Neue Verbindungen mit KCu4S3-Struktur

TlCu₄S₃, TlCu₄Se₃, KCu₄Se₃, RbCu₄Se₃, CsCu₄S₃ and CsCu₄Se₃ were prepared by direct synthesis or by the carbonate melt method. They are isotypic with KCu₄S₃, space group P4/mmm,Z=1. The lattice parameters are: TlCu₄S₃:a=3.894(1)Å,c=9.33(1)Å, TlCu₄Se₃:a=3.974(4)Å,c=9.84(2)Å, KCu₄Se₃:a=3.963(4)Å,c=9.81(3)Å, RbCu₄Se₃:a=4.048(2)Å,c=9.86(1)Å, CsCu₄S₃:a=3.964(3)Å,c=9.67(1)Å,and CsCu₄Se₃:a=4.091(2)Å,c=10.08(1)Å. The crystal structure of TlCu₄S₃ was refined from single crystal diffractometer data. Isotypy of the other compounds was checked by visual inspection of rotating crystal orDebye Scherrer film intensities. The relationship between the crystal structures of the MCu₄ X ₃-phases, the TlT₂ X ₂-phases (ThCr₂Si₂ type) and the anti-CaF₂ type is shown.

Hern Professor Dr.H. Bittner zum 60. Geburtstag in Verehrung gewidmet.     

Über LaCo2P2 und andere Neue Verbindungen mit ThCr2Si2- und CaBe2Ge2-Struktur

On LaCo₂P₂ and Other New Compounds with ThCr₂Si₂- and CaBe₂Ge₂-Type Structure The compounds MCo₂P₂ (M = La, Ce, Pr, Nd, Sm, Th, U), MFe₂P₂ (M = La, Ce, U), and ThCo₂As₂ were prepared for the first time. Structure determinations from single crystal X-ray data of LaCo₂P₂ (R = 0.011; 325 F-values), CeCo₂P₂ (R = 0.023; 160 F), PrCo₂P₂ (R = 0.044; 441 F), LaFe₂P₂ (R = 0.024; 511 F), and CeFe₂P₂ (R = 0.016; 183 F) with 11 variable parameters each resulted in atomic positions within the range of the ThCr₂Si₂-type. The powder patterns of ThCo₂P₂, and ThCo₂As₂ show superstructure reflections indicating a CaBe₂Ge₂-type structure. The other compounds can be assigned to the ThCr₂Si₂-type. Chemical bonding of these can be rationalized by a simple band structure model where bonding transition metal – transition metal interactions are important.     

Ternäre Verbindungen des Natriums und Kaliums mit CaCu4P2-Struktur

Ternary Compounds of Sodium and Potassium with CaCu₄P₂-type Structure NaCu₄As₂, NaCu₄Sb₂, KCu₄As₂, and KCu₄Sb₂ were prepared and investigated by single crystal methods. They crystallize rhombohedrally and are isotypic to CaCu₄P₂ (space group R3 m). The (hexagonal) lattice constants are By reaction of the same element compositions but alterated conditions six further compounds could be synthesized in the systems Na(K)/Cu(Ag)/P(As, Sb). They crystallize hexagonally, their structure which has not been determined seems to be related to the structure of CaCu₄P₂.     

Neue AB2X2-Verbindungen mit CaBe2Ge2-Struktur

New AB₂X₂ Compounds with CaBe₂Ge₂ Structure Crystal structure of ternary RELi₂Sb₂ compounds (RE = Ce, Pr, Nd) is reported. The compounds are isotypic and crystallize tetragonally in the CaBe₂Ge₂ structure (space group P4/nmm), which is a modified type of the ThCr₂Si₂ structure.     

Silicide und Germanide mit Gd6Cu8Ge8-Struktur

Zusammenfassung Die Verbindungen {Sc,Y,Tb,Dy,Ho,Er,Tm,Yb,Lu}₆Cu₈Si₈ sowie {Y,Yb}₆Cu₈Ge₈ werden hergestellt. Diese sind isotyp mit der Gd₆Cu₈Ge₈-Struktur. Die Gitterparameter werden ermittelt.

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Silicides and germanides with Gd₆Cu₈Ge₈-structure type

The compounds {Sc,Y,Tb,Dy,Ho,Er,Tm,Yb,Lu}₆Cu₈Si₈ and {Y,Yb}₆Cu₈Ge₈ have been prepared. They were found to be analogous with the Gd₆Cu₈Ge₈-structure type. The lattice parameters have been determined.

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Neue Verbindungen mit Zr2Fe12P7-Struktur und Verfeinergung der Kristallstrukturen von Er2Co12P7 und Er2Ni12P7

New Compounds Zr₂Fe₁₂P₇-Type Structure and Refinement of the Crystal Structures of Er₂Co₁₂P₇ and Er₂Ni₁₂P₇ The compounds Y₂Ni₁₂P₇ and Ln₂Ni₁₂P₇ (Ln = Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Lu) were prepared for the first time and characterized by their lattice constants. Their crystal structure corresponds to that of Zr₂Fe₁₂P₇. The structure of Er₂Co₁₂O₇ and Er₂Ni₁₂P₇ were refined from single-crystal counter data. Chemical bonding and the question of the proper space group for those and the closely related compounds V₁₂P₇ and Cr₁₂P₇ are discussed.     

Neue Boride mit Cr23C6-Struktur

Ohne Zusammenfassung     

Neue Fluorozirconate und ‐hafnate mit V2+ und Ti2+

New Fluorozirconates and ‐hafnates with V²⁺ and Ti²⁺ During investigations of the systems MF₂/KF/MF₄ e. g. MF₂/NaF/MF₄ (M²⁺ = Ti²⁺, V²⁺, M⁴⁺ = Zr⁴⁺, Hf⁴⁺) we obtained blue crystals of VZrF₆, VHfF₆, KVZrF₇, blue‐green crystals of NaVHf₂F₁₁, yellow crystals of TiHfF₆ and NaTiHf₂F₁₁, and yellow to rubyred crystals of TiZrF₆, respectively. According to single crystal data, VZrF₆ VHfF₆ and TiZrF₆ crystalizes in the ordered ReO₃‐type (cubic, Fm3m, a = 812,1(5), 804,2(8), and 821,0(2) pm, Z = 4). TiHfF₆ crystalizes in a high‐temperature‐modification (cubic, ReO₃‐type, Pm3m, a = 392,3(2) pm, Z = 2). KVZrF₇ is isotyic to KPdZrF₇ (orthorhombic, Pnna, a = 1109,8(6), b = 788,0(7), c = 648,0(15) pm, Z = 4). NaTiHf₂F₁₁ and NaVHf₂F₁₁ crystalizes monoclinic (C2/m, a = 910,5(7), b = 675,9(7), c = 773,6(5) pm, β = 116,10(6)° and a = 917,7(5), b = 685,7(5), c = 752,4 pm, β = 118,28(1)°, Z = 2, respectively) and are also isotypic to already known AgPdZr₂F₁₁.     

SrNi10P6, EuNi10P6 und BaCo10As6: Phasenumwandlungen und Kristallstrukturen

SrNi₁₀P₆, EuNi₁₀P₆, and BaCo₁₀As₆: Phase Transitions and Crystal Structures SrNi₁₀P₆, EuNi₁₀P₆ and BaCo₁₀As₆ were prepared by heating mixtures of the elements in the range of 800°–1000 °C and were investigated by means of single‐crystal X‐ray methods. At higher temperatures the isotypic Ni phosphides (HT‐SrNi₁₀P₆: a = 6.481(2), b = 16.080(4), c = 8.763(2) Å (350 °C); HT‐EuNi₁₀P₆: a = 6.509(2), b = 16.063(4), c = 8.766(4) Å (500 °C)) crystallize in the BaNi₁₀P₆ type structure (Cmca; Z = 4), which can be described as an arrangement of Ni₁₄P₁₂ cages with Sr or Eu atoms in the centres. The cages are linked to layers separated by additional Ni atoms, which are coordinated tetrahedrally by P atoms of different cages. Cooling down both compounds undergo from about 270 °C (SrNi₁₀P₆) and 410 °C (EuNi₁₀P₆) respectively a second‐order phase transition involved with a change to an orthorhombic P lattice. In the structure of the NT phases (Pnma; Z = 4; NT‐SrNi₁₀P₆: a = 15.993(1), b = 6.473(1), c = 8.735(1) Å; NT‐EuNi₁₀P₆: a = 15.925(1), b = 6.478(1), c = 8.720(1) Å (25 °C)) the Ni₁₄P₁₂ cages are slightly distorted in comparison with the high temperature modifications. BaCo₁₂As₆ (a = 16.405(9), b = 6.858(4), c = 8.955(7) Å) crystallizes in the same structure (Pnma), but doesn't exhibit a comparable phase transition up to 600 °C. Measurements of the suszeptibiliy of EuNi₁₀P₆ between 4 K and 850 K showed divalent Europium and no magnetic order down to 4 K.     

Komplexboride mit ReB2-Struktur

Ohne Zusammenfassung

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Complex borides with anReB ₂ structure

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Neue ternäre Verbindungen des Caesiums mit Elementen der 8. Nebengruppe und 5. Hauptgruppe

New Ternary Compounds of Cesium and Elements of the 8^th Transition Metal Group and the 5^th Main Group In the ternary systems Cesium/element of the 8^th transition metal group/element of the 5^th main group some new compounds were found and investigated. Compounds of the formula Cs₂MX₂ (M = Pt, Pd, Ni; X = P, Sb, Bi) can be placed in a line with the K₂PdP₂-type structure. The new compound with the formula CsFe₂Sb₂ crystallizes in the ThCr₂Si₂-type structure. By single crystal measurements CsFe₂As₂ was found to crystallize in the space group I4/mmm with the lattice constants a = 389.43 pm and c = 1 509.97 pm.     

Neue rhodanilatähnliche Verbindungen mit Morpholin

Substitution reactions of K₃[Cr(NCS)₆] with morpholine were studied. The formula of the complex anion, [Cr(NCS)₄(morph)₂]^–, was established.23 new complex compounds of these types have been prepared from the hydrochlorides of some aliphatic or heterocyclic amines, alkaloids and cobalt(III)ammine bases resp.Their thermal behaviour and the mechanism of pyrolysis of these salts was studied by derivatographic methodes. From UV and IR spectra some structural problems are resolved and discussed.

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Neue Abkömmlinge der TiSi2-Struktur

Zusammenfassung In Mn-Defektdisiliciden führt Substitution von Mn durch Cr, Fe oder Co zur Ausbildung neuer Phasen, die durch bestimmte Vielfache derc-Achse einer charakteristischen Unterzelle repräsentiert werden. Das Verhältnis Metall/Silicium ist eine Funktion der Valenzelektronenkonzentration. Os₂Ge₃ erweist sich als isotyp mit Os₂Si₃ und gehört damit ebenfalls zu den TiSi₂-Abkömmlingen.

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Substitution of Mn by Cr, Fe or Co within Mn-defect disilicides leads to a series of new phases characterized by various multiples of thec-axis of the subcell. The metal/silicon ratio depends on the valence electron concentration. Os₂Ge₃ has been found to be isotypic with Os₂Si₃, another derivative of the TiSi₂-structure type.

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Neue stellungsisomere reineckesalzähnliche Verbindungen mit Toluidinen

Zusammenfassung Es wurden eine Reihe von Substitutionsreaktionen mit entwässertem K₃[Cr(NCS)₆] und aromatischen Aminen, ohne Verwendung von Lösungsmitteln, durchgeführt. Es wurde beobachtet, da die sehr schwachen Basen mit p_K-Werten 14–16, wie die isomeren Mono- und Dinitro-aniline, die Anthranil- und Sulfanilsäuren, für diese Substitutionsreaktionen ungeeignet sind. Die Alkyl-anilinderivate, wie daso-, m- undp-Toluidin (p_K=10–11) bilden dagegen leicht reineckesalzähnliche Verbindungen: Amin· H[Cr(Toluidin)₂(NCS)₄]. Die Zusammensetzung der neuen Komplexanionen wurde bei einer Reihe von doppelten Umsetzungsreaktionen mit den Chlorhydraten einiger heterocyclischen Aminen festgestellt.Für die Klärung einiger Strukturfragen wurden spektrophotometrische Untersuchungen im UV und IR durchgeführt und die thermische Stabilität bzw. der Mechanismus des Pyrolysenvorganges auf thermogravimetrischem Wege verfolgt.

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Substitution reactions of anhydrous K₃[Cr(NCS)₆] with aromatic amines without applying of solvents were studied.It was observed, that the very weak bases (pK-values 14–16, e.g. isomeric mono- and dinitro-anilines, the anthranilic and sulfanilic acids) are unsuitable for substitution reactions. The alkylaniline derivates e.g.o-, m- andp-toluidine (pK=10–11) form easily reineckesalt analogous compounds: Amin· ·H[Cr(toluidine)₂(NCS)₄]·The formula of the 3 new complex anions: [Cr(toluidine)₂ (NCS)₄]- was established by preparative methods, with a series of double decomposition reactions, using chlorohydrates of some heterocyclic amines for this purpose. From spectroscopical investigations (UV and IR) some structural problems are resolved and discussed.The thermal stability and the mechanism of pyrolysis of these salts was studied by thermogravimetric analysis.

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Neue Verbindungen mit Granatstruktur. VI. Vanadate

New Compounds with Garnet Structure. VI. Vanadates The preparation of vanadate-garnets of the following three types is reported: (I) {Na₃}[B₂^III](V₃)O₁₂ (B^III = Cr, Sc), (II) {LiCa₂}[B₂^II](V₃)O₁₂ (B^II = Mg), (III) {Ca₂A^III}[Li₂] (V₃)O₁₂ (A^III = In, Sc). The Cr-compound of type (I) decomposes above 690°C into a mixture of Cr₂O₃ and NaVO₃. The analogous Fe-compound decomposes in a similar way already at 400°C; therefore the preparation by solid state reaction is not possible. Employing larger B^III-ions (Y, Yb, Lu) no garnets of type (I), but mixtures of B^IIIVO₄ (zircon structure) and Na₃B^IIIV₂O₈ are formed. Garnets of type (II) do not exist, when B^II are Co and Ni. Mixtures of {Ca₃}[LiB^II](V₃)O₁₂ (garnet structure), LiB^IIVO₄ (spinel structure) and B₃^II(VO₄)₂ are formed. With type (III) for A^III = Y reaction occurs forming a mixture of YVO₄, Ca₃(VO₄)₂ and Li₃VO₄.     

Ein neues Oxochromat: SrNi2Cr8O15 vom Strukturtyp BaV10O15

Summary A new quaternary oxochromate(III) was prepared by solid state reaction. Single crystal X-ray investigations of SrNi₂Cr₈O₁₅ show that this compound belongs to the BaV₁₀O₁₅ type. [Space group D _2h ¹⁸ - Ccmb,a=10.042;b=11.413;c=9.260 Å;Z=4.] Ni²⁺ and Cr³⁺ occupy the octahedrally coordinated point positions statistically. The surrounding of Sr²⁺ is similar to the iso- and heteropolyacids.

     

Weitere metastabile Verbindungen mit Tunnelstruktur BaCa2Er10O18 und BaCa2Yb10O18

Single crystals of the unknown compounds BaCa₂Er₁₀O₁₈ (A) and BaCa₂Yb₁₀O₁₈ (B) were prepared by a high-temperature CO₂-laser technique and investigated by X-ray work. (A) and (B) are metastable compounds with an Ln₁₀O₁₈⁶⁻ framework. Two types of tunnels built up by this framework are occupied statistically and in a disordered manner by Ba²⁺, Ca²⁺ and Ln³⁺ ions. The relationship with compounds of the formula AB₂Ln₆O₁₂ are discussed.     

Neue Reineckesalzanaloge Verbindungen mit tertiären aromatischen Aminen

Substitution reactions of anhydrous K₃[Cr(NCS)₆] with tertiary aromatic monoamines such as N,N-dimethylaniline and N,N-diethylaniline were carried out in the absence of solvents. The tertiary amines readily form compounds analogous to Reinecke salts,amine ₂H[Cr(NCS)₄(N,N-dimethylaniline)₂] andamine ₂H[Cr(NCS)₄(N,N-Diethylaniline)₂] respectively. The formula of the new complex anions was established by a series of double decomposition reactions with the hydrochlorides of some heterocyclic N-bases, alcaloids and cobalt(III)-ammine complexes. Some structural problems were resolved by UV and IR spectroscopic studies.