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 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.     

Darstellung und Kristallstruktur von Na2Mn3O7

Synthesis and Crystal-Structure of Na₂Mn₃O₇ Single crystals of Na₂Mn₃O₇ have been grown hydrothermally applying high oxygen pressure (p = 2 kbar). The new compound cystallizes triclinic; space group P1 ; a = 6.636(6) Å, b = 6.854(6) Å, c = 7.548(6) Å, α = 105.76(6)°, β = 106.86(6)°, γ = 111.60(6)°; Z = 2. The crystal structure has been solved and refined to R = 7.9% and R_w = 6.2% (diffractometer data, 1044 independent reflexions). The crystal structure consists of Mn₃O₇^2? anions with manganese coordinated octahedrally by oxygen. These layered anions are hold together by Na⁺ ions (coordination numbers 5 and 6).     

Na2Mn(NH2)4: Ein neuer Schichtenstrukturtyp

Na₂Mn(NH₂)₄: A New Type of Layered Structure The structure of Na₂Mn(NH₂)₄ was solved by X-ray single crystal data including H-positions: P2₁/c, Z = 4, a = 6.331(1) Å, b = 14.542(3) Å, c = 7.212(1) Å, β = 116.29(1)°, Z(F ≥ 3σ = (F)) = 1343, Z(parameters) = 96, R/R_W = 0.023/0.029. The compound crystallizes in a new type of structure. Within layered blocks the amide ions are arranged with the motif of a hexagonal closest packing of spheres. Within these blocks alternating layers contain sodium in all octahedral sites and manganese in an ordered way in a quarter of tetrahedral sites.     

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.     

Rapid and Simple Isolation of the Crystalline Molybdenum-Blue Compounds with Discrete and Linked Nanosized Ring-Shaped Anions: Na15[MoMoO462H14(H2O)70]0.5 [MoMoO457H14(H2O)68]0.5 · ca. 400 H2O and Na22[MoMoO442H14(H2O)58] · ca. 250 H2O

The blue mixed-crystal title compound Na₁₅[MoMoO₄₆₂H₁₄ (H₂O)₇₀]_0.5[MoMoO₄₅₇H₁₄ · (H₂O)₆₈]_0.5 · ca. 400 H₂O ≡ Na₁₅[ 1 a ]_0.5[ 1 b ]_0.5 · ca. 400 H₂O 1 , which crystallizes in the triclinic space group P 1 (a = 30.785(2), b = 32.958(2), c = 47.318(3) Å, α = 90.53(1), β = 89.86(1), γ = 96.85(1)°, V = 47665(6) ų, Z = 2, D_calc = 2.149 g cm^–3), precipitates within one day when an acidic (pH ≈ 1) aqueous solution of sodium molybdate (because of the extremely high solubility of the reaction product used in relatively high concentration) is reduced by sodium dithionite. 1 contains hitherto unknown pure molybdenum-oxide based, nanosized, ring-shaped, crystallographically independent cluster anions of the type {Mo₁₅₄} 1 a and {Mo₁₅₂} 1 b , the lacunary-type analogue of 1 a . Using the same reducing agent but in the presence of a reagent with a high affinity to the specific {Mo₂}-type building unit (also a leaving group) of 1 a , such as formic acid, the compound Na₂₂[MoMoO₄₄₂H₁₄(H₂O)₅₈] · ca. 250 H₂O 2 (space group P 1, a = 24.724(1), b = 35.726(2), c = 44.608(3) Å, α = 93.25(1), β = 93.51(1), γ = 106.72(1)°, V = 37552(4) ų, Z = 2, D_calc = 2.401 g cm^–3) is obtained in which the giant rings, having four missing {Mo₂} units compared to 1 a , are linked to chains. Until now, similar chain-type compounds could only be obtained using a non-well-defined synthetic method.     

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.     

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.     

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.     

