehen zentrosymmetrische Dimere {[Pr(CH3COO)(H2O)6]2}4+, die durch vier „einsame“ Cl--Ionen und zwei weitere Wassermoleküle pro Dimer zusammengehalten werden. Die Chloridionen sind von fünf (Cl1) bzw. sechs (Cl2) Wasserliganden umgeben, das „zeolithische“ Wasser (O9z) hat vier Wassermoleküle und zwei Chloridionen (Cl1 und Cl2) als nächste Nachbarn.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 590 (1990), S. 103-110 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The System NazGdClHx/S. I. Crystal Structure of NaGdCl4NaGdCl4 is obtained together with Gd2S3 through oxidation of Na0.25GdClH0.75 with sulfur (sealed tantalum container, 850°C, 7 d) as colourless single crystals or as a white powder by thermal decomposition of (NH4)2NaGdCl6 (320°C). The crystal structure (triclinic, P1, a = 702.81(6), b = 676.25(5), c = 666.72(5) pm, α = 100.852(7), β = 91.702(7), γ = 89.760(7)°, R = 0.040, Rw = 0.032) may be derived from the fluorite type although both Na+ and Gd3+ have coordination numbers (C.N.) of seven (monocapped trigonal prism). The structure may also be described as a layer structure where puckered layers are stacked along [100] in the sequence Cl2GdCl2NaCl2GdCl2 with Cl3 and Cl4 in four-fold cationic coordination and Cl1 and Cl2 with C.N. 3.
    Notes: NaGdCl4 entsteht neben Gd2S3 bei der Oxydation von Na0,25GdClH0,75 mit Schwefel (Tantal-Ampulle, 850°C, 7 d) in Form von farblosen, derben Einkristallen oder durch thermischen Abbau von (NH4)2NaGdCl6 (320°C) als weißes Pulver. Die Kristallstruktur (triklin, P1; a = 702,81(6); b = 676,25(5); c = 666,72(5) pm; α = 100,852(7); β = 91,702(7); γ = 89,760(7)°; R = 0,040; Rw = 0,032) leitet sich vom Fluorit-Typ ab, jedoch weisen Na+ und Gd3+ jeweils die Koordinationszahl 7 (bekapptes trigonales Prisma) auf. Sie kann auch als Schichtstruktur beschrieben werden: Gewellte Schichten werden gemäß Cl2GdCl2NaCl2GdCl2 längs [100] gestapelt, wobei Cl1 und Cl2 C.N. 3, Cl3 und Cl4 aber C.N. 4 aufweisen.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 590 (1990), S. 111-119 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The System NazGdClHx/S. II. Single Crystals of U2S3-Type Gd2S3Single crystals of Gd2S3 are obtained as black rods via the oxidation of Na0.25GdClH0.75 with sulfur (sealed tantalum container, 850°C, 7 d) where NaGdCl4 is the other main product. Gd2S3 produced in this way crystallizes with the U2S3-type structure (orthorhombic, space group: Pnma (No. 62), a = 1074.47(7), b = 389.85(3), c = 1054.62(6) pm, Z = 4, R = 0.031, Rw = 0.027). Two crystallographically independent Gd3+ cations (Gd1 and Gd2) are surrounded by seven and eight (better: seven plus one) sulfide anions, respectively. Both polyhedra of coordination may be described as trigonal prisms with one or two sulfur atoms capping rectangular faces. Three crystallographically independent S2- anions have five (S1 and S2, for S3 better: four plus one) nearest Gd3+ neighbours.
    Notes: Gd2S3 wird neben NaGdCl4 in Form von schwarzen, stäbchenförmigen Einkristallen bei der Umsetzung von Na0,25GdCl0,75 mit Schwefel (verschweißte Tantalampulle, 850°C, 7 d) erhalten. Das so gewonnene Gd2S3 kristallisiert isotyp mit U2S3 (orthorhombisch, Raumgruppe: Pnma (Nr. 62); a = 1074,47(7); b = 389,85(3); c = 1054,62(6) pm; Z = 4; R = 0,031; Rw = 0,027). Es liegen zwei kristallographisch unterschiedliche Gd3+ vor, von denen eines (Gd1) von sieben, das zweite (Gd2) von acht (besser: sieben plus eins) Sulfid-Ionen umgeben ist. Beide Koordinationspolyeder können als trigonale Prismen aufgefaßt werden, deren Rechtecksflächen ein- bzw. zweifach von Schwefel bekappt sind. Die drei kristallographisch unterschiedlichen Sulfid-Ionen weisen jeweils fünf (S1 und S2) bzw. vier plus eins (S3) nächste Gd3+-Nachbarn auf.
