Ein Wechsel des Strukturtyps in den Oxiden BaCoGd2O5, BaCoDy2O5 und BaCoY2O5

A Change of Structure Type in the Oxides BaCoGd₂O₅, BaCoDy₂O₅, and BaCoY₂O₅ (I) BaCoGd₂O₅, (II) BaCoDy₂O₅, and (III) BaCoY₂O₅ were prepared for the first time and examined by single crystal work. (I) and (II) belong to the BaNiLn₂O₅-type. (I): a = 3.770; b = 5.860; c = 11.620 Å; Z = 2; (II): a = 3.755; b = 5.798; c = 11.514 Å; Z = 2; space group D–Immm. (III) crystallizes in the BaCuLn₂O₅-type, space group D–Pnma, a = 12.287; b = 5.713; c = 7.067 Å; Z = 4. The coordination of Co²⁺ changes from (I, II) to (III) from octahedral to tetragonal pyramidal.     

Zur Kristallchemie der Kupfer-Lanthanoid-Oxowolframate: (I) triklin-α-CuTbW2O8, (II) monoklin-CuInW2O8 und (III) monoklin-CuYW2O8

The Crystal Chemistry of Copper Rare-Earth Oxotungstates: (I): triclinic-α-CuTbW₂O₈, (II): monoclinic-CuInW₂O₈ and (III): monoclinic-CuYW₂O₈ Single crystals of (I), (II) and (III) were prepared by recrystallisation in closed systems and examined by X-ray technique. (I): space group C? P1 , a = 7.3080, b = 7.8945, c = 7.1476 Å, α = 115.23, β = 116.21, γ = 56.98°, Z = 2; (II): space group C? C2/c, a = 9.6576, b = 11.6496, c = 4.9863 Å, β = 91.17°, Z = 4; (III): space group C? P2/n, a = 10.0504, b = 5.8214, c = 5.0224 Å, β = 94.23°, Z = 2. The crystal structures are discussed with respect to calculations of the coulombterms of lattice energy and possible valence states of Cu²⁺ and Mo⁵⁺.     

Ein Beitrag über CuPrMo2O8 und CuTbMo2O8

A Contribution on CuPrMo₂O₈ and CuTbMo₂O₈ Single crystals of (I): CuPrMo₂O₈ and (II): CuTbMo₂O₈ were prepared by solid state reactions in closed copper tubes. They crystallize with orthorhombic symmetry, space group D-Pbca, (I): a = 10.4114, b = 9.8917, c = 14.8287 Å, (II): a = 10.2243, b = 9.7385, c = 14.6000, Z = 8. Both compounds are isotypic to CuYMo₂O₈, showing isolated MoO₄ tetrahedra, square antiprismatic coordination of Ln³⁺ and Cu⁺ besides one edge of an O^2? triangle. Calculations of the coulombterm of lattice energy support the oxidation state Cu²⁺ in combination with mixed valences of Mo⁶⁺ and Mo⁵⁺ on the molybdenum point positions.     

Ein Beitrag zur Kristallstruktur von CuYW2O8, CuHoW2O8 und CuYbW2O8

A Contribution on the Crystal Structure of CuYW₂O₈, CuHoW₂O₈, and CuYW₂O₈ Single crystals of (I) CuY₂O₈, (II), CuHoW₂O₈, and (III) CuYbW₂O₈ were prepared and investigated by X-ray technique. (I) crystallizes with triclinic symmetry, space group C? P1 (a = 5.939 Å, b = 6.042 Å, c = 5.025 Å; α = 112.30°, β = 111.77°; Z = 1). (II) and (III) belong to monoclinic symmetry, space group C? P2/n (II) (a = 10.045 Å, b = 5.808 Å, c = 5.021 Å; β = 94.38°; z = 2 (III) a = 9.948 Å, b = 5.824 Å, c = 5.008 Å; β = 93.36°; Z = 2). The crystal structures will be discussed with respect to other to copper rare earth tungstates.     

Ein Beitrag Über die Verbindung CaBeNd2O5 und Phasen der Zusammensetzung M1−xM′xBeLn2O5 (M = Ca,Ba; M′ = Sr; x = 0,5)

A Contribution on the Compound CaBeNd₂O₅ and Phases of the Composition M_1?xM_x'BeLn₂O₅ (M = Ca, Ba; M′ = Sr; x = 0.5). CaBeNd₂O₅ and the phases (I): Ba_0,5Sr_0,5BeLa₂O₅ and (II): Ca_0,5Sr_0,5BeDy₂O₅ have been prepared by high temperature reactions using a CO₂-LASER. They crystallize with orthorhombic symmetry, space group D-Pnma, CaBeNd₂O₅: a = 9.448(1), b = 7.155(1), c = 6.483(1) Å; (I) a = 9.821(4), b = 7.436(3), c = 6.734(3) Å; (II): a = 9.352(2), b = 7.016(2), c = 6.375(2) Å; Z = 4, and belong to the isotypic series CaBeLn₂O₅ and SrBeLn₂O₅. Calculations of Coulomb energies of ordered BaBeLn₂O₅ and EuBeLn₂O₅ and disordered CaBeLn₂O₅, SrBeLn₂O₅ and EuBeNd₂O₅ show dependencies of the ionic radii of the M²⁺ and Ln³⁺ ions as well as of the order/disorder state.     

