Synthese und Kristallstruktur von Sr3Ga2O5Cl2 und Sr3Fe1.18Al0.82O5Cl2

Solid state reactions, by using a flux, lead to the new compounds Sr₃Ga₂O₅Cl₂ (A) and Sr₃Fe_1.18Al_0.82O₅Cl₂ (B). By means of single crystal X-Ray determinations a monoclinic symmetry (space group C ₂ ² -P2₁, (A):a=9.569 (2) Å; (B):a=9.550 (2) Å,Z=4) was found. Both compounds are not isotypic to Sr₃Fe₂O₅Cl₂ but crystallize like Ba₃Fe₂O₅Cl₂.

     

Zur Kenntnis von Ba10Fe8Pt2Cl2O25

About Ba₁₀Fe₈Pt₂Cl₂O₂₅ The crystal structure of Ba₁₀Fe₈Pt₂Cl₂O₂₅ has been solved by direct methods, using intensity data collected by means of an automatic diffractometer (MoKα). It crystallizes in the hexagonal space group D–P6₃/mmc: a = 5.8034(4) Å, c = 24.997(5) Å, Z = 1. Fe³⁺ ions occur in both octahedral and tetrahedral coordination. Two types of Ba²⁺ ions are formed, with ten and twelve neighbouring atoms. The structure consists of plane connected FeO₆ and PtO₆ octahedra which are connected by corner shared FeO₄ tetrahedra.     

Synthese und Kristallstruktur von Ba4,5Ca1,5La2Fe4O15, Ba5CaEu2Fe4O15 und Ba5CaNd2Co4O15

Synthesis and Crystal Structure of Ba_4.5Ca_1.5La₂Fe₄O₁₅, Ba₅CaEu₂Fe₄O₁₅ and Ba₅CaNd₂Co₄O₁₅ The compounds (I) Ba_4.5Ca_1.5La₂Fe₄O₁₅, (II) Ba₅CaEu₂Fe₄O₁₅ and (III) Ba₅CaNd₂Co₄O₁₅ were prepared and investigated by single crystal X-Ray technique. They belong to the Ba₆Nd₂Al₄O₁₅ typ, space group C? P6₃mc, (I): a = 11.677, c = 6.959 Å; (II): a = 11.570, c = 6.892 Å; (III): a = 11.604, c = 6.839 Å, Z = 2. The crystal chemistry of these substances will be discussed.     

Über Oxocuprate. XI. Zur Kenntnis von Ba3Cu2O4Cl2

On Osocuprates. XI. Ba₃Cu₂O₄Cl₂ A new oxohalogenocuprat, Ba₃Cu₂O₄Cl₂ mas prepared and investigated by X-ray single crystal methods. The hitherto unknown compound has orthorhombic symmetry (Space group: D_2h⁵—Pmma; a = 6.653, b = 6.000, c = 10.563 Å). It shows angled chains of O^2?-squares around Cu²⁺. One of the Cu²⁺ positions is completed by Cl^minus; to a tetragonal pyramid. The coordination polyhedrals of Ba_I–III and the connection with the Cu/O-chains are described and discussed.     

Geordnete Oktaederbesetzung in Ba6La2Al1,5Fe2,5O15

Ordered Occupation of Octahedra in Ba₆La₂Al_1,5Fe_2,5O₁₅ Ba₆La₂Al_1.5Fe_2.5O₁₅ was prepared and investigated by X-ray single crystal technique. It crystallizes in the space group C – P6₃mc; a = 11.814, c = 7.1003 Å; Z = 2. The M³⁺O₆ octahedra are occupied exclusively by Fe³⁺ ions, the M³⁺O₄ tetrahedra in contrast are statistically filled by Fe³⁺ and Al³⁺ ions. Ba₆La₂Al_1.5Fe_2.5O₁₅ is a partially ordered mixed crystal of the pure iron and aluminium compounds.     

Ein neues Oxohalogenoferrat: Sr3Fe2O5Cl2

About a New Oxohalogenoferrite: Sr₃Fe₂O₅Cl₂ The preparation and single crystal X-ray investigation of Sr₃Fe₂O₅Cl₂ are described. This compound belongs to the Sr₃Ti₂O₇ structure with a = 3.942(2) and c = 23.786(12) Å; space group D?I4/mmm. Sr₃Fe₂O₅Cl₂ shows an one-sided streched FeO₅Cl octahedron in respect to the Fe? Cl distances. This particularity is discussed in comparison to other K₂NiF₄-type compounds.     