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  • 6
    ISSN: 0044-2313
    Keywords: Lanthanides ; crystal structure ; acetate halides ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: [La2Cl3(OAc)2(H2O)7]Cl: The First Lanthanide-Acetate-Halide-Hydrate with Chloride in Inner-Sphere Coordination[La2Cl3(OAc)2(H2O)7]Cl has been obtained as single crystals through the reaction of LaCl3 · 7H2O with diluted acetic acid or from La2O3 with acetyl chloride. In the crystal structure (triclinic, Z = 2, P1 (no. 2), a = 919.6(2), b = 950.7(2), c = 1178.9(2) pm, α = 82.52(1), β = 84.14(1), γ = 64.69(1)°, R = 0.021, Rw = 0.020), La3+ is surrounded by nine ligands (O, Cl). La1 has two chloride and seven oxygen ligands whereas La2 has one chloride and eight oxygen atoms as nearest neighbours. Four of the oxygen ligands of each lanthanum cation originate from a „tetradentate“ acetate anion, the others from crystal water molecules. The „tetradentate“ acetate groups are coordinated not only to one central La3+ as chelate ligands, but also to the „left“ and „right“ La3+ neighbours. Thereby, a one-dimensional infinite cationic chain, 1∞[La2Cl3(OAc)2(H2O)7]+, is formed that runs in the [011] direction. These chains are held together by „lonesome“ chloride ions which are surrounded by (4 + 1) water molecules and connected to the chains via hydrogen bonds.
    Notes: [La2Cl3(OAc)2(H2O)7]Cl wurde in einkristalliner Form durch Umsetzung von LaCl3 · 7H2O mit und in verdünnter Essigsäure oder von La2O3 mit Acetylchlorid erhalten. In der Kristallstruktur (triklin, Z = 2, P1 (Nr. 2); a = 919,6(2); b = 950,7(2); c = 1178,9(2) pm; α = 82,52(1), β = 84,14(1); γ = 64,69(1)°; R = 0,021; Rw = 0,020) ist La3+ von jeweils neun Liganden (O, Cl) umgeben. Dabei weist La1 zwei Chlorid- und sieben Sauerstoff-, La2 dagegen nur einen Chlorid-, jedoch acht Sauerstoff-Liganden als nächste Nachbarn auf. Je vier der Sauerstoff-Liganden in der Koordinationssphäre des Lanthans stammen von einer „vierzähnigen“ Acetatgruppe, die übrigen von Hydratwasser-Molekülen. Die Acetatgruppen koordinieren sowohl am zentralen (chelatisierend) als auch zu den „rechts“ und „links“ benachbarten La3+-Kationen. Hierdurch entstehen eindimensional unendliche, kationische Ketten 1∞[La2Cl3(OAc)2(H2O)7]+, die in Richtung [011] verlaufen. Diese Ketten werden durch „einsame“ Chlorid-Ionen zusammengehalten, die ihrerseits von (4 + 1) Hydratwasser-Molekülen umgeben sind, zu denen Wasserstoffbrücken-Bindungen ausgebildet werden.