Ein Beitrag zur Kristallstruktur von CuSmMo2O8 und CuGdMo2O8

A Contribution on the Crystal Structure of CuSmMo₂O₈ and CuGdMo₂O₈ Single crystals of (I) CuSmMo₂O₈ and (II) CuGdMo₂O₈ were prepared and investigated using an X-ray technique. Both compounds crystallize with orthorhombic symmetry, space group D-Pbca with Z = 8. ((I): a = 10.302, b = 9.796, c = 14.697 Å; (II): a = 10.200, b = 9.779, c = 14.646 Å). The crystal structure and the classification into the already known Copper(I) Lanthanoidemolybdates are discussed.     

Synthese und Struktur des ersten ternären Blei(II)-Oxocuprats(I): PbCu2O2

Synthesis and Structure of the First Ternary Lead(II) Copper(I) Oxide: PbCu₂O₂ PbCu₂O₂ can be prepared by solid state reaction or by precipitation from a basic aqueous solution. Single crystals of the new compound were prepared by recrystallisation from a molten mixture (PbO? Cu₂O) and investigated by X-ray diffractometer technique. PbCu₂O₂ crystallizes isotypically with the homologue silver compound PbAg₂O₂ (monoclinic with a = 8.22₃ Å, b = 8.28₉ Å, c = 6.01₅ Å, β = 132.6₂°, Z = 4, space group C? C 1 2/c 1). The crystallographic data from the X-ray investigation are reported. The structure is built by endless [PbO_4/4]- and [CuO_2/4]-chains. Pb²⁺ has a one-sided asymmetric coordination with four next oxygen neighbours and Cu⁺ forms a stretched dumbbell with two oxygen atoms.     

Ein neuer Strukturtyp zur Formel ABLn2O5 Zur Kenntnis von BaNiNd2O5

A New Crystal Structure of ABLn₂O₅ Compounds. About BaNiNd₂O₅ The compound BaNiNd₂O₅ was prepared by solid state reaction. Single crystal examination show a new structure type (a = 3.829(2), b = 5.932(3), c = 11.649(3) Å space group D–Immm, Z = 2) with Ni²⁺ in octahedral coordination. The surrounding of Ba²⁺ and Nd³⁺ conforms to BaPtNd₂O₅ with significant differences of the polyhedra connection.     

Synthese und Untersuchung von NiNb2O6-Einkristallen mit Columbit- und Rutilstruktur

Synthesis and Investigation of NiNb₂O₆ Single Crystals of Columbite and Rutil Type C-NiNb₂O₆ (columbite type) and R-NiNb₂O₆ (rutil type) single crystals were prepared by solid state reactions. C-NiNb₂O₆ a = 14.032; b = 5.687; c = 5.033 Å, space group D—Pbcn. R-NiNb₂O₆ a = 4.710; c = 3.038 Å, space group D—P4₂/mnm. The metal positions of the rutil structure are statisticaly occupied by Ni²⁺ and Nb⁵⁺ ions. R-NiNb₂O₆ is in respect to lower temperatures a metastable compound.     

Zur Atomverteilung in Ba2SrIn2O6 mit einem Beitrag zur Existenz des Calciumferrat(III)-Typs bei Oxoindaten

On the Atomic Distribution in Ba₂SrIn₂O₆ with a Contribution to the Existence of the Calciumferrite-Type of Oxoindates (I) Ba₂SrIn₂O₆ and (II) Sr_0.93Ba_0.07In₂O₄ were prepared and investigated by single crystal X-ray technique. I crystallizes with tetragonal symmetry, space group D – I4/mmm, a = 4.168; c = 21.290 Å; Z = 2; II belongs to the orthorhombic space group D – Pnma, a = 9.858; b = 3.273; c = 11.520 Å; Z = 4. I shows in respect to the formerly investigated compound BaSr₂In₂O₆ an unexpected statistically distribution of Ba²⁺ and Sr²⁺ with the La₂SrCu₂O₆ type. II marks the range of existence of the calciumferrite type within the alkaline earth oxoindates in direction of large radii of M²⁺ ions.     

