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.     

Die erste Verbindung mit Mn2+ der Stoffklasse BaMLn2O5: BaMnDy2O5

The First Compound of BaMLn₂O₅-Type Containing Mn²⁺: BaMnDy₂O₅ Single crystals of the hitherto unknown compound BaMnDy₂O₅ were prepared by CO₂-Laser technique and H₂ atmosphere. Four circle diffractometer measurements led to space group D¹⁶_2h-Pnma, a = 12.428; b = 5.766; c = 7.143 Å; Z = 4. It is isotypic to BaCuSm₂O₅ and shows Mn²⁺ in square pyramids of oxygen.     

Über eine neu entdeckte Dimorphie an BaCoEr2O5

On a New Observed Dimorphism of BaCoEr₂O₅ Single crystals of BaCoEr₂O₅ were prepared by CO₂-LASER technique under N₂-atmosphere and investigated by X-ray single crystal methods. It crystallizes with orthorhombic symmetry, space group D-Pnma (a = 12.2787, b = 5.6826, c = 7.0344 Å; Z = 4). The so far unknown crystal structure of BaCoEr₂O₅ belongs to the BaCuLn₂O₅ type forming the dimorphic substance to the previously described Ni type of BaCoEr₂O₅.     

Eu3+ und Eu2+ in Oxometallaten der Zusammensetzung MBeLn2O5: SrBeEu2O5 und EuBeNd2O5

Eu³⁺ and Eu²⁺ in Oxides of the Composition MBeLn₂O₅: SrBeEu₂O₅ and EuBeNd₂O₅ Single crystals of (I): SrBeEu₂O₅ and (II): EuBeNd₂O₅ were prepared by CO₂-LASER (I) in air and plasma torch (II) technique in H₂ atmosphere. X-ray investigations led to orthorhombic symmetry, space group D-Pnma; (I): a = 9.488, b = 7.156, c = 6.495 Å; (II): a = 9.534, b = 7.225, c = 6.544 Å, Z = 4. Sr²⁺ and Eu³⁺ as well as Eu²⁺ and Nd³⁺ are in statistical distribution within a Kagomé framework. Both compounds are discussed with respect to the monoclinic form of MBeLn₂O₅.     

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.     

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 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.     

Ein Beitrag über Oxometallate mit trigonal planaren BO3-Polyedern Ni2MBO5 (M = Ga,Fe, Al,Cr)

A Contribution about Oxometallates Containing Trigonal Planar BO₃-Polyhedra. Ni₂MBO₅ (M = Ga, Fe, Al, Cr) (I) Ni₂AlBO₅, (II) Ni₂FeBO₅, and (III) Ni₂GaBO₅ were investigated by single crystal X-ray technique. They crystallize with orthorhombic symmetry, space group D—Pbam; I: a = 9.102; b = 12.011; c = 2.944 Å; II: a = 9.200; b = 12.210; c = 3.006 Å; III: a = 9.200; b = 12.154; c = 2,986 Å; Z = 4. X-ray powder data indicate that Ni₂CrBO₅ is isotypic. It was possible to study the metal distribution in Ni₂AlBO₅. Ni²⁺ and Al³⁺ ions occupy the point positions partly disordered.     

Neue Oxogallate der Alkalimetalle: Über K6[Ga2O6] und Rb6[Ga2O6], sowie Na3GaO3 und Cs6[Ga2O6]

New Oxogallates of Alkaline Metals: On K₆[Ga₂O₆] and Rb₆[Ga₂O₆] as well as Na₃GaO₃ and Cs₆[Ga₂O₆] Due to powder and single crystal data K₆[Ga₂O₆] a = 7.09₉; b = 11.11₆; c = 6.48₄ Å; ß = 101.6₆° and Rb₆[Ga₂O₆] a = 7.39₃; b = 11.47₅; c = 6.79₈ Å; ß = 103.5° crystallize isotypic with K₆[Fe₂O₆]; space group C2/m-C₃^2h; As well has been prepared the hitherto unknown Na₃GaO₃ a = 11.48, b = 10.82, c = 6.13 Å, space-group Imcm or I2cm Z = 8; and Cs₆[Ga₂O₆] a = 7.2₆, b = 12.1, c = 7.6₈ Å, ß = 105°, Z = 4, space-group P2₁/a.     

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.     

Syntheses and structural study of trinuclear iron acetates [Fe3O(CH3COO)6(H2O)3]Cl· 6H2O and [Fe3O(CH3COO)6(H2O)3] [FeCl4]· 2CH3COOH

The structure of two trinuclear iron acetates [Fe₃O(CH₃COO)₆(H₂O)₃]Cl· 6H₂O (I) and [Fe₃O(CH₃COO)₆(H_2O)₃][FeCl₄] · 2CH₃COOH (II) was determined by X-ray diffraction analysis. Crystals I and II are ionic and belong to the orthorhombic system with parameters a = 13.704(3), b = 23.332(5), c = 9.167(2) Å, R = 0.0355, space goup P2₁2₁2 for I and a = 10.145(4), b = 15.323(6), c = 22.999(8) Å, R = 0.0752, space group Pbc2₁ for II. The complex cation [Fe₃O(CH₃COO)₆(H₂O)₃]⁺ has a μ₃-O-bridged structure typical for trinuclear iron (III) compounds. As shown by Mössbauer spectroscopy, the iron(III) ions are in the high-spin state. In trinuclear cations, antiferromagnetic exchange interaction takes place between the Fe(III) ions with the exchange parameter J = -26.69 cm^?1 for II (Heisenberg-Dirac-Van Vleck model for D_3h, symmetry).     