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  • 7
    ISSN: 0044-2313
    Keywords: Lanthanides ; sulfide and selenide disilicates ; crystal structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: M4X3[Si2O7]-Type Lanthanide Chalcogenide Disilicates (M = Ce—Er; X = S, Se)Attempts to produce single crystals of MSe2 (or MSe2-X) by vapour phase transport with iodine or the oxidation of MCl2 (or MClH) with sulfur in the presence of NaCl in sealed evacuated quartz containers often yielded well-grown single crystals with the composition M4X3[Si2O7] (M = pr, Sm, Gd, X = Se, and M = Nd, Er, X = S) as by-products. The crystal structures (tetragonal, 141/amd (no. 141)), Z = 8, contain two crystallographically independent M3+ Cations that are interconnected by chalcogenide (X2-) and disilicate anions ([Si2O7]6-). (M1)3+ is surrounded by eight (five X2- and three terminal O2- of the disilicate group), (M2)3+ by nine (three X2- and six terminal O2- of the [Si2O7]6- anion) chalcogenide anions. The disilicate anion itself exhibits the eclipsed conformation with non-linear Si—O—Si bridges (angles: 128 - 133°).
    Notes: Bei Versuchen zum chemischen Transport von MSe2 (bzw. MSe2-x) mit I2 bzw. bei der Oxidation von MCl2 bzw. MClHx mit S in Gegenwart von NaCl in evakuierten, geschlossenen Quarz-Ampullen wurden jeweils gut ausgebildete Einkristalle der Zusammensetzung M4X3[Si2O7] (M = Pr, Sm, Gd, X = Se bzw. M = Nd, Er, X = S) als Nebenprodukte erhalten. In den Kristallstrukturen (tetragonal, I41/amd (Nr. 141)), Z = 8; liegen zwei kristallographisch unterschiedliche M3+-Kationen vor, die über Chalkogenid- (X2-) und Disilicat-Anionen ([Si2O7]6-) verknüpft sind. Dabei ist (M1)3+ von insgesamt acht (fünf X2- und drei terminale O2- der Disilicat-Gruppe), (M2)3+ von neun (drei X2- und sechs terminale 02- des [Si2O7]6--Anions) Chalkogenid-Anionen umgeben. Das Disilicat-Anion selbst weist die ekliptische Konformation mit nicht gestrecktem Si—O—Si-Winkel (128 - 133°) auf.
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  • 8
    ISSN: 0044-2313
    Keywords: Chlorides ; lanthanides ; synthesis ; crystal structure ; X-ray absorption spectroscopy ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Chlorides Na3xM2-xCl6 (M = La—Sm) and NaM2Cl6 (M = Nd, Sm): Derivatives of the UCl3-Type of Structure. Synthesis, Crystal Structure and X-Ray Absorption Spectroscopy (XANES)Single crystals of the derivatives of the UCl3-type structure Na3xM2-xCl6 (M = La/x = 0.364(4); Ce/0.349(5); Pr/0.318(8); Nd/0.305(5); Sm/0.246(4)) and NaSm2Cl6 were grown by different methods generally under reducing conditions. They are addition [Na(Sm2)Cl6] and addition/substitution variants [Na2x(NaxM2-x)Cl6] of the UCl3 structure type [□(U2)Cl6]. X-Ray Absorption Spectroscopy (XANES) at the LIII edge characterizes NaSm2Cl6 and NaNd2Cl6 as mixed-valence compounds with valences of +2 and +3 in statistical distribution (approximately 1:1) for Sm and Nd, respectively.
    Notes: Einkristalle der Derivate des UCl3-Typs Na3xM2-xCl6 (M = La/x = 0,364(4); Ce/0,349(5); Pr/0,318(8); Nd/0,305(5); Sm/0,246(4)) sowie von NaSm2Cl6 wurden auf unterschiedlichen Wegen, im allgemeinen unter reduzierenden Bedingungen erhalten. Sie sind Additions- [Na(Sm2)Cl6] bzw. Additions- / Substitutionsvarianten [Na2x(NaxM2-x)Cl6] des UCl3-Strukturtyps [□(U2)Cl6]. Röntgenabsorptionsspektren (XANES) an der Lm-Kante charakterisieren NaSm2Cl6 und NaNd2Cl6 als gemischtvalente Verbindungen mit Valenzen von +2 und +3 in statistischer Verteilung (etwa 1:1) für Sm bzw. Nd.
