Neue ternäre Phosphide und Arsenide des Caesiums mit Elementen der 8. Nebengruppe

New Ternary Phosphides and Arsenides of Cesium and Element of the 8th Transition Metal Group In the ternary systems Cesium/8^th transition metal group/5^th main group some new compounds were found and investigated. By single crystal measurements CsRh₂P₂ was found to crystallize in the space group 14/mmm with the lattice constants a = 390.11 pm and c = 1429.36 pm. The new compounds with the formula CsM₂X₂ (M = Fe, Co, Ru, Rh, Ir; X = P or As) crystallize in the ThCr₂Si₂-type structure, compounds of the formula Cs₂MX₂ (M = Ni, Pd, Pt; X = P or As) can be placed in a line with the K₂PdP₂-type structure.     

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 ternäre Phasen von Platinmetallen mit Lithium und Elementen der 4. Hauptgruppe

Novel Ternary Phases of Platinum Metals with Lithium and Main Group IV Elements The elements palladium, platinum, and iridium (Me) form ternary compounds with lithium and the elements germanium, tin or lead (X) of the formulas Li₂MeX and/or LiMe₂X. The lattice constants of the cubic fc. crystallizing compounds see ?Inhaltsübersicht”?. Besides the cubic form of LiPd₂Ge there exists a tetragonal structure with a = 6.25₄ and c = 6.41₀ Å. X-ray investigations on single crystals showed that LiPd₂Ge crystallizes in a Heusler lattice (L2₁A type), Li₂PdSn has a modified Li₃Bi structure (L2₁C type). The homogeneity range between the compositions Li₂PdX and LiPd₂X was investigated.     

Neue ternäre Kupferpnictide mit modifizierten BaAl4-Strukturen

New Ternary Copper Pnictides with Modified BaAl₄ Type Structures EuCu₂As₂ (a = 4.215(1) Å, c = 10.185(2) Å) and EuCu₂Sb₂ (a = 4.504(1) Å, c = 10.824(2) Å) were prepared by heating (900°C) mixtures of CuCl and arsenic (antimony) with europium. The by-products were dissolved by dilute acetic acid. The arsenide crystallizes in the ThCr₂Si₂ type structure (I4/mmm; Z = 2) with holes in the copper arrangement, whereas the antimonide forms the CaBe₂Ge₂ type structure (P4/nmm; Z = 2). The stability ranges of both phases were determined by mixed crystal formation in accordance with EuCu₂As_2–xSb_x. Magnetic measurements showed, that Europium is divalent and that the compounds order magnetically at low temperatures. BaCu₂Sb₂ (I4/mmm; a = 4.655(1) Å, c = 32.709(6) Å; Z = 6) was prepared by heating a mixture of binary antimonides of barium and copper in a melt of NaCl/KCl. The structure of this compound consists building elements of the CaBe₂Ge₂ and the ThCr₂Si₂ type structure. The already known compounds SrCu₂As₂ and BaCu₂As₂ were produced in a homogeneous form for the first time and their structures (ThCr₂Si₂ type) redetermined by means of single crystal X-ray methods.     

Neue ternäre Selenide der Lanthanide durch Reduktion der Sesquiselenide

New Ternary Selenides of Lanthanoides by Reduction of Sesquiselenides The compounds MLn₂Se₃ (M = Na; Ln = La? Sm) and MLn₈Se₁₂ (M = Na, Ca; Ln = La? Sm) were prepared by reduction of the corresponding lanthanide sesquiselenides with sodium and calcium, respectively, for the first time. Further-more MLa₈Se₁₂ (M = Sr, Eu) could be obtained in an analogous way. All compounds were characterized by chemical analysis and X-ray powder diffraction. The electronic structures of these compounds were investigated by band structure calculations and magnetic measurements.     