Molecular and crystal structure of 5-phenyl, 5-m-nitrophenyl,and 5-spirocyclopentane derivatives of 3-amino-2,4,4-tricyanobicyclo [4,4,0] deca-2,10-diene

To examine the ability of 3-amino-2,4,4-tricyanobicyclo[4,4,0]deca-2,10-dienes (I) to form dimeric associates, we have investigated molecular and crystal structure of three derivatives of (I): 5-phenyl (II), 5-m-nitrophenyl (III), and 5-spirocyclopentano (IV). Hydrogen bonding via the aminonitrile fragment leads to formation of centrosymmetric dimeric associates in compounds (II, III) and a chain structure in (IV). Crystal data for (II): space group P2₁/c, a=8.726(3), b=15.879(5), c=15.597(5) Å, α=γ=90, β=105.13(2)⁰, V=2086.2 ų, Z=4, R=0.093; for (III): space group C2/c, a=24.725(8), b=9.004(5), c=24.391(8) Å, α=γ=90, β=125.36(2)⁰, V=4428.2ų, Z=8, R=0.080; for (IV): space group C2/c, a=24.443(8), b=10.240(5), c=16.645(6) Å, α=γ=90, β=108.89(2)⁰, V=3941.8 ų, Z=8, R=0.089.     

Chemischer Transport und Struktur von UNb2O7 – einem neuen MM′2O7-Typ

Chemical Transport and Structure of UNb₂O₇ – a New Type of MM′₂O₇ Powdery UNb₂O₇ could be obtained by heating an äquimolar mixture of UO₂ and Nb₂O₅ in an evacuated silica tube at 1 100°C. Chemical transport in a small temperature gradient with NbCl₅/Cl₂ as transport agent was successfully used for crystal synthesis. UNb₂O₇ crystallizes with orthorhombic symmetry; the lattice constants are a = 3.8012(7) Å; b = 21.170(8) Å; c = 6.440(2) Å and Z = 4. Structure determination in the space group Cmcm (nr. 63) let to R = 0.021 (R_w = 0.019). U and Nb1 have CN = 7, Nb2 has CN = 6 (5 + 1). Uranium is surrounded by oxygen like an doma-octahedron, niobium1 like an pentagonal-bipyramid and niobium2 like an distorted octahedron.     

Complexation of the 2, 4, 6‐Triallyloxy‐1, 3, 5‐triazine with Copper(I,II) Chlorides. Syntheses and Crystal Structures of [CuCl2·2C3N3(OC3H5)3], [Cu7Cl8·2C3N3(OC3H5)3], and [Cu8Cl8·2C3N3(OC3H5)3]·2C2H5OH

Interaction of copper(II) chloride with 2, 4, 6‐triallyloxy‐1, 3, 5‐triazine leads to formation of copper(II) complex [CuCl₂·2C₃N₃(OC₃H₅)₃] ( I ). Electrochemical reduction of I produces the mixed‐valence Cu^{I, II} π, σ‐complex of [Cu₇Cl₈·2C₃N₃(OC₃H₅)₃] ( II ). Final reduction produces [Cu₈Cl₈·2C₃N₃(OC₃H₅)₃]·2C₂H₅OH copper(I) π‐complex ( III ). Low‐temperature X‐ray structure investigation of all three compounds has been performed: I : space group P1¯, a = 8.9565(6), b = 9.0114(6), c = 9.7291(7) Å, α = 64.873(7), β = 80.661(6), γ = 89.131(6)°, V = 700.2(2) ų, Z = 1, R = 0.0302 for 2893 reflections. II : space group P1¯, a = 11.698(2), b = 11.162(1), c = 8.106(1) Å, α = 93.635(9), β = 84.24(1), γ = 89.395(8)°, V = 962.0(5) ų, Z = 1, R = 0.0465 for 6111 reflections. III : space group P1¯, a = 8.7853(9), b = 10.3602(9), c = 12.851(1) Å, α = 99.351(8), β = 105.516(9), γ = 89.395(8), V = 1111.4(4) ų, Z = 1, R = 0.0454 for 4470 reflections. Structure of I contains isolated [CuCl₂·2C₃N₃(OC₃H₅)₃] units. The isolated fragment of I fulfils in the structure of II bridging function connecting two hexagonal prismatic‐like cores Cu₆Cl₆, whereas isolated Cu₆Cl₆(CuCl)₂ prismatic derivative appears in III . Coordination behaviour of the 2, 4, 6‐triallyloxy‐1, 3, 5‐triazine moiety is different in all the compounds. In I ligand moiety binds to the only copper(II) atom through the nitrogen atom of the triazine ring. In II ligand is coordinated to the Cu^II‐atom through the N atom and to two Cu^I ones through the two allylic groups. In III all allylic groups and nitrogen atom are coordinated by four metal centers. The presence of three allyl arms promotes an acting in II and III structures the bridging function of the ligand moiety. On the other hand, space separation of allyl groups enables a formation of large complicated inorganic clusters.     

