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  • Inorganic Chemistry  (5)
  • Preparation  (2)
  • Palladium
  • 1990-1994  (5)
  • 1
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Sulfur Dichloride as a Ligand. The Molecular and Crystal Structures of Trans-bis(dichlorsulfan)platin (IV) chloride PtCl4(SCl2)2 and Trans-bis(dichlorsulfan) palladium (II) chloride PdCl2(SCl2)2The compounds PtS2Cl8 and PdS2Cl6 have been obtained by reactions of the metals with an excess of sulfur and chlorine in closed quarz ampoules at 150-200°C. The crystal structure of the red PtS2Cl8 (monoclinic; a = 6.271(2) Å; b = 7.177(3)Å; c = 12.368(5)Å; β = 100.15(2)°; Z = 4; spacegr. P22/c) consists of octahedral transconfigurated PtCl4(SCl2)2 molecules. The crystal structure of the yellow PdS2Cl6 (triclinic; a = 4.3387(8)Å; b = 6.8213(14)Å; c = 8.1737(11)Å; α = 104.16(3)°; β = 98.15(3)°; γ = 94.42(3)°; Z = 1; spacegr. P-1) contains transconfigurated PdCl2(SCl2)2 complexes. The compounds decompose by heating to the binary components PtCl4 resp. PdCl2 and SCl2.
    Notes: Die Verbindungen PtS2Cl8 und PdS2Cl6 wurden bei Umsetzungen der Metalle mit einem Überschuß an Schwefel und Chlor in Quarzampullen bei 150-200°C erhalten. Die Kristallstruktur des roten PtS2Cl8 (monoklin; a = 6,271(2)Å; b = 7,177(3)Å; c = 12,368(5)Å; β = 100,15(2)°; Z = 4; Raumgr. P21/c) wird aus oktaedrischen, transkonfigurierten PtCl4(SCl2)2-Molekülen aufgebaut. In der Kristallstruktur des gelben PdS2Cl6 (triklin; a = 4,3387(8)Å; b = 6,8213(14)Å; c = 8,1737(11)Å; α = 104,16(3)°; β = 98,15(3)°; γ = 94,42(3)°; Z = 1; Raumgr. P-1) sind transkonfigurierte PdCl2(SCl2)2-Baugruppen enthalten. Die Verbindungen zerfallen oberhalb 150°C in die binären Komponenten PtCl4 (bzw. PdCl2) und SCl2.
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  • 2
    ISSN: 0044-2313
    Keywords: Bis(octaaquocalcium)-tridecachlorohexamercurate-tridecachloropentamercurate ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Crystal Structure of 2CaCl2 · 11HgCl2 · 16H2O, a Cubic Mercury-rich Chloromercurate with Icosahedral Hg6Cl13 and Hg5Cl13 GroupsThe mercury-rich chloromercurate 2CaCl2 · 11HgCl2 · 16H2O has been obtained by crystallization from concentrated aqueous solutions of CaCl2 and HgCl2 at room temperature. In the cubic crystal structure (a = 18.170(3) Å, space group F23, Z = 4) a three-dimensional framework is formed by Hg6Cl13- and Hg5Cl133- anions with large cavities, in which the dodecahedral Ca(H2O)82+ cations are accomodated. 96 out of 104 Cl atoms in the cell form a lattice complex cP2[12i] with 8 Cl12 icosahedra, which are centered by Cl atoms. In four of these Hg atoms are situated on 6 edges thus forming Cl(HgCl2)6- anions, while the remaining four icosahedra hold 3 Hg atoms on edges and two on faces. Here the central Cl- anions are coordinated by 3 HgCl2 and 2 HgCl3 groups. The Hg5Cl13 and Ca(H2O)8 polyhedra are crystallographically disordered.