Kristallstrukturuntersuchungen an Verbindungen des Typs A3(M,Nb)8O21 (A  Tl,Ba; M  Fe,Ni)

Crystal Structure Investigations of Compounds with the A₃(M, Nb)₈O₂₁-Type (A ? Tl, Ba; M ? Fe, Ni) Tl₃Fe_0,5Nb_7,5O₂₁ (A), a hitherto unknown phase of the A₃(M, Nb)₈O₂₁-type, and Ba₃Fe₂Nb₆O₂₁ (B), Ba₃Ni_1.33Nb_6,66O₂₁ (C) were prepared and investigated by single crystal X-ray technique. ((A): a = 9.145(1), c = 11.942(1) Å; (B): a = 9.118(2), c = 11.870(1) Å; (C) a = 9.173(3), c = 11.923(1) Å, space group D? P6₃/mcm, Z = 2). There is a statistic occupation of the M-positions by Nb⁵⁺ and Fe³⁺ or Nb⁵⁺ and Ni²⁺, respectively. An other compound Ba₃Fe₂Ta₆O₂₁ is partially ordered in respect to Ta⁵⁺ and Fe³⁺. Calculations of the Coulomb-part of lattice energy are discussed.     

Ba3Li2V2O7Cl4, a new vanadate with a channel structure

The tribarium dilithium divanadate tetrachloride Ba₃Li₂V₂O₇Cl₄ is a new vanadate with a channel structure and the first known vanadate containing both Ba and Li atoms. The structure contains four non‐equivalent Ba²⁺ sites (two with m and two with 2/m site symmetry), two Li⁺ sites, two nonmagnetic V⁵⁺ sites, five O²⁻ sites (three with m site symmetry) and four Cl⁻ sites (m site symmetry). One type of Li atom lies in LiO₄ tetrahedra (m site symmetry) and shares corners with VO₄ tetrahedra to form eight‐tetrahedron Li₃V₅O₂₄ rings and six‐tetrahedron Li₂V₄O₁₈ rings; these rings are linked within porous layers parallel to the ab plane and contain Ba²⁺ and Cl⁻ ions. The other Li atoms are located on inversion centres and form isolated chains of face‐sharing LiCl₆ octahedra.     

Über ternäre Oxocuprate. X. Zur Kenntnis von Ba2Cu3O4Cl2

About Ternary Oxocuprates. X. On Ba₂Cu₃O₄Cl₂ The preparation of Ba₂Cu₃O₄Cl₂ and results by single crystal X-ray methods are described (a = 5.517, c = 13.808 Å; Space group D–I4/mmm). A so far unknown arrangement of square coordinated Cu²⁺ was detected. The Cu²⁺/O^2?-squares are partly completed to a distorted octahedral coordination by two Cl^?.     

Zur Kristallstruktur von Ba3In2O6

About the Crystal Structure of Ba₃In₂O₆ Single crystals of Ba₃In₂O₆ could be prepared by recrystallization of a flux and by solid state reaction in closed platinium tubes, respectively. Ba₃In₂O₆ crystallizes with tetragonal symmetry (space group 14/mmm, a = 4.1868; c = 21.7041 Å, Z = 2). Single crystal X-ray work lead to a crystal structure like La_2-xSr_1+xCu₂O_6-δ therefor Ba₃In₂O₆ is a modified member of the Sr₃Ti₂O₇-Type. The coordinations of Ba²⁺ and In³⁺ are described and the relations to the Sr₃Ti₂O₇-type are discussed.     

Ein Halogenooxoruthenat (IV,V): Ba6Ru2, 5Mn0, 5O12Cl2 mit neuem Strukturtyp

About a Halogenooxoruthenat (IV, V): Ba₆Ru_2,5Mn_0,5O₁₂Cl₂ with a New Structure Type Ba₆Ru_2.5Mn_0.5O₁₂Cl₂ was prepared and investigated by single crystal X-ray work (space group D—P3 m1; a = b = 5.799; c = 14.853 Å; Z = 1). This structure type is characterized by «isolated», face-sharing (Ru/Mn)₃O₁₂-octahedratriple. Calculations of the Coulomb term of lattice energy support the charge distribution (5⁺/4⁺/5⁺) within the groups (Ru/Ru_0.5Mn_0.5/Ru)₃O₁₂^10?. The coordination of barium by oxygen and chlorine within three different polyhedra is discussed in detail.     

Synthesis and Structure of Mixed Ba12F19ClδBr5–δ Crystals

In the structure Ba₁₂F₁₉Cl₅ [hexagonal space group P6 2m] the two chlorides on the sites Cl(1) and Cl(2) can partially be replaced by bromide ions. Single crystals of the type Ba₁₂F₁₉Cl_δBr_5–δ with a chloride to bromide ratio up to 2 : 3 could be obtained by cooling a flux of 75 mol% BaF₂ and 25 mol% BaX₂ with X = Cl, Br. The crystal quality decreases with increasing bromide concentration. Structural parameters of five selected single crystals with different chloride/bromide ratio were studied by single crystal X-ray diffraction methods. The refined total Cl^?/Br^? population ratio in the crystals is close to the one of the flux. The lattice parameters and interatomic distances change in various ways, when the smaller chloride ion is replaced by the bigger bromide ion. The refinements show a statistical disorder on the halide sites with preferential bromide substitution on site Cl(1).     