Ternäre Verbindungen des Lithiums und Natriums mit Mangan und Elementen der 5. Hauptgruppe

Es wird über Darstellung und Kristallstruktur ternärer AMnX-Verbindungen (A ? Li, Na; X ? P, As, Sb, Bi) berichtet. Sie kristallisieren tetragonal in Raumgruppe P4/nmm-D_4h⁷, wobei sich LiMnX und NaMnX durch unterschiedliche Punktlagen der Alkaliatome unterscheiden. Die AMnX-Strukturen werden mit denen verwandter AMX-Verbindungen verglichen (A ? Li, Na, K, Rb; M ? Be, Mg, Zn, Cd; X ? 5b-Element). Ternary Compounds of Lithium and Sodium with Manganese and Elements of the Fifth Main Group Formation and crystal structure of ternary AMnX compounds (A ? Li, Na; X ? P, As, Sb, Bi) are reported. These compounds crystallize in the tetragonal space group P4/nmm-D. The structures of LiMnX and NaMnX differ by the positions of the alkali atoms. Structural relationship to AMX compounds (A ? Li, Na, K, Rb; M ? Be, Mg, Zn, Cd; X ? 5b element) are discussed.     

Neue ternäre Rhodium‐ und Iridium‐Phosphide und ‐Arsenide mit U4Re7Si6‐Struktur

New Ternary Rhodium‐ and Iridium‐Phosphides and ‐Arsenides with U₄Re₇Si₆ Type Structure Single crystals of Mg₄Rh₇P₆ (a = 7.841(1) Å), Mg₄Rh₇As₆ (a = 8.066(1) Å), Yb₄Rh₇As₆ (a = 8.254(1) Å) and Mg₄Ir₇As₆ (a = 8.082(2) Å) were prepared by heating mixtures of the elements in a lead flux and were investigated by means of X‐ray methods. The compounds are isotypic and they crystallize in the U₄Re₇Si₆ type structure (Im 3 m; Z = 2), which is formed by CeMg₂Si₂ analogous units, which are twisted against each other. The Rh(Ir) atoms building these units are coordinated tetrahedrally by the non‐metal. The P(As) atoms of six units form a regular octahedron, which is centred by an additional Rh(Ir) atom. This second structural segment corresponds to the perovskit type structure.     

Über ternäre Thalliumchalkogenide mit Thalliumselenidstruktur

On Ternary Thallium Chalcogenides with Thallium Selenide Structure. By means of single crystal investigations, it has been confirmed that the compounds TlGaTe₂, TIInSe₂, and TIInTe₂ crystallize in the TISe type (B37). As an univalent cation thallium is surrounded by eight chalcogen atoms. Gallium and indium are trivalent with tetrahedral coordination and covalent bonds. The interatomic distances as well as coordination and bonding resulting from them are discussed.     

Neue ternäre Germanide des Lithiums mit Lanthanoiden im Fe2P-Typ: LiErGe,LiHoGe, LiNdGe und LiSmGe

Ternary Germanides of Lithium and Rare-Earth-Metals with Fe₂P-Type Structure: LiErGe, LiHoGe, LiNdGe and LiSmGe In the systems Li? M? Ge (M ? Er, Ho, Nd, Sm) the compounds LiErGe, LiHoGe, LiNdGe and LiSmGe were prepared. They crystallize hexagonally (space group P-6 2m), and a C22-(Fe₂P-type) lattice was found. The crystal structure of LiErGe was determined by X-ray single crystal investigation. Structural features of the compounds are discussed in comparison.     

Synthese und Kristallstrukturen ternärer Phosphide und Arsenide des Rhodiums und Iridiums

Ternary Phosphides and Arsenides of Rhodium and Iridium: Synthesis and Crystal Structures Single crystals of eight new compounds were prepared by heating mixtures of the elements in a lead flux. They were investigated by X‐ray methods. Ca₂Ir₁₂P₇ (a = 9.512(1), c = 3.923(1) Å)is an additional representative of the Zr₂Rh₁₂P₇ type structure, micro domains required refinements of the structural parameters in space group P6₃/m. Ca₅Rh₁₉P₁₂ (a = 12.592(1), c = 3.882(1) Å) and Ca₅Ir₁₉P₁₂ (a = 12.577(2), c = 3.954(1) Å) crystallize with the Ho₅Ni₁₉P₁₂ type structure (P6¯2m; Z = 1), whereas the compounds A₆Rh₃₀X₁₉ form a slightly modified structure of the Yb₆Co₃₀P₁₉ type. The lattice constants are: Ca₆Rh₃₀P₁₉: a = 15.532(1) Å, c = 3.784(1) Å Sr₆Rh₃₀As₁₉: a = 16.135(2) Å, c = 3.916(1) Å Eu₆Rh₃₀P₁₉: a = 15.566(1) Å, c = 3.821(1) Å Eu₆Rh₃₀As₁₉: a = 16.124(1) Å, c =5 3.903(3) Å Yb₆Rh₃₀P₁₉: a = 5 15.508(1) Å, c =5 3.770(1) Å Because one of the four non‐metal atoms, located on different crystallographic sites, is disordered along [001] micro domains are formed. Therefore the parameters were not refined in space group P6¯ (Yb₆Rh₃₀P₁₉ type), but in space group P6₃/m. The metal:non‐metal ratio of all compounds is in the range of 2:1. Accordingly most of the non‐metal atoms are coordinated by nine metal atoms, which form tricapped trigonal prisms. These polyhedra are combined with each other in a different way.     