Die Kristallstruktur von Perowskiten ANiIIMVIO6. II. Das Sr2NiWO6

The Crystal Structure of Perovskites A Ni^IIM^VIO₆. II. Sr₂NiWO₆ The results of an X-ray single crystal study of the perovskite Sr[Ni^IIW^VI]⁽⁶⁾O₆, ordered in the octahedral sites, are given. While Sr[Ni^IITe^VI]⁽⁶⁾O₆ crystallizes in a monoclinically deformed structure of the perovskite (elpasolite) type, showing a phase transition to a tetragonal lattice at 675 °K, Sr[Ni^IIW^VI]⁽⁶⁾O₆ is tetragonal already at 298°K (space group: C; a = b = 5.559 Å; c = 7.918 Å; Z = 2). The Ni? O distances found for the tungsten compound are nearly identical with those of the tellurium perovskite. In contradiction to crystal field theory very different values of the ligand field parameter Δ (ca. 25%) are observed for these two compounds however. Obviously this effect is caused by the rather different kind of bonding within the NiO₆ polyhedra in the two compounds. On the basis of the structural results the Ni? O-bonding in the two perovskites is discussed in dependence of the next nearest cationic environment.     

Synthese und Kristallstruktur von Sr2Zn(OH)6 und Ba2Zn(OH)6

Synthesis and Crystal Structure of Sr₂Zn(OH)₆ and Ba₂Zn(OH)₆ Crystallization from supersaturated sodium hydroxozincate solutions by adding solutions of alkali earth metal hydroxides yields crystals of Sr₂Zn(OH)₆ and Ba₂Zn(OH)₆. The X-ray structure determination on these crystals was successful including all hydrogen positions: Sr₂Zn(OH)₆: P2₁/n, Z = 2, a = 5.794(1) Å, b = 6.160(1) Å, c = 8.141(1) Å, b = 91.23(1)°, N(F ³° 2σ F) = 1127, N(Var.) = 53, R₁/wR₂ = 0.047/0.081Ba₂Zn(OH)₆: P2₁/n, Z = 2, a = 6.043(1) Å, b = 6.336(1) Å, c = 8.451(2) Å, b = 91.23(2)°, N(F ° 2σ F) = 1669, N(Var.) = 54, R₁/wR₂ = 0.029/0.067. Sr₂Zn(OH)₆ and Ba₂Zn(OH)₆ crystallize isotypic in a distorted Li₂O structure type. Sr²⁺ resp. Ba²⁺ form a cubic primitive arrangement. Distorted octahedra of OH^– around Zn²⁺ fill therein alternating cubic gaps in an ordered way.     

Crystal Structures of {[Cd(phen)](C6H8O4)3/3} and {[Cd(phen)](C7H10O4)3/3} · 2H2O with C6H10O4 = Adipic Acid and C7H12O4 = Pimelic Acid

Two coordination polymers {[Cd(phen)](C₆H₈O₄)_3/3} ( 1 ) and {[Cd(phen)](C₇H₁₀O₄)_3/3} · 2H₂O ( 2 ) were structurally characterized by single crystal X‐ray diffraction methods. In 1 (C2/c (no. 15), a = 16.169(2)Å, b = 15.485(2)Å, c = 14.044(2)Å, β = 112.701(8)°, U = 3243.9(7)ų, Z = 8), the Cd atoms are coordinated by two N atoms of one phen ligand and five O atoms of three adipato ligands to form mono‐capped trigonal prisms with d(Cd‐O) = 2.271‐2.583Å and d(Cd‐N) = 2.309, 2.390Å. The [Cd(phen)] moieties are bridged by adipato ligands to generate {[Cd(phen)](C₆H₈O₄)_3/3} chains, which, via interchain π—π stacking interactions, are assembled into layers. Complex 2 (P1¯(no. 2), a = 9.986(1)Å, b = 10.230(3)Å, c = 11.243(1)Å, α = 66.06(1)°, β = 87.20(1)°, γ = 66.71(1)°, U = 955.7(2)ų, Z = 2) consists of {[Cd(phen)](C₇H₁₀O₄)_3/3} chains and hydrogen bonded H₂O molecules. The Cd atoms are pentagonal bipyramidally coordinated by two N atoms of one phen ligand and five O atoms of three pimelato ligands with d(Cd‐O) = 2.213—2.721Å and d(Cd‐N) = 2.329, 2.372Å. Through interchain π—π stacking interactions, the {[Cd(phen)](C₇H₁₀O₄)_3/3} chains resulting from [Cd(phen)] moieties bridged by pimelato ligands are assembled in to layers, between which the hydrogen bonded H₂O molecules are sandwiched.     