Ba2BiV3O11 mit Bismut in geschlossener Koordination

Ba₂BiV₃O₁₁ containing Bismuth within closed Coordination A new barium bismuth oxovanadate, Ba₂BiV₃O₁₁, was prepared and investigated by X-Ray single crystal technique. It crystallizes with monoclinic symmetry space group C—P2₁/a, lattice constants a = 24.6473; b = 7.7347; c = 5.6375 Å, β = 103.16°; Z = 4. Octahedra arround Bi³⁺, tetrahedra and double tetrahedra arround V⁵⁺ form a tunnel structure. The tunnel positions are occupied by Ba(2).     

Zur Struktur von Ba3SmRu2O9, Ba3SmIrRuO9 und Ba2InIrO6

On the Structure of Ba₃SmRu₂O₉, Ba₃SmIrRuO₉, and Ba₂InIrO₆ The compounds Ba₃SmRu₂O₉, Ba₃SmIrRuO₉, and Ba₂InIrO₆ have a hexagonal BaTiO₃ structure (sequence (hcc)₂) with an ordered cationic distribution. The 6 L stacking polytypes Ba₃BM₂O₉ show an 1:2 order (M₂O₉ double octahedra and BO₆ single groups) and crystallize in the space group P6₃/mmc. The refined, intensity related R′ values are 6.9% (Ba₃SmRu₂O₉) and 6.5% (Ba₃SmIrRuO₉). The 1:1 ordered Ba₂InIrO₆, with InIrO₉ double groups and InO₆^?, IrO₆-single octahedra, belongs to the space group P3 m1; the refined R′ is 7,3%.     

Über Erdalkalimetalloxothallate. II. Darstellung und Kristallstruktur von Ba2Tl2O5

On Alkaline Earth Metal Oxothallates. II. Preparation and Crystal Structure of Ba₂Tl₂O₅ Ba₂Tl₂O₅ was prepared and investigated by X-ray single crystal methods (space group D? Pcmn, a = 6.264, b = 17.258, c = 6.05 Å) Ba₂Tl₂O₅ is isotypic with Ca₂Fe₂O₅.     

Neue Suboxid-Cluster [O5Ba18] in den Kristallstrukturen von Ba21M2O5 (M = Si,Ge)

Novel Suboxide Clusters [O₅Ba₁₈] in the Crystal Structures of Ba₂₁M₂O₅ (M = Si, Ge) The compounds Ba₂₁M₂O₅ (M = Si, Ge) crystallize in the cubic system with space group Fd3m, lattice constants 2 038.3(10) pm (Si), 2 039.8(9) pm (Ge) resp. and Z = 8. The crystal structure contains isolated Si/Ge atoms coordinated by barium atoms in an icosahedral arrangement. The oxygen atoms are situated in the centers of barium octahedra, four of which share common faces with an additional central octahedron. The novel clusters [O₅Ba₁₈] in principal are related to those in the crystal structures of the binary Cs/Rb suboxides.     

Alkoholyse von [Fe2(OtBu)6] als einfacher Weg zu neuen Eisen(III)‐Alkoxo‐Verbindungen: Synthesen und Kristallstrukturen von [Fe2(OtAmyl)6], [Fe5OCl(OiPr)12], [Fe5O(OiPr)13], [Fe5O(OiBu)13], [Fe5O(OCH2CF3)13], [Fe5O(OnPr)13] und [Fe9O3(OnPr)21] · iPrOH