    Notes: Das quecksilberreiche Chloromercurat 2CaCl2 · 11HgCl2 · 16H2O ist durch Kristallisation aus konzentrierten wäßrigen Lösungen von CaCl2 und HgCl2 bei Raumtemperatur zu erhalten. In der kubischen Kristallstruktur (a = 18,170(3) Å, Raumgr. F23, Z = 4) bilden Hg6Cl13-- und Hg5Cl133--Anionen ein Gerüst mit großen Hohlräumen, in denen sich Ca(H2O)82+-Kationen mit dodekaedrischer Konformation befinden. Von den 104 Cl-Atomen in der Zelle bilden 96 einen Bauverband cP2[12i] mit acht Cl12-Ikosaedern, die jeweils durch ein Cl-Atom zentriert sind. Bei vier der Ikosaeder befinden sich 6 Hg-Atome auf Kanten, so daß Cl(HgCl2)6--Anionen resultieren. Bei den Hg5Cl133--Anionen besetzen jeweils 3 Hg-Atome Kanten und 2 Hg-Atome Flächen der Ikosaeder, so daß die zentralen Cl--Anionen von 3 HgCl2- und 2 HgCl3-Gruppen koordiniert sind. Die Hg5Cl13- und Ca(H2O)8-Baugruppen sind kristallographisch fehlgeordnet.
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  • 3
    ISSN: 0044-2313
    Keywords: Palladium(II) disulfidechloride ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: PdSCl, a Molecular Palladium(II) Disulfidechloride with Octanuclear Pd8(S2)4Cl8 Groups and with Tetra Metal-coordinated bridging Disulfide GroupsBlack crystals of PdSCl have been obtained by reaction of Pd with S2Cl2 in closed quartz ampoules at 200°C. The compound is to be formulated as a Palladium(II)-disulfidechloride consisting of Pd8(S2)4Cl8 molecules with approximately D4h symmetry. In the octanuclear complexes Pd atoms form a cube, where bridging disulfide groups are found in front of 4 faces and μ2-bridging Cl atoms on 8 edges. In the monoclinic crystal structure (a = 8.763(2) Å; b = 9.082(2) Å; c = 13.662(4) Å; β = 91.748(23)°; V = 1086.8 Å3; Z = 16 PdSCl; Space gr. P21/n) the molecules form a cubic closed arrangement.
    Notes: Schwarze Kristalle von PdSCl wurden durch Umsetzung von Pd-Metall mit S2Cl2 in geschlossenen Ampullen bei 200°C erhalten. Die Verbindung ist ein Palladium(II)-disulfidchlorid, aufgebaut aus molekularen Pd8(S2)4Cl8-Gruppen mit annähernd D4h-Symmetrie. In den achtkernigen Komplexen bilden Pd-Atome einen Würfel mit S2-Gruppen vor vier Flächen und Cl-Atomen vor 8 Kanten. In der monoklinen Kristallstruktur (a = 8,763(2) Å; b = 9,082(2) Å; c = 13,662(4) Å; β = 91,748(23)°; V = 1086,8 Å3; Z = 16 PdSCl; Raumgr. P21/n) sind die Moleküle kubisch dichtest gepackt.
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  • 4
    ISSN: 0044-2313
    Keywords: Iodoplatinates ; Preparation ; Crystal Structure ; Raman Spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Characterization of Iodoplatinates MexNH4-xPtI4 (x = 2-4), Mixed Valence Octaiododiplatinates(II,IV) with Pt2I8 GroupsIodoplatinates APtI4 (A = MexNH4-x with x = 2-4) have been prepared by partial oxidation of the correspondent hexaiododiplatinates(II) A2Pt2I6 with I2 in methanolic solutions. X-ray structure analyses of the bronze-coloured needle-shaped crystals of the compounds showed rows of dinuclear anions Pt2I82-, built up by edgesharing planar PtI4 groups with PtII und octahedral PtI6 groups with PtIV. The different space requirement of the cations leads to the formation of three different structures. Within the anion stacks weak intermolecular PtIV—I … PtII interactions are detectable by Raman spectroscopy.
    Notes: Iodoplatinate APtI4 (A = MexNH4-x mit x = 2-4) wurden durch partielle Oxidation der entsprechenden Hexaiododiplatinate(II) A2Pt2I6 mit I2 in methanolischer Lösung erhalten. Röntgenstrukturanalysen der in Form bronzefarbener Nadeln kristallisierenden Verbindungen ergaben, daß gemischtvalente Octaiododiplatinate(II,IV) mit zweikernigen Anionen Pt2I82- vorliegen, bei denen jeweils eine planare PtI4- und eine oktaedrische PtI6-Gruppe über eine gemeinsame Kante verknüpft sind. Der unterschiedliche Platzbedarf der Kationen führt zur Ausbildung von drei verschiedenen Strukturen, bei denen die komplexen Baugruppen und die Kationen jeweils getrennt stapelförmig angeordnet sind. Mit Hilfe der Ramanspektroskopie sind schwache intermolekulare PtIV—I … PtII- Wechselwirkungen innerhalb der Anionenstapel feststellbar.
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  • 5
    ISSN: 0044-2313
    Keywords: Tetrabromoferrate(III) ; Preparation ; Characterization ; Raman spectra ; X-ray powder diagramms ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Characterization of Tetrabomoferrates(III) AFeBr4 with Monovalent Cations A = Cs, Rb, Tl, NH4, K, Na, Li, AgTetrabromoferrates(III) AFeBr4 of the monovalent cations A = Cs, Rb, Tl, NH4, Na, Ag, Li have been prepared in closed ampoules by reaction of the appropriate bromides with iron and an excessive amount of bromine. The dark red compounds were characterized by DTA, Raman spectroscopy and X-ray powder diffraction. Their crystal structures have been assigned to five structure types, containing FeBr4 anions. The coordination number runs from 12 (Cs+, Rb+) over 10 (NH4+) and 8 (K+), to 6 (Na+, Ag+, Li+). Lattice parameters for all compounds see “Inhaltsübersicht”. CsFeBr4 and RbFeBr4 crystallize orthorhombic in the BaSO4-type, NH4FeBr4 monoclinic in the KAlBr4-type, KFeBr4 orthorhombic in the GaGaCl4-type, NaFeBr4 monoclinic in the NaGaBr4-type, AgFeBr4 and LiFeBr4 monoclinic in the LiAlCl4-type, while the structure of TlFeBr4 is still unknown.
    Notes: Tetrabromoferrate(III) AFeBr4 mit einwertigen Kationen A = Cs, Rb, Tl, NH4, Na, Ag, Li wurden durch Umsetzungen der Bromide ABr und von Fe-Metal1 in Gegenwart eines Br2-Überschusses in geschlossenen Ampullen erhalten. Die dunkelroten Verbindungen wurden analytisch, thermisch, ramanspektroskopisch sowie durch Auswertung der Röntgenpulverdiagramme charakterisiert. Es wurden fünf Strukturen gefunden, jeweils mit tetraedrischen FeBr4-Anionen, aber unterschiedlicher Koordination der Kationen A. Die Koordinationszahlen fallen von 12 (Cs+, Rb+) über 10 (NH4+) und 8 (K+), bis zu 6 (Na+, Ag+, Li+). CsFeBr4 (a = 12,1905(2) Å, b = 7,510(19) Å, c = 9,8832(16) Å) und RbFeBr4 (a = 11,659(1) Å, b = 7,495(1) Å, c = 9,896(1) Å) kristallisieren im orthorhombischen BaSO4-Typ, NH4FeBr4 (a = 13,17(3) Å, b = 7,433(3) Å, c = 9,148(1) Å, β = 106,95(2)°) monoklin im KAlBr4-Typ, KFeBr4 (a = 7,688(1) Å, b = 10,373(2) Å, c = 10,206(2) Å) orthorhombisch im GaGaCl4-Typ, NaFeBr4 (a = 13,9261(3) Å, b = 7,470(2) Å, c = 7,4016(14) Å) orthorhombisch im NaGaBr4-Typ, AgFeBr4 (a = 7,538(2) Å, b = 6,869(1) Å, c = 13,852(2) Å, β= 92,73(2)°) und LiFeBr4 (a = 7,478(2) Å, b = 6,801(1) Å, c = 13,606(2) Å, β = 93,21(2)°) monoklin im LiAlCl4-Typ. Der Aufbau von TlFeBr4 konnte bisher nicht geklärt werden.
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