Ternäre intermetallische Phasen des Lithiums mit Elementen der 4. Neben- und 5. Hauptgruppe mit statistischer Metallverteilung im „Kationen”︁-Teilgitter

Ternary Intermetallic Phases of Lithium, Transition Metals of the 4^th Group and Elements of the 5^th Maingroup with Statistical Metal Distribution in the ?Cation”?-Substructure The results of X-ray investigations and neutron diffraction on new and in some cases already known [1, 2] ternary intermetallic phases of Lithium with transition metals of the 4^th group (b) and those of the 5^th main group (X = P, As, Sb, Bi) will be reported. They crystallize in a partly ?filled”? antifluorite type structure with a statistical Li/B-distribution in the tetrahedral sites. The structures are obviously stabilized by small amounts of enclosed d-elements.     

Untersuchungen über ternäre Chalkogenide. XXIV. Zur Struktur des TlGaSe2

On Ternary Chalcogenides. XXIV. The Structure of TlGaSe₂ TlGaSe₂ is monoclinic with a = 10.772(3), b = 10.771(5), c = 15.636(8) Å, ß = 100.6(3)°, Z = 16, space group Cc. The refinement yielded an R value of 0.082 for 1366 unique observed reflections (MoKα). The compound crystallizes with a layer structure with two anion layers perpendicular to c* in the unit cell. The structural motive of the layers are large corner-linked Ga₄Se₁₀- tetraeder consisting of four corner-linked GaSe₄ tetrahedra. Two adjacent layers are turned relative to each other by 90°. They are kept together by Tl¹⁺ ions, which are situated on straight lines parallel to the edges of the Ga₄Se₁₀ groups. They are surrounded by six selenium atoms forming trigonal-prismatic TlSe₆ polyhedra. 4₂ screw-axes within the layers are the reason for a strongly pronounced pseudo tetragonal symmetry. Different possibilities of stacking cause a onedimensional disorder along the c* direction. The relations between the TlGaSe₂ type and the TlSe type and also the high-pressure modifications of some compounds with the TlGaSe₂ structure are discussed.     

Ba8Cu16P30 – eine neue ternäre Variante des Clathrat I-Strukturtyps

Ba₈Cu₁₆P₃₀ – a New Ternary Variant of the Clathrate I Type Structure Ba₈Cu₁₆P₃₀ (a = 14.117(1) Å, b = 10.093(1) Å, c = 28.022(2) Å) was prepared by heating a mixture of the elements (800°C; excess of Ba and P; removal of the by-products by acetic acid/H₂O₂). The compound crystallizes orthorhombically (Pbcn; Z = 4) in a new superstructure of the cubic clathrate I type structure with an ordered distribution of the atoms. The structure is characterized by a three-dimensional framework of CuP₄ tetrahedra with cavities in the form of pentagonal dodecahedra and tetrakaidecahedra, which are occupied by the Ba atoms. The compound shows semiconduction, therefore the composition should be Ba₈Cu_15.5P_30.5.     