Alcoholysis of [Fe₂(O^tBu)₆] as a Simple Route to New Iron(III)‐Alkoxo Compounds: Synthesis and Crystal Structures of [Fe₂(O^tAmyl)₆], [Fe₅OCl(OⁱPr)₁₂], [Fe₅O(OⁱPr)₁₃], [Fe₅O(OⁱBu)₁₃], [Fe₅O(OCH₂CF₃)₁₃], [Fe₅O(OⁿPr)₁₃], and [Fe₉O₃(OⁿPr)₂₁] · ⁿPrOH New alkoxo‐iron compounds can be synthesized easily by alcoholysis of [Fe₂(O^tBu)₆] ( 1 ). Due to different bulkyness of the alcohols used, three different structure types are formed: [Fe₂(OR)₆], [Fe₅O(OR)₁₃] and [Fe₉O₃(OR)₂₁] · ROH. We report synthesis and crystal structures of the compounds [Fe₅OCl(OⁱPr)₁₂] ( 2 ), [Fe₂(O^tAmyl)₆] ( 3 ), [Fe₅O(OⁱPr)₁₃] ( 4 ), [Fe₅O(OⁱBu)₁₃] ( 5 ), [Fe₅O(OCH₂CF₃)₁₃] ( 6 ), [Fe₉O₃(OⁿPr)₂₁] · ⁿPrOH ( 7 ) and [Fe₅O(OⁿPr)₁₃] ( 8 ). Crystallographic Data: 2 , tetragonal, P 4/n, a = 16.070(5) Å, c = 9.831(5) Å, V = 2539(2) ų, Z = 2, d_c = 1.360 gcm^?3, R₁ = 0.0636; 3 , monoclinic, P 2₁/c, a = 10.591(5) Å, b = 10.654(4) Å, c = 16.740(7) Å, β = 104.87(2)°, V = 1826(2) ų, Z = 2, d_c = 1.154 gcm^?3, R₁ = 0.0756; 4 , triclinic, , a = 20.640(3) Å, b = 21.383(3) Å, c = 21.537(3) Å, α = 82.37(1)°, β = 73.15(1)°, γ = 61.75(1)°, V = 8013(2) ų, Z = 6, d_c = 1.322 gcm^?3, R₁ = 0.0412; 5 , tetragonal, P 4cc, a = 13.612(5) Å, c = 36.853(5) Å, V = 6828(4) ų, Z = 4, d_c = 1.079 gcm^?3, R₁ = 0.0609; 6 , triclinic, , a = 12.039(2) Å, b = 12.673(3) Å, c = 19.600(4) Å, α = 93.60(1)°, β = 97.02(1)°, γ = 117.83(1)°, V = 2600(2) ų, Z = 2, d_c = 2.022 gcm^?3, R₁ = 0.0585; 7 , triclinic, , a = 12.989(3) Å, b = 16.750(4) Å, c = 21.644(5) Å, α = 84.69(1)°, β = 86.20(1)°, γ = 77.68(1)°, V = 4576(2) ų, Z = 2, d_c = 1.344 gcm^?3, R₁ = 0.0778; 8 , triclinic, , a = 12.597(5) Å, b = 12.764(5) Å, c = 16.727(7) Å, α = 91.94(1)°, β = 95.61(1)°, γ = 93.24(2)°, V = 2670(2) ų, Z = 2, d_c = 1.323 gcm^?3, R₁ = 0.0594.     

Structural study of Ba11Fe8Ti9O41 by X-ray diffraction

The crystal structure of Ba₁₁Fe₈Ti₉O₄₁ was determined using single crystal and powder X-ray diffraction methods. This new phase crystallizes in the hexagonal space group P6₃/mmc (No 194) (a=5.7506(3) Å, c=61.413(2) Å; Z=2; ρ_calc.=5.75 g cm⁻³) and exhibits a 26-layer structure built from close-packed [O,(Ba,O)] layers with a stacking sequence (chcchchchcchc)₂. Octahedral sites are occupied by a mixture of Fe³⁺ and Ti⁴⁺, with some preferential ordering of the Fe ions, and tetrahedral sites are occupied by Fe³⁺. The magnetic Fe ions were observed to concentrate within four contiguous cp layers around z=1/4 and 3/4. Unusual structural features, including cation disorder associated with unreasonably short cation–cation separations, were observed to occur within these magnetic sections of the structure. Indexed X-ray powder diffraction data for polycrystalline Ba₁₁Fe₈Ti₉O₄₁ are given. Complementary structural studies of this compound using neutron and electron diffraction are underway and will be described elsewhere along with the results of dielectric and magnetic property measurements.     

Zur Kenntnis von Ba4Ir3O10

About Ba₄Ir₃O₁₀ Single crystals of Ba₄Ir₃O₁₀ were prepared by a flux technique. X-ray investigations show monoclinic symmetry, space group C_2h⁵–P2₁/a; a = 5.788; b = 13.222; c = 7.242 Å; β = 112.98°; Z = 2. Ir₃O₁₂ tripel, built up by face-sharing of IrO₆ octahedra, are edge-connected into wave-like twodimensional planes. Ba₄Ir₃O₁₀ is related to Ba₄(Ti, Pt)₃O₁₀.     

Ein neuer Strukturtyp eines neuen Ruthenium(V)-Oxidchlorids: Ba5Ru2O9Cl2

Ba₅Ru₂O₉Cl₂ — a New Structure Type of a New Ruthenium(V) Oxidechloride For the first time an alkaline earth-halogenooxo-ruthenate(V) with the formula Ba₅Ru₂O₉Cl₂ was prepared and investigated by X-ray single crystal technique. It builds up a new type of structure with an orthorhombic symmetrie (space group D—Pnma, a = 15.310; b = 5.945; c = 14.197 Å). The crystal structure show a threedimensional Ba/O/Cl frame, which contains isolated Ru₂O₉-double-octahedra. The relations to other structures are discussed.