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  • 9
    ISSN: 0044-2313
    Keywords: Rare Earth Elements ; Halides ; Clusters ; Cesium Scandium Chloride Carbide ; Cesium Praseodymium Iodide Dicarbide ; Crystal Structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cs4[Sc6C]Cl13 and Cs4[Pr6(C2)]I13  -  Two Examples for the Missing Link in the Connectivity of [M6Z]X12iX6a Building UnitsCs4[Sc6C]Cl13 (tetragonal, I41/amd, a = 1 540.5(4), c = 1 017.9(7) pm, c/a = 0.661, Z = 4, R = 0.038, Rw = 0.026) and Cs4[Pr6(C2)]I13 (a = 1 804.9(3), c = 1 259.5(3) pm, c/a = 0.698, R = 0.106, Rw = 0.068) are obtained as green-black and blue-black single crystals with brass-like metallic lustre through metallothermic reduction of ScCl3 and PrI3, respectively, with cesium in the presence of carbon in sealed tantalum containers. The, overall, isotypic compounds contain isolated [Sc6C] and [Pr6(C2)] clusters, respectively, that are surrounded by 18 halide (X) ligands (12 Xi and 6 Xa; X = Cl or I). The connection is carried out via the motif [M6Z]X8iX4/21-aX4/2a-1X2/2a-a (M = Sc and Pr; Z = C and C2, respectively) and is thereby the missing link of the motifs of connection for the composition Ax[M6Z]X13. Analogous interconnection of [TiO6] octahedra is found in the anatase-type of structure of TiO2.
    Notes: Cs4[Sc6C]Cl13 (tetragonal, I41/amd; a = 1 540,5(4); c = 1 017,9(7) pm; c/a = 0,661; Z = 4; R = 0,038; Rw = 0,026 und Cs4[Pr6(C2)]I13 (a = 1 804,9(3); c = 1 259,5(3) pm; c/a = 0,698; R = 0,106; Rw = 0,068) werden bei der metallothermischen Reduktion von ScCl3 bzw. PrI3 mit Caesium in Gegenwart von Kohlenstoff in verschweißten Tantalampullen in Form von grünschwarzen bzw. blauschwarzen, messingglänzenden Einkristallen erhalten. Die weitgehend isotypen Kristallstrukturen enthalten isolierte [Sc6C]- bzw. [Pr6(C2)]-Cluster, die von 18 Halogenid-Ionen (X-, 12 Xi und 6 Xa; X = Cl bzw. I) umgeben sind. Die Verknüpfung erfolgt gemäß dem Motiv [M6Z]X8iX4/21-aX4/2a-1X2/2a-a (M = Sc bzw. Pr; Z = C bzw. C2) und stellt damit ein noch unbekanntes Verknüpfungsmuster für Verbindungen der Zusammensetzung Ax[M6Z]X13 dar, das jenem der [TiO6]-Oktaeder in der Anatas-Struktur von TiO2 entspricht.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 554 (1987), S. 118-122 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Eu4OCl6 and Eu4OBr6: Kristallzüchtng und -strukturZartgelbe, transparente Einkristalle von Eu4OCl6 (1) and Eu4OBr6 (2) wachsen aus Schmelzen, die bei der metallothermischen Reduktion von EuX3 (X = Cl, Br) in Gegenwart von Eu2O3 mit metallischem Lithium im molaren Verhältnis 6:1:8 bei höheren Temperaturen in Tantalampullen entstehen. Beide Oxidhalogenide kristallisieren isotyp mit Ba4OCl6 (hexagonal, P63mc, Z = 2, 1: a = 944,07(4); c = 715,60(4) pm und 2: a = 982,04(4); c = 749,69(5) pm) mit „isolierten“ von O2- zentrierten Eu4-Tetraedern.
    Notes: Faint yellow transparent single crystals of Eu4OCl6 (1) and Eu4OBr6 (2) grow from fluxes that emerge from reaction mixtures containing EuX3 (X = Cl, br), Eu2O3 and lithium metal in 6:1:8 molar ratios at elevated temperatures in tantalum ampoules. Both crystallize with the Ba4OCl6 type structure (hexagonal, P63mc, Z = 2, 1: a = 944.07(4), c = 715.60(4) pm and 2: a = 982.04(4), c = 749.69(5) pm) with „isolated“ O2- centered Eu4 tetrahedra.
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