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  • crystal structures  (5)
  • preparation  (4)
  • 1
    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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  • 2
    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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  • 3
    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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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 603 (1991), S. 49-56 
    ISSN: 0044-2313
    Keywords: Rhenium halide hydrates ; synthesis ; crystal structures ; thermal properties ; i.r. spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: [Re3Br9(H2O)]·H2O  - a Precursor to ReBr3 in the ReCl3-Type StructureThe reaction of ReBr3 or “ReCl3·2H2O” with an aqueous solution of HBr leads on slow evaporation to dark brown single crystals of ReBr3·2/3 H2O. The crystal structure (monoclinic, C2/m (No. 12); Z = 4; a = 1399.0(2), b = 1062.4(1), c = 1030.0(2), β = 96.12(1)°, Vm = 229.2(4) cm3/mol; R = 0.067, Rw = 0.050) contains building units [Re3(μ-Br)3Br8(H2O)] that are connected via two edges to chains according to ∞1[Re3(μ-Br)3/1Br4/1Br4/2(H2O)] which are further connected by crystal water molecules. The IR spectrum clearly distinguishes between the two types of water molecules. The topotactic dehydration of ReBr3·2/3 H2O at 200°C yields in one step ReBr3 crystallizing with the ReCl3-type structure which has been unknown so far for ReBr3. This metastable modification of ReBr3 transforms to the ReI3-type at 420°C.
    Notes: Bei der Umsetzung von ReBr3 oder „ReCl3 · 2H2O“ mit wäßriger HBr-Lösung erhält man beim Eindunsten auf dem Sandbad dunkelbraune Einkristalle von ReBr3 · 2/3 H2O. In der Kristallstruktur (monoklin, C2/m (Nr. 12); Z = 4; a = 1399,0(2), b = 1062,4(1), c = 1030,0(2), β = 96,12(1)°, Vm = 229,2(4)cm3/mol; R = 0,067, Rw = 0,050) liegen Baugruppen [Re3(μ-Br)3Br8(H2O)] vor, die über zwei gemeinsame Kanten zu Ketten gemäß ∞1[Re3(μ-Br)3/1Br4/1Br4/2 (H2O)] verknüpft und die ihrerseits durch Kristallwasser miteinander verbunden sind. In den IR-Spektren lassen sich die beiden Arten von Wasserliganden deutlich unterscheiden. Die topotaktische Entwässerung von ReBr3 · 2/3 H2O führt in einem Schritt bei 200°C zu ReBr3 im ReCl3-Typ, der bislang für ReBr3 nicht beobachtet wurde. Diese metastabile Form wandelt sich bei 420°C in den ReI3-Typ um.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 652-660 
    ISSN: 0044-2313
    Keywords: Ternary chlorides ; synthesis ; 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. II. The System Ag3-xNaxYCl6: Synthesis, Structures, Ionic Conductivity.The influence of the substitution of Ag+ by Na+ ions on the crystal structure and the ionic conductivity of Ag3YCl6 (stuffed LiSbF6-type structure) has been investigated. The system Ag3-xNaxYCl6 forms a complete solid solution. The stuffed LiSbF6-type structure is stable for all compositions. For compounds with Na+ contents of x 〉 1.67, the cryolite-type structure is observed as the high-temperature form. The transition temperature decreases steadily with increasing Na+ content. The “end member” phase Na3YCl6 transforms at 243 K from the monoclinic cryolite-type structure to the stuffed LiSbF6-type structure (trigonal, R3; a = 697.3(1), c = 1 868.4(14) pm, Z = 3; R = 0.094; Rw = 0.069). The crystal structures of Ag1.3Na1.7YCl6 (trigonal, R3; a = 691.5(2), c = 1 853.7(6) pm, Z = 3; R = 0.099, Rw = 0.081) and AgNa2YCl6 (trigonal, R3; a = 691.7(1), c = 1 853.9(5) pm, Z = 3; R = 0.099, Rw = 0.064) have also been determined. Both chlorides crystallize like Ag3YCl6 and Na3YCl6-I in the stuffed LiSbF6-type structure. The monovalent cations, Ag+ and Na+, are distributed over the five octahedral voids that are occupied by the Ag+ ions alone in Ag3YCl6. The ionic conductivity for compounds within the solid solution Ag3-xNaxYCl6 decreases with increasing Na+ content. The values for Na3YCl6 (σ = 1 · 10-6 Ω-1 cm-1 at T = 500 K) are by 2.5 to 3.5 orders of magnitude smaller than those for Ag3YCl6 (σ = 6 · 10-4 Ω-1 cm-1 at T = 500 K).
