Synthese,Charakterisierung und EPR-spektroskopische Untersuchung von Heteropolyverbindungen mit tetraedrisch bzw. oktaedrisch koordiniertem Eisen(III)

Synthesis, Characterization, and EPR Studies of Heteropoly Compounds with Iron(III) in Tetrahedral and Octahedral Coordination The heteropoly compounds H₅[FeO₄W₁₂O₃₆] · 6 H₂O (a₀ = 1216 pm), H₃[Fe(OH)₆Mo₆O₁₈] · 4 H₂O, Na₅[FeO₄W₁₂O₃₆] · nH₂O and FeH₂[FeO₄W₁₂O₃₆] · 17 H₂O, for the first time obtained in this work by freeze-drying and characterized by means of chemical analysis, i.r. and u.v. spectroscopy, X-ray powder-photographs, and magnetic measurements, appear as suitable model systems for EPR investigations. They contain, like a number of known Fe^III-heteropoly compounds, Fe^III in FeO₄ or/and FeO₆ units, which are isolated from each other by structural reasons. In the Keggin-compounds M₅[E^IIIO₄W₁₂O₃₆] · nH₂O ( I ) (M = Na, Rb, TMA, TEA; E = Fe, Al, B) Fe^III occupies slightly distorted tetrahedral positions (g′ ≈? 2), which are characterized by zfs-values of ≈? 10 mT and line widthes ΔB of 2.0 ?15 mT. Unlike as for I cations with different physico-chemical characteristics have only little effect on the Fe^III-zfs. This holds for the Anderson-complexes M₃[Fe(OH)₆Mo₆O₁₈]·nH₂O, (M = H, K, NH₄, TMA; g′ ≈? 4.3 ΔB ≈? 67 mT) and for M5[SiO₄W₁₁O₃₅FeO₅(OH₂)]·nH₂O, (M = K, TMA; g′ = 4.3 ΔB = 26.5 mT). The FeO₆ octahedra are more distorted than the FeO₄ tetrahedra in I and therefore less susceptible for structural changes.     

Das erste KEGGIN-Anion mit tetraedrischer. Kupfer(II)—Sauerstoff-Koordination: [α-Cu0,4(H2)0,6O4W12O36]6−

The First KEGGIN-Anion with Tetrahedral Coordination of Copper(II)-Oxygen: [α-Cu_0,4(H₂)_0.6O₄W₁₂O₃₆]^6? The solution of the Cu^II-containing heteropolyanion was prepared starting from an aqueous solution of Na₂WO₄, adjusting to pH 5–6 by adding slowly a solution of Cu(NO₃)₂ in HNO₃. The addition of the corresponding amount of N(CH₃)₄Br to the concentrated solution led to the crystallization of the greenish-yellow mixed crystals (TMA)₆[α-Cu_0.4(H₂)_0.6O₄W₁₂O₃₆] · 9 H₂O. After repeated recrystallization it has been investigated by chemical, spectroscopic (IR/Raman, UV, ¹⁸³W/¹H-NMR, ESR) and X-ray diffraction methods (monoclinic; space group P2₁; a = 13.117(4), b = 21.466(4), c = 13.223(3) Å, β = 91.60°; Z = 2; D_c = 3.041 g · cm^?3; R = 8.0%). The distances of the four “tetrahedral” oxygen atoms to the position (0, 0, 0) range from 1.67 to 1.93 Å. The alternative occupation of the central KEGGIN position with copper(II) and two protons, respectively, accounts for the different distances. The prepared solid solution represents the first example for the tetrahedral copper(II)-oxygen coordination in any heteropolyanion compound.     

Peroxofluorokomplexe der Übergangsmetalle. IX. Kristallstruktur von Ba3[Ti(O2)F5]2 · 2 H2O

Transition Metal Peroxofluoro Complexes. IX. Crystal Structure of Ba₃[Ti(O₂)F₅]₂ · 2 H₂O The pale yellow hydrat Ba₃[Ti(O₂)F₅]₂ · 2 H₂O crystallizes tetragonal (space group P4₂/mbc, a = 1 248.5(3), c = 812.2(2) pm; Z = 4; R = 0.026 for 404 independent reflections). It contains isolated [Ti(O₂)F₅]^3? anions. Thermal decomposition leads directly to α-Ba₃Ti₂O₂F₁₀, which is isotypic to α-Ba₃Al₂F₁₂.     