Neue gemischtvalente ternäre Bromide und Iodide mit Dysprosium und Thulium vom Typ A5M3X12

New Mixed‐Valence Ternary Bromides and Iodides of Dysprosium and Thulium of the Type A₅M₃X₁₂ The new ternary mixed‐valence bromides and iodides of dysprosium and thulium Rb₅Dy₃Br₁₂, Rb₅Tm₃Br₁₂, K₅Dy₃I₁₂, K₅Tm₃I₁₂, Rb₅Dy₃I₁₂ and Rb₅Tm₃I₁₂ were obtained by metallothermic reduction of DyBr₃, TmBr₃, DyI₃ and TmI₃, respectively, with potassium and rubidium in the presence of the respective alkali metal halides in sealed niobium containers. The crystal structure was determined for the example of K₅Dy₃I₁₂ (hexagonal, P 6 2m, Z = 1; a = 1446.7(2), c = 473.3(1) pm): DyI₆ octahedra are connected via common trans edges to chains. Magnetic measurements on X‐ray pure samples show Curie‐Weiss behaviour at sufficiently high temperatures. Antiferromagnetic coupling occurs at low temperatures.     

Neue ternäre Phosphide und Arsenide mit einem Metall : Nichtmetall‐Verhältnis im Bereich von 2 : 1

New Ternary Phosphides and Arsenides with a Metal : Non‐Metal Ratio in the Range of 2 : 1 Six new compounds were prepared by heating mixtures of the elements or by reaction of them in a tin(lead) flux. They were investigated by single crystal X‐ray methods. Sc₂Ni₁₂P₇ (a = 9.013(1), c = 3.590(1) Å) crystallizes in the Zr₂Fe₁₂P₇ type structure (P6; Z = 1), which is basically built up likewise by Eu₂Pd₁₂As₇ (a = 10.040(1), c = 4.100(1) Å) and Sr₂Rh₁₂P₇ (a = 9.626(1), c = 3.844(1) Å), but one of seven non‐metal atoms has a somewhat modified environment and is disordered along [001]. Therefore their crystal structure corresponds to the Ho₂Rh₁₂As₇ type structure (P6₃/m; Z = 1). Ca₂Ni₇P₄ (a = 3.703(1), b = 9.209(1), c = 10.378(1) Å) forms the Nd₂Ni₇P₄ type structure (Pmn2₁; Z = 2), whereas the atomic arrangements of Ca₄Rh₁₃As₉ (a = 3.903(2), b = 11.221(1), c = 19.411(4) Å) and Sm₄Rh₁₃As₉ (a = 3.913(2), b = 11.242(6), c = 19.440(6) Å) correspond basically to the Ho₄Ir₁₃Ge₉ type structure (Pmmn; Z = 2), but the disorder of Rh8 required the occupation of splitting positions. The transition metals have three, four or five neighbouring atoms of phosphorus or arsenic and form together with them three‐dimensional covalent frameworks, of which holes are occupied by the atoms of the electropositive metal. Most of the polyhedra around the P and As atoms respectively consist of trigonal prisms of metal atoms with additional metal atoms capping the rectangular faces of the prisms. This environment ist characteristic for ternary phosphides and arsenides with a metal : non‐metal ratio in the range of 2 : 1.     

Neue ternäre Käfigverbindungen aus den Systemen Barium–Indium/Zink/Cadmium–Germanium: Zintl-Verbindungen mit Phasenbreite?

New Ternary Clathrate Compounds in the Systems Barium–Indium/Zinc/Cadmium–Germanium: Zintl Compounds with Phase Width? By systematic investigations in the systems barium–indium/zinc/cadmium–germanium we found a couple of new electrovalent ternary compounds with A₈X₄₆ clathrate (I) type structures. They crystallize cubically in space-group Pm3n. For Ba₈In₁₆Ge₃₀ (a = 1 075.8 pm), Ba₈Zn₈Ge₃₈ (a = 1 082.0 pm) and Ba₈Cd₈Ge₃₈ (a = 1 096.0 pm) the structures were verified by X-ray single crystal diffraction data. According to valence and bounding distances the new clathrates should be Zintl compounds. Measurements of the temperature dependence of the electrical resistivity proved, that they are indeed semiconductors. A part of the 2B/3B metal atoms can be substituted by germanium. Charge balance will be retained by creation of vacancies in the A₈X₄₆ type structures. By phase analysis the limits of the composition range were determined as Ba₈In₄Ge₉[]₃Ge₃₀ (a = 1 084.9 pm), Ba₈Zn₄Ge₁₀[]₂Ge₃₀ (a = 1 073.6 pm) and Ba₈Cd₄Ge₁₀[]₂Ge₃₀ (a = 1 082.0 pm).