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.     

Darstellung,Kristallstrukturen und Schwingungsspektren von [(Mo6X)Y]2–; Xi = Cl,Br; Ya = NO3, NO2

Synthesis, Crystal Structures, and Vibrational Spectra of [(Mo₆X)Y]^2–; Xⁱ = Cl, Br; Y^a = NO₃, NO₂ By treatment of [(Mo₆X)Y]^2–; Xⁱ = Y^a = Cl, Br with AgNO₃ or AgNO₂ by strictly exclusion of oxygene in acetone the hexanitrato and hexanitrito cluster anions [(Mo₆X)Y]^2–, Y^a = NO₂, NO₃ are formed. X-ray structure determinations of (Ph₄As)₂[(Mo₆Cl)(NO₃)] · 2 Me₂CO ( 1 ) (monoclinic, space group P2₁/n, a = 12.696(3), b = 21.526(1), c = 14.275(5) Å, β = 115.02(2)°, Z = 2), (n-Bu₄N)₂[(Mo₆Br)(NO₃)] · 2 CH₂Cl₂ ( 2 ) (monoclinic, space group P2₁/n, a = 14.390(5), b = 11.216(5), c = 21.179(5)Å, β = 96.475(5)°, Z = 2) and (Ph₄P)₂[(Mo₆Cl)(NO₂)] (3) (monoclinic, space group P2₁/n, a = 11.823(5), b = 13.415(5), c = 19.286(5) Å, β = 105.090(5)°, Z = 2) reveal the coordination of the ligands via O atoms with (Mo–O) bond lengths of 2.11–2.13 Å, and (MoON) angles of 122–131°. The vibrational spectra of the nitrato compounds show the typical innerligand vibrations ν_as(NO₂) (∼ 1500), ν_s(NO₂) (∼ 1270) and ν(NO) (∼ 980 cm^–1). The stretching vibrations ν(N=O) at 1460–1490 cm^–1 and ν(N–O) in the range of 950–1000 cm^–1 are characteristic for nitrito ligands coordinated via O atoms.     

Die Kristallstruktur von NaBiO2

The crystal structure of NaBiO₂ NaBiO₂ crystallizes monoclinic in C with a = 7.39₄, b = 7.26₂, c = 5.88₆ Å, β = 127.7°; Z = 4. Parameters were refined by least-squares (555 hkl with |h?l| = 0 to 4; R = 10.9%). Angular groups [BiO₂] are twisted by 180°, forming chains [BiO_2/2O_2/2] along [001]. The MADELUNG part of lattice energy (MAPLE) is calculated and discussed.     

NaAuIn2, ein ternäres Aurid mit ethananalogen In2Au6-Baueinheiten und [In2/2]-Ketten

NaAuIn₂, a Ternary Auride with Ethane Analogous In₂Au₆ Building Units and [In_2/2] Chains Silver coloured, brittle single crystals of NaAuIn₂ were synthesized by the reaction of NaN₃, gold-sponge and indium at 500°C. The structure was determined from X-ray single-crystal diffractometry data: space group Cmcm, Z = 4, a = 4.482(1) Å, b = 10.366(2) Å, c = 7.869(2) Å, R/R_w(w = 1) = 0.017/0.020, Z(F) ≥ 3σ(F) = 547 and N(var.) = 16. NaAuIn₂ crystallizes in the MgCuAl₂-structure type. Gold and indium form a framework structure. [AuIn_6/3] layers with trigonal prismatically coordinated gold are connected via In—In contacts along [010] which consist of ethane analogous In₂Au₆-building units. The In-partial structure consists of saw tooth like [In_2/2] chains along [001]. The sodium atoms occupy channel-like cavities within the Au—In framework structure.     