Die Kristallstruktur des Natriumoxohydroxoaluminathydrates Na2[Al2O3(OH)2] · 1,5 H2O

The Crystal Structure of the Sodium Oxohydroxoaluminate Hydrate Na₂[Al₂O₃(OH)₂] · 1.5 H₂O The crystal structure of the sodium oxohydroxoaluminate hydrate Na₂[Al₂O₃(OH)₂] ·s 1.5 H₂O (up to now described as Na₂O · Al₂O₃ · 2.5 H₂O and Na₂O · Al₂O₃ · 3 H₂O, respectively) was solved. The X-ray single crystal diffraction analysis (tetragonal, space group P-42₁m, a = 10.522(1) Å, c = 5.330(1) Å, Z = 4) results in a polymeric layered structure, consisting of AlO_3/2(OH) tetrahedral groups. Between these layers the Na⁺ ions are situated, which form tetrameric groups of face-linked NaO₆ octahedra. The involved O^2? ions are due to Al? O? Al bridges, Al? OH groups and water of crystallization. ²⁷Al and ²³Na MAS NMR investigations confirm the crystal structure analysis. The relations between the crystallization behaviour of the compound and the constitution of the aluminate anions in the corresponding sodium aluminate solution and in the solid, respectively, are discussed.     

Pentapotassium dodecatungsto­borate(III) hexadecahydrate

The title compound, K₅[BW₁₂O₄₀]·16H₂O, contains a [BW₁₂O₄₀]^5? polyanion of 222 crystallographic symmetry, with a central tetrahedrally coordinated B^III atom surrounded by four groups of three edge‐sharing octahedra (W₃O₁₃ subunits), which are linked in turn to each other and to the central BO₄ tetrahedron by shared O atoms at the vertices. There is a crystallographically unique B—O bond of 1.554 (10) Å, while the average W—O distances are 2.344 (17) Å for four coordinate O atoms, 1.917 (12) and 1.89 (2) Å for two coordinate O atoms within and connecting the W₃O₁₃ subunits, respectively, and 1.709 (8) Å for terminal O atoms. Not all of the K⁺ ions and H₂O groups were located.     

Oxalato‐ und Quadratato‐Komplexe hochkoordinierter Metallionen: Die Raumnetzstrukturen von La2(C2O4)(C4O4)2(H2O)8 · 2,5 H2O und K[Bi(C2O4)2] · 5 H2O

Oxalato‐ and Squarato‐Bridged Threedimensional Networks: The Crystal Structures of La₂(C₂O₄)(C₄O₄)₂(H₂O)₈ · 2.5 H₂O and K[Bi(C₂O₄)₂] · 5 H₂O The title compounds have been formed by hydrolysis of amino‐ and thioderivatives of squaric acid in the presence of La^III and Bi^III ions. Both compounds are threedimensional coordination polymers in the solid state, as shown by single crystal X‐ray crystallography. In La₂(C₂O₄)(C₄O₄)₂(H₂O)₈ · 2.5 H₂O oxalato‐bridged pairs of LaO₉ polyhedra are connected with identical neighbouring polyhedra by squarate ions. In K[Bi(C₂O₄)₂] · 5 H₂O each Bi atom is fourfold linked to other Bi atoms by the oxalate ions. The resulting 3D network shows a diamond‐like topology with square‐shaped channels. In both structures the channels are partially filled by water molecules.     

Tri­potassium hexa­hydrogen­hexa­molybdo­cobaltate(III) potassium nitrate tetra­hydrate,K3[H6CoMo6O24]·KNO3·4H2O

The title double salt was obtained from the reaction of Y(NO₃)₃ and K₆[H₄Co₂Mo₁₀O₃₈]·5H₂O at a pH of about 2.0. The [H₆CoMo₆O₂₄]^3? anion is a typical B‐type Anderson‐structure heteropolyanion, and has an inversion center, with Co—O bond lengths in the range 1.907 (4)–1.919 (4) Å and Mo—O bond lengths in the ranges 1.709 (5)–1.721 (5), 1.902 (5)–1.951 (5) and 2.274 (4)–2.312 (4) Å.     

[Ho5(H2O)16(OH)2As6W64O220]25−, ein großes neuartiges Polyoxoanion aus trivakanten Keggin‐Fragmenten

[Ho₅(H₂O)₁₆(OH)₂As₆W₆₄O₂₂₀]^25?, a Large Novel Polyoxoanion from Trivacant Keggin Fragments The novel polyoxotungstate Na₇K₁₈[Ho₅(H₂O)₁₆(OH)₂As₆W₆₄O₂₂₀] · 56 H₂O ( 1 ) was synthesized in aqueous solution and characterized by X‐ray structure analysis, elemental analysis and IR spectroscopy. The anion in 1 represents one of the largest polyoxoanions known yet and exhibits an unusual arrangement of six Keggin units. It consists of six trivacant lacunary α‐B‐(AsW₉O₃₃)^9? Keggin fragments which are connected by a bridging [Ho₅W₁₀(H₂O)₁₆(OH)₂O₂₂]²⁹⁺ unit. The five Ho^III atoms are coordinated by eight oxygen atoms, forming a square‐antiprism.     