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.     

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.     

Structure and resonance raman spectrum of the linear metal-chain compound bis(1,2-benzoquinonedioximato)-palladium triiodide,Pd(bqd)2I0.5 or Pd(bqd)2(I3)0.17

Struktur und Resonanz-Raman-Spektrum der Linear-Metallketten-Verbindung Bis(1,2-benzochinondioximato)palladiumtriiodid, Pd(bcd)₂I_0,5 bzw. Pd(bcd)₂(I₃)_0,17 Die Gitterstruktur der Titelverbindung wurde durch Beugung von Röntgenstrahlen am Einkristall unter Verwendung von MoKα-Strahlung auf einem Syntex P2₁, computerkontrollierten Diffraktometer ermittelt. Die kristallographischen Daten lauten: (PdC₁₂H₁₀N₄O₄)₂I, Molgew. = 888,19; tetragonale Raumgruppe P4/mcc (D_2h⁴); a = b = 15,977 Å, c = 6,371 Å; Z = 2; V = 1626,3 ų; D_rö = 1,81 g/cm³, D_beob = 1,79 g/cm³. Das Gitter kristallisiert mit ausgedehnten, geradlinigen Ketten von partiell oxidierten Pd-Ionen (dessen durchschnittliche Oxydationszahl rund +2,17 beträgt), d. h. die planaren Pd(bcd)₂-Komplexe sind entlang der c-Achse übereinander gestapelt mit einem regelmäßigen Pd—Pd-Abstand von 3,185 Å (1/2 c). Resonanz-Raman-Spektren der Verbindung (polykristalline Proben) wurden mit Hilfe einer Laser-Anregungsquelle (ν₀ = 5145 Å) bei Raumtemperatur aufgenommen. Die Spektren zeigen ausschließlich die charakteristischen Absorptionsbanden von unsymmetrischen I₃^?-Ionen an. Die Ergebnisse lassen darauf schließen, daß der Beitrag der Iodketten zu elektronischen Festkörperanisotropien in dieser Art von quasi-eindimensionalen Materialien vernachlässigbar klein ist.     

Das erste Alkali-Erdalkali-Oxocuprat(II,III): NaBa2Cu22+Cu3+O6

The first Alkaline Alkaline-Earth Oxocuprate (II, III): NaBa₂Cu₂²⁺Cu³⁺O₆ The compound NaBa₂Cu₃O₆ was prepared by heating of Na₂O₂, BaO₂, Cu₂O in closed Ag-tubes. X-ray single crystal investigations led to orthorhombic symmetry, space group D-Fmmm; a = 8.4229; b = 11.4418; c = 14.4063 Å; Z = 8. Cu²⁺ and Cu³⁺ show square planar polygones of four and Na⁺ trigonal prisms of six O^2?. The two barium point positions show coordination numbers C.N. = 8 and 6 + 4. The crystal structure is discussed.     

BaIr0,67Be0,33O3: Eine stabilisierte kubische Form von BaIrO3

Inhaltsübersicht. Es ist gelungen, ein durch BeO stabilisiertes Bariumoxoiridat der Zusammensetzung BaIr_0,67Be_0,33O₃ in der Kristallform eines kubischen Perowskits mit kleiner Elementarzelle erstmals darzustellen. Raumgruppe O¹_h–Pm3m, a = 4,1009 Å, Z = 1. Ir⁵⁺ und Be² + besetzen die Oktaederposition des Perowskits statistisch. BaIr_0,67Be_0,33O₃: A Stabilized Cubic Form of BaIrO₃ For the first time it was possible to prepare a new barium-oxoiridate of the formula BaIr_0,67Be_0,33O₃, stabilized by BeO. It crystallizes in a small cubic unit cell of the perovskite type. Space group O¹_h–Pm3m; a = 4.1009 Å; Z = 1. Ir⁵⁺ and Be²⁺ occupy the octahedra positions of the perovskite structure statistically.     

Synthese und Kristallstruktur von Calcium-Kupfer-Diarsenat CaCuAs2O7

Synthesis and Crystal Structure of the Calcium Copper Diarsenate CaCuAs₂O₇ Solid state reactions led to single crystals of CaCuAs₂O₇. X-ray investigations revealed monoclinic symmetry, space group C⁵_2h-P2₁/c, lattice constants a = 7.272(1); b = 8.946(2); c = 9.307(2) Å; β = 109.48(2)°; Z = 4. CaCuAs₂O₇ is characterized by ¹_∞[CaO₆] chains, connected by As₂O₇ double tetrahedra and elongated square CuO₅ pyramids. The hitherto unknown crystal structure shows relationships to CaCuP₂O₇ but not to CaCuV₂O₇.