Synthese und Kristallstruktur eines Natrium-tetraoxonitridowolframats(VI), Na5WO4N

Synthesis and Crystal Structure of Sodium Tetraoxo Nitrido Tungstate(VI), Na₅WO₄N Colourless crystals of Na₅WO₄N are obtained besides Na₄WO₂N₂ [1] by the reaction of WO₃ with NaNH₂ (15:1) at 350°C ≥ T ≥ 750°C in autoclaves to prevent early decomposition of sodium amide. X-ray single crystal investigations are characterized by the following data:

• Na₅WO₄N: Cmc2₁ (No. 36), Z = 4
• a = 9.873(2) Å, b = 5.769(1) Å, c = 10.648(2) Å
• Z(F)≥ 3σ(F) = 2182, Z(Var.) = 55, R/R_w = 0.029/0.039

The structure contains the tetragonal pyramidal ion WO₄N^5? with nitrogen at the apex connected via Na⁺ ions irregularly coordinated by one nitrogen and four oxygen atoms of different anions.     

Synthesis and structure of The Novel Layered Phase CsTi2Cl7

Reactions in the CsCl? TiCl₃? Ti system afford CsTiCl₃ (CsNiCl₃ type, a = 7.3086(7) Å, c = 6.0670(8) Å) and the new phase CsTi₂Cl₇, the structure of which was determined by single crystal X-ray diffraction means (P2/c, Z = 2, a = 7.0076(4) Å, b = 6.2256(4) Å, c = 12.000(2) Å, β = 92.175(6)°, R/R_w = 0.026/0.035 for 1403 reflections, 2Θ ≤ 60°, MoKα). The structure can be generated by condensation of TiCl₆ groups first through cis edges to form TiCl₂Cl_4/2 ribbons and then by interconnection of these with one chlorine per titanium to give layers, viz., [Ti(Cl)Cl_4/2Cl_1/2]^?. The remaining, singly bonded chlorine projects into the interlayer region and has a Ti? Cl distance 0.208 Å less than the average for the five, 2.466 Å, reflecting significant pi bonding of the chlorine to titanium. Possible interaction of the d orbitals on adjacent titanium(III) atoms is also considered.     

Über hexagonale Perowskite mit Kationenfehlstellen. XXVI. Ba12Ba2 2/3M 1/3□2O33□3 (MV = Nb,Ta) – die ersten Stapelvarianten eines rhomboedrischen 36 L-Typs

On Hexagonal Perovskites with Cationic Vacancies. XXVI. Ba₁₂Ba_{2 2/3}M _1/3□₂O₃₃□₃ (M^V = Nb, Ta) – the First Stacking Polytypes of a Rhombohedral 36 L-Type In the systems BaO? MO₅(M^V = Nb, Ta) for a Ba:M^V ratio of 2:1 polymorphism is observed. Here the low temperature modifications are described. They crystallize in a rhombohedral 36 L structure with three formula units Ba₁₂Ba_{2 2/3}M _1/3□₂O₃₃□₃ for the trigonal setting (M^V = Nb: a = 5.92₂ Å; c = 93.₂₅ Å; Ta: a = 5,92₂ Å; s = 93.4 Å).     

Zur Kenntnis von Na4Br(NH2)3: Ein Amidbromid im System NaNH2/NaBr

Na₄Br(NH₂)₃: An Amide Bromide in the System NaNH₂/NaBr The pseudobinary system NaNH₂/NaBr was investigated by X-ray methods. The crystal structure of Na₄Br(NH₂)₃ was solved by single crystal data: Pnnm, Z = 4, a = 6.579(2) Å, b = 12.755(4) Å, c = 8.776(2) Å Z(F_o) with (F_o)² ≥ 3σ = (F_o)² = 503, Z(parameter) = 39, R/R_w = 0.082/0.106. It is a new type of structure, built up by a three-dimensional network of [Na₄(NH₂)₃⁺] containing the bromide ions.