Self‐Assembly of Polyoxometalate‐Supported Ln‐H nydroxo/Oxo Clusters with 1D Extended Structure: [LnIII(H2O)7Cr(OH)6Mo6O18]n·4nH2O (Ln = Ce,Sm, Eu)

Three novel polyoxometalate compounds consisting of Anderson‐type anions and trivalent lanthanide cations, [Ln(H₂O)₇Cr(OH)₆Mo₆O₁₈]_n·4nH₂O (Ln = Ce 1 ; Sm 2 ; Eu 3 ), have been synthesized in aqueous solution and characterized by single crystal X‐ray diffraction, elemental analyses, IR spectra, and TG analyses. Single crystal X‐ray diffractions reveal that the structures of the 1:1 composite compound formed by the heteropolyanion [Cr(OH)₆Mo₆O₁₈]^3? as the building unit and the [Ln(H₂O)₇]³⁺ complex fragment as the linker, which exhibit a type of zig‐zag chain with alternating cations and anions through the Mo‐Ot′‐Ln‐Ot′‐Mo linkage in the crystal. The magnetic properties of 1 ? 3 have been studied by measuring their magnetic susceptibility over the temperature range of 2‐300 K. The UV‐vis spectra of 1 give the Mo‐O and Cr^III‐O charge transfer transitions at 203 and 543 nm, respectively. In addition, the fluorescent characteristic transition of the Eu³⁺ ions in compound 3 is reported.     

Darstellung der freien Dodekawolframatoaluminiumsäure H5[AlO4W12O36] · 6 H2O mittels Gefriertrocknung

Preparation of the Free 12-Tungstoaluminium Acid H₅[AlO₄W₁₂O₃₆] · 6 H₂O by Means of the Cryogenic Method The title compound was first prepared in solid state from its aqueous solution by means of the cryogenic method and characterized by chemical and thermal analyses, IR and UV spectroscopy. From X-ray heating patterns the formation of a new cubic phase 1/2 Al₂O₃ · 12 WO₃ (I) at 400°C was found, being stable till 830°C: a = 378 pm (600°C). High-resolution ²⁷Al NMR (MAS-technique) was used to determine the tetrahedral coordination of aluminium in the title compound and the octahedral coordination in I. The degradation of the doped WO₃-phase I into Al₂(WO₄)₃ begins at 600°C. Above 830°C tetragonal WO₃ and Al₂(WO₄)₃ coexist.     

Zur Kenntnis der Phase BaO · Al2O3 · 7 H2O

On the Compound BaO · Al₂O₃ · 7 H₂O On the basis of investigations using ²⁷Al, ¹H NMR, IR and thermoanalytical methods for the compound BaO · Al₂O₃ · 7 H₂O a constitution as Ba_n[Al₂(OH)₈]_n · 3n H₂O with condensed AlO₆ groups, sharing edges, is proposed. Relations between the Ba/Al ratio and the constitution of anions of barium aluminate hydrates are discussed.     

Die Kristallstruktur der hydratisierten Cyanokomplexe NMe4MnII[(Mn, Cr)III(CN)6] · 3 H2O und NMe4Cd[MIII(CN)6] · 3 H2O (MIII = Fe,Co): Verwandte des Berliner Blaus

The Crystal Structure of the Hydrated Cyano Complexes NMe₄Mn^II[(Mn, Cr)^III(CN)₆] · 3 H₂O and NMe₄Cd[M^III(CN)₆] · 3 H₂O (M^III = Fe, Co): Compounds Related to Prussian Blue The crystal structures of the isotypic tetragonal compounds (space group I4, Z = 10) NMe₄Mn^II · [(Mn, Cr)^III(CN)₆] · 3 H₂O (a = 1653.2(4), c = 1728.8(6) pm), NMe₄Cd[Fe(CN)₆] · 3 H₂O (a = 1642.7(1), c = 1733.1(1) pm) and NMe₄Cd[Co(CN)₆] · 3 H₂O (a = 1632.1(2), c = 1722.4(3) pm) were determined by X‐rays. They exhibit ⊥ c cyanobridged layers of octahedra [M^III(CN)₆] and [M^IIN₄(OH₂)₂], which punctually are interconnected also || c to yield altogether a spaceous framework. The M^II atoms at the positions linking into the third dimension are only five‐coordinated and form square pyramids [M^IIN₅] with angles N–M^II–N near 104° and distances of Mn–N: 1 × 214, 4 × 219 pm; Cd–N: 1 × 220 resp. 222, 4 × 226 resp. 228 pm. Further details and structural relations within the family of Prussian Blue are reported and discussed.     