CuTb[B5O10]: Das erste „Metaborat”︁ mit einem [B5O10]5− -Anion

CuTb[B₅O₁₀]: The first “Metaborate” with a [B₅O₁₀]^5? Anion Single crystals of the new compound CuTb[B₅O₁₀] were obtained by a B₂O₃ flux-technique. They crystallize in a so far unknown structure. X-ray investigations on single crystals led to the space group C–I ba2 (Nr. 45); a = 6.294(1) Å; b = 8.406(8) Å; c = 12.733(2) Å; Z = 4. The structure contains [B₅O₁₀]^5? chains isolated from each other. These chains include twelf membered rings of boron and oxygen. Each ring consists of two tetrahedral BO₄ and two planar B₂O₅ groups and is connected with the next one via the BO₄ units. Tb³⁺ is eightfold- and Cu²⁺ elongated octahedraly coordinated by oxygen.     

Zwei neue Verbindungen mit Zink in tetragonal pyramidaler Koordination: BaZnDy2O5 und Ba1,25ZnHo2O5,25 (Ba5Zn4Ho8O21)

New Compounds with Zinc in Square Pyramidal Coordination: BaZnDy₂O₅ and Ba_1.25ZnHo₂O_5.25 (Ba₅Zn₄Ho₈O₂₁). Single crystals of (I): BaZnDy₂O₅ and (II): Ba₅Zn₄Ho₈O₂₁ were prepared by high temperature reactions and investigated by X-ray technique. (I) belongs to the BaCuLn₂O₅ type, space group D-Pbnm; a = 7.084; b = 12.368; c = 5.728 Å, Z = 4. (II) is isotypic to Ba₅Mn₄Ln₈O₂₁, space group C-I4/m; a = 13.779; c = 5.707 Å, Z = 2. The two different structure types are caused by the small difference in the composition of 0.25 BaO. Analogies and differences will be discussed. In addition the lattice constants of powder samples of Ba₅Zn₄Ln₈O₂₁ (Ln = Eu, Gd, Dy, Ho, Er and Y) are given.     

Zur Kenntnis eines Barium-Lanthanoid-Oxozinkat/Platinats(IV): Ba2Eu2ZnPtO8

On a Barium Rare Earth Oxozincate/Platinate(IV): Ba₂Eu₂ZnPtO₈ High temperature reactions of BaCO₃, ZnO and Eu₂O₃ in platinum crucibles led to single crystals of Ba₂Eu₂ZnPtO₈. It crystallizes with orthorhombic symmetry, space group D-Pnma, a = 13.390(1), b = 5.764(1), c = 10.387(1) Å, Z = 4 and is isotypic to Ba₂Y₂CuPtO₈. Ba₂Eu₂ZnPtO₈ is characterized by isolated _∞¹[ZnPtO₈]^10? anions formed by ZnO₅-pyramids and PtO₆-octahedra. The space between the [ZnPtO₈]^10? groups is filled by Eu³⁺ and Ba²⁺ ions. Relationships to zinc and platinum containing oxometallates are discussed.     

Zur Kristallchemie der Blei-Lanthanoid-Oxoaluminate. Zur Kenntnis von Pb2HoAl3O8 und Pb2LuAl3O8

Crystal Chemistry of the Lead Lanthanide Oxoaluminates. On Pb₂HoAl₃O₈ and Pb₂LuAl₃O₈ . Single crystals of (I) Pb₂HoAl₃O₈ and (II) Pb₂LuAl₃O₈ were prepared by flux technique and investigated by X-ray methods. It crystallizes with cubic symmetry, space group O–P4₂/n 3 2/m, (I): a = 9.4164(13) Å, (II): a = 9.3486(8) Å, Z = 4. The new structure type shows AlO₄ tetrahedra, LnO₈ hexagonal bipyramids and one sided coordinated Pb²⁺ within heterocubane units. The crystal chemical relationships to other lead oxides containing heterocubane Pb₄O₄ units are discussed.     

Synthese und Struktur einer neuen Form von CuYMo2O8

Synthesis and Structure of a New form of CuYMo₂O₈ Single crystals of a new form of CuYMo₂O₈ were prepared and investigated by X-ray diffractometer technique [space group D-Pbca; a = 10.160 Å, b = 9.701 Å, c = 14.527 Å; Z = 8]. CuYMo₂O₈ represents a new structure type characterised by MoO₄-tetrahedrons, Cu⁺ with coordination number 2 + 1 and square antiprisms around Y³⁺. The crystal structure and the Cu⁺ coordination are discussed.     

LaCl(BO2)2 und Er2Cl2[B2O5]: Zwei Chlorid‐Oxoborate dreiwertiger Lanthanide

LaCl(BO₂)₂ and Er₂Cl₂[B₂O₅]: Two Chloride Oxoborates of Trivalent Lanthanides Er₂Cl₂[B₂O₅] is obtained as single crystals by the reaction of ErCl₃, Er₂O₃ and B₂O₃ with an excess of ErCl₃ as flux in evacuated silica tubes after two weeks at 850 °C. The compound crystallizes as long, pale pink needles and appears to be air‐ and water‐resistant. Single‐crystalline LaCl(BO₂)₂ emerges from the reaction of La₂O₃, LaCl₃, and B₂O₃ with an excess of B₂O₃ as flux in evacuated silica tubes after four weeks at 900 °C. LaCl(BO₂)₂ crystallizes as thin, colourless, air‐ and water‐resistant needles which tend to severe twinning due to their fibrous habit. The crystal structure of Er₂Cl₂[B₂O₅] (orthorhombic, Pbam; a = 1489.65(9), b = 1004.80(6), c = 524.86(3) pm; Z = 4) contains two crystallographically different erbium cations. (Er1)³⁺ resides in pentagonal‐bipyramidal coordination of seven anions while (Er2)³⁺ is surrounded by only six anions with the shape of an octahedron. The planar oxodiborate units [B₂O₅]^4— consisting of two vertex‐shared [BO₃]^3— triangles are isolated according to {([BOO]₂)^4—}. LaCl(BO₂)₂ crystallizes isostructurally with PrCl(BO₂)₂ in the triclinic space group P1¯ (a = 423.52(4), b = 662.16(7), c = 819.33(8) pm; α = 82.081(8), β = 89.238(9), γ = 72.109(7)°; Z = 2). The characteristic unit consists of endless chains built up by corner‐linked [BO₃]^3— triangles. These quasi‐planar zigzag chains of the composition {[(B1)OO(B2)OO]^2—} (≡ {[BO₂]^—} run parallel [100]. The La³⁺ cations exhibit coordination numbers of ten and are coordinated by three Cl^— and seven O^2— anions.     

Das erste Erdalkalimetall-Mercurato(II)-Palladat(II,IV): Ba2Hg3Pd52+ Pd24+ O14

On the First Alkaline Earth Mercurato(II)-Palladate(II, IV): Ba₂Hg₃Pd₅²⁺Pd₂⁴⁺O₁₄ Single crystals of Ba₂Hg₃Pd₇O₁₄ were prepared by oxygen high-pressure technique (3900 bar) and investigated by X-ray technique. It crystallizes with monoclinic symmetry, space group C–C2/m; Z = 2 (a = 10.583; b = 6,207; c = 10.919 Å, β = 90.56°). The Hg²⁺ ions show partially dumb-bell like and one sided 3 fold coordination respectively. Pd⁴⁺ /Pd²⁺ show an octahedric or square planar surrounding.     

Zur Kristallstruktur von Cu2M(BO3)O2 (M = Fe3+, Ga3+)

The Crystal Structure of Cu₂M(BO₃)O₂ (M = Fe³⁺, Ga³⁺) Single Crystals of the compounds Cu₂M(BO₃)O₂ (M = Fe³⁺ (I), Ga³⁺ (II)) were obtained by a B₂O₃ flux-technique. They crystallize in a monoclinic distorted variant of a Ludwigite structure with a partly ordered metal distribution. X-ray investigations on single crystals led to the space group C–P2₁/c (No. 14); I: a = 3.108(1); b = 12.003(1); c = 9.459(3) Å; b? = 96.66(3)°; Z = 4 and II: a = 3.1146(2); b = 11.921(3); c = 9.477(2) Å; b? = 97.91(2)°; Z = 4. All metal-sites are distorted octahedraly coordinated by oxygen-ions. The structure contains isolated planar BO₃-units and oxygen which is not coordinated to boron.     

Zwei neue Erdalkalimetall-Oxoindate: BaCa2In6O12 und BaSr2In6O12

Two New Alkaline-Earth-Oxoindates: BaCa₂In₆O₁₂ and BaSr₂In₆O₁₂ The hitherto unknown compounds (I): BaCa₂In₆O₁₂ and (II): BaSr₂In₆O₁₂ were prepared and examined by single crystal X-Ray work. (I) and (II) crystallize with hexagonal symmetry, space group C? P6₃/m, with (I): a = 9.880, c = 3.211 Å; (II): a = 9.9443; c = 3.2671 Å, Z = 1. Both compounds are isotypic to the metastable oxide AM₂Ln₆O₁₂, but without metastable behavior. The [In₆O₁₂]^6? network is occupied by the alkaline earth ions. One of the tunnels is stuffed by Ca²⁺ and Sr²⁺ respectively, the other one by Ba²⁺ in a statistical distribution on possible point positions. (I) and (II) prove the existence of the AM₂Ln₆O₁₂-type in respect to small Ln³⁺ ions.     

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.