    Notes: Es wurde der Einfluß der Substitution von Ag+ durch Na+ auf die Kristallstruktur und die Ionenleitfähigkeit von Ag3YCl6 (aufgefüllter LiSbF6-Typ) untersucht. Das System Ag3-xNaxYCl6 zeigt vollständige Mischkristallbildung. Der aufgefüllte LiSbF6-Typ tritt über den gesamten Bereich auf. Erst bei Verbindungen mit einem Na+-Gehalt von x 〉 1,67 tritt der Kryolith-Typ als Hochtemperaturform auf, wobei mit steigendem Na+-Gehalt die Phasenumwandlungstemperatur stetig abnimmt. Die „Randphase“ Na3YCl6 wandelt bei 243 K vom monoklinen Kryolith-Typ in den aufgefüllten LiSbF6-Typ (trigonal, R3; a = 697,3(1), c = 1 868,4(14) pm, Z = 3; R = 0,094, Rw = 0,069) um. Es wurden ferner die Kristallstrukturen von Ag1,3Na1,7YCl6 (trigonal, R3; a = 691,5(2), c = 1 853,7(6) pm, Z = 3; R = 0,099, Rw = 0,081) und AgNa2YCl6 (trigonal, R3; a = 691,7(1), c = 1 853,9(5) pm, Z = 3; R = 0,099, Rw = 0,064) bestimmt. Beide Chloride kristallisieren, ebenso wie Ag3YCl6-I bzw. Na3YCl6-I, im aufgefüllten LiSbF6-Typ. Die einwertigen Kationen, Ag+ und Na+, sind jeweils statistisch auf die fünf Oktaederlücken verteilt, die in Ag3YCl6 von Ag+-Ionen eingenommen werden. Die Ionen-Leitfähigkeit von Verbindungen im Mischkristallsystem Ag3-xNaxYCl6 nimmt mit steigendem Na+-Gehalt ab. Die Werte für Na3YCl6 (σ = 1 · 10-6 Ω-1 cm-1 bei T = 500 K) sind etwa 2,5-3,5 Größenordnungen kleiner als jene für Ag3YCl6 (σ = 6 · 10-4 Ω-1 cm-1 bei T = 500 K).
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  • 6
    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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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 622 (1996), S. 1646-1650 
    ISSN: 0044-2313
    Keywords: Synthesis ; crystal structures ; complex fluorides ; silicon ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Crystal Structures of NH4[Si(NH3)F5] and [Si(NH3)2F4]Single crystals of NH4[Si(NH3)F5] and [Si(NH3)2F4] are obtained by reaction of silicon powder with NH4HF2 in sealed Monel ampoules at 400°C. NH4[Si(NH3)F5] crystallizes with the tetragonal space group P4/n (no. 85) with a = 614.91(7) pm, c = 721.01(8) pm, Z = 2. Characteristic for the structure is the anionic octahedron [Si(NH3)F5]-. Si(NH3)2F4 crystallizes with the monoclinic space group P21/c (no. 14) with a = 506.9(1) pm, b = 728.0(1) pm, c = 675.9(1), β = 93,21(2)°, Z = 2. Trans-[Si(NH3)2F4] molecules are characteristic for this structure.
    Notes: Einkristalle von NH4[Si(NH3)F5] und Si(NH3)2F4 erhält man durch Umsetzung von pulverförmigem Silicium mit NH4HF2 in verschlossenen Monelampullen bei 400°C. NH4[Si(NH3)F5] kristallisiert tetragonal in der Raumgruppe P4/n (Nr. 85) mit a = 614,91(7) pm, c = 721,01(8) pm; Z = 2. Charakteristische Baueinheit ist der anionische Oktaeder [Si(NH3)F5]-. Si(NH3)2F4 kristallisiert monoklin in der Raumgruppe P21/c (Nr. 14) mit a = 506,9(1) pm, b = 728,0(1) pm, c = 675,9(1), β = 93,21(2)°, Z = 2. Es liegt eine Molekülstruktur mit trans-[Si(NH3)2F4]-Oktaedern vor.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 457-463 
    ISSN: 0044-2313
    Keywords: Ternary halides ; synthesis ; 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. III [1, 2]. Synthesis, Structures, and Ionic Conductivity of the Halides Na3MX6 (X = Cl, Br)The bromides Na3MBr6 crystallize with the stuffed LiSbF6-type structure (type I; M = Sm—Gd) or with the structure of the mineral cryolite (type II; M = Gd—Lu). The structure types were refined from single crystal X-ray data (Na3SmBr6: trigonal, space group R3, a = 740.8(2) pm, c = 1 998.9(8) pm, Z = 3; Na3YBr6: monoclinic, space group P21/n, a = 721.3(4) pm, b = 769.9(2) pm, c = 1 074.8(4) pm, β = 90.60(4)°, Z = 2). Reversible phase transitions from one structure to the other occur. The phase transition temperatures were determined for the bromides as well as for the chlorides Na3MCl6 (M = Eu—Lu). The refinement of both structures for one compound was possible for Na3GdBr6 (I: trigonal, space group R3, a = 737.1(5) pm, c = 1 887(2) pm, Z = 3; II: monoclinic, space group P21/n, a = 725.2(1) pm, b = 774.1(3) pm, c = 1 080.1(3) pm, β = 90.76(3)°, Z = 2). All compounds exhibit ionic conductivity of the sodium ions which decreases with the change from type I to type II. The conductivity of the bromides is always higher when compared with the respective chlorides.
    Notes: Die Bromide Na3MBr6 kristallisieren im aufgefüllten LiSbF6-Typ (Typ I; M = Sm—Gd) oder im Kryolith-Typ (Typ II; M = Gd—Lu). Die Strukturen wurden anhand von Einkristalldaten verfeinert (Na3SmBr6: trigonal, Raumgruppe R3, a = 740,8(2) pm, c = 1 998,9(8) pm, Z = 3; Na3YBr6: monoklin, Raumgruppe P21/n, a = 721,3(4) pm, b = 769,9(2) pm, c = 1 074,8(4) pm, β = 90,60(4)°, Z = 2). Beide Strukturen sind reversibel ineinander umwandelbar. Die Umwandlungstemperaturen der Bromide wurden ebenso wie die der Chloride Na3MCl6 (M = Eu—Lu) bestimmt. An Na3GdBr6 wurden beide Strukturen an Einkristallen bestimmt (I: trigonal, Raumgruppe R3, a = 737,1(5) pm, c = 1 887(2) pm, Z = 3; II: monoklin, Raumgruppe P21/n, a = 725,2(1) pm, b = 774,1(3) pm, c = 1 080,1(3) pm, β = 90,76(3)°, Z = 2). Alle Verbindungen zeigen Natrium-Ionenleitfähigkeit, die beim Übergang vom Typ I in den Typ II stark abnimmt. Die Bromide zeigen, verglichen mit den Chloriden, jeweils eine bessere Leitfähigkeit.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 546-549 
    ISSN: 0044-2313
    Keywords: Ternary halides ; synthesis ; crystal structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Crystal Structures of the Ternary Rare Earth Chlorides NaMCl4 (M = Eu - Yb, Y)Single crystals of NaErCl4 were obtained from the melt of NaCl and ErCl3 (1:1 molar ratio) by slow cooling. It crystallizes in the monoclinic crystal system (space group P2/c) with the structure of α-NiWO4 with a = 632.24(9) pm, b = 759.78(9) pm, c = 674.2(1) pm, b̃ = 92.310(3)°, Z = 2. Two preparative routes to pure powder samples of the chlorides NaMCl4 are described. At room temperature, these are found to be isotypic with NaErCl4 (M = Tm - Yb; II) while the triclinic structure of NaGdCl4 is adopted with M = Gd - Ho, Y (I). Phase transitions from one structure to the other are observed for all compounds. The transition temperatures decrease with decreasing size of the ion M3+.
    Notes: Einkristalle von NaErCl4 erhält man durch langsames Abkühlen einer Schmelze von NaCl und ErCl3 (molares Verhältnis 1:1). NaErCl4-II kristallisiert monoklin (Raumgruppe P2/c) im α-NiWO4-Typ mit a = 632,24(9) pm, b = 759,78(9) pm, c = 674,2(1) pm, b̃ = 92,310(3)°, Z = 2. Zwei Wege zu reinen Pulverproben der Chloride NaMCl4 werden beschrieben. Bei Raumtemperatur sind diese für M = Tm - Yb isotyp zu NaErCl4 (II), mit M = Gd - Ho, Y kristallisieren sie in der triklinen Struktur von NaGdCl4 (I). Beide Modifikationen lassen sich reversibel ineinander umwandeln. Die Umwandlungstemperaturen werden mit abnehmendem Ionenradius von M3+ kleiner.
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