Co(en)3[B4O5(OH)4]Cl·3H2O和[Ni(en)3][B5O6(OH)4]2·2H2O的合成、结构以及热力学性质

利用水热法合成了两种过渡金属配合物为模板剂的含水硼酸盐晶体Co(en)3[B4O5(OH)4]Cl·3H2O(1) 和 [Ni(en)3][B5O6(OH)4]2·2H2O (2),并通过元素分析、X射线单晶衍射、红外光谱及热重分析对其进行了表征。化合物1晶体结构的主要特点是在所有组成Co(en)33+, [B4O5(OH)4]2–, Cl– 和 H2O之间通过O–H…O、O–H…Cl、N–H…Cl和N–H…O四种氢键连接形成网状超分子结构。化合物2晶体结构的特点是[B5O6(OH)4]–阴离子通过O–H…O氢键连接形成沿a方向有较大通道的三维超分子骨架,模板剂[Ni(en)3]2+阳离子和结晶水分子填充在通道中。     

Alkalimolybdotellurate: Darstellung und Kristallstruktur von Rb6[TeMo6O24] · 10H2O und Rb6[TeMo6O24] · Te(OH)6 · 6H2O

Alkaline Molybdotellurates: Preparation and Crystal Structures of Rb₆[TeMo₆O₂₄] · 10H₂O and Rb₆[TeMo₆O₂₄] · Te(OH)₆ · 6H₂O Single crystals of Rb₆[TeMo₆O₂₄] · 10 H₂O and Rb₆[TeMo₆O₂₄] · Te(OH)₆ · 6 H₂O, respectively, were grown from aqueous solution. Rb₆[TeMo₆O₂₄] · 10 H₂O possesses the space group P1 . The lattice dimensions are a = 963.40(13), b = 972.56(12), c = 1 056.18(13) pm, α = 97.556(10), β = 113.445(9), γ = 102.075(10)°; Z = 1, 2 860 reflections, 215 parameters refined, R_g = 0.0257. The centrosymmetrical [TeMo₆O₂₄]^6? anions are stacked parallel to [010]. Rb(2) is coordinated with one exception by water molecules only. Folded chains consisting of [TeMo₆O₂₄]^6? anions and Rb(2) coordination polyhedra which are linked to pairs represent the prominent structural feature. Rb₆[TeMo₆O₂₄] · Te(OH)₆ · 6 H₂O crystallizes monoclinically in the space group C2/c with a = 1 886.4(3), b = 1 000.9(1), c = 2 126.5(3) pm, and β = 115.90(1)°; Z = 4, 3 206 reflections, 240 parameters refined, R_g = 0.0333. It is isostructural in high extent with (NH₄)₆[TeMo₆O₂₄] · Te(OH)₆ · 7 H₂O. Hydrogen bonds between Te(OH)₆ molecules and [TeMo₆O₂₄]^6? anions establish infinite strands. The [TeMo₆O₂₄]^6? anions gather around Te(OH)₆ providing channel-like voids extending parallel to [001].     

Crystal Structure and Characterization of a Large Polyoxotungstate (NH4)21{La(H2O)5[Ni(H2O)]2As4W40O140}·53H2O

The heteropolytungstate (NH4)₂₁{La(H₂O)₅[Ni(H₂O)]₂As₄W₄₀O₁₄₀}·53H₂O is obtained by the reaction of Na₂₇[NaAs₄W₄₀O₁₄₀]· 60H₂O with NiCl₂·6H₂O, La(NO₃)₃·6H₂O and NH₄Cl at pH‐4.5. The structure and chemical composition are determined by X‐ray diffraction analysis and elemental analysis. The crystal data and main structure refinement are a = 1.9551(3) nm, b = 2.4156(4) nm, c= 3.7068(6) nm, β = 91.505(3)°, V = 17.500 (5) nm³, monoclinic crystal system with space group P2₁/n, Z = 4, R₁ = 0.0573, wR₂ = 0.0717 [I >2<s?(I)], R₁, = 0.2463 and wR₂ = 0.1199 (all data). [La(H₂O)₅] {Ni(H₂O)}₂AS₄W₄₀O₁₄₀ has C₂, symmetry. IR spectra of the ligand [NaAs₄W₄₀O₁₄₀]^27‐ and its three complexes were discussed.     

Über die Kristallstruktur von Barium-Acetylendicarboxylat Monohydrat – Ba[C2(COO)2] · H2O

On the Crystal Structure of Barium Acetylene Dicarboxylate Monohydrate – Ba[C₂(COO)₂] · H₂O Ba[C₂(COO)₂] · H₂O crystallizes in the monoclinic space group P2₁/a. The lattice constants are a = 753.4(2), b = 921.8(2), c = 881.8(2) pm and β = 102.00(2)°. The crystal structure is characterized by an intricate three-dimensional framework made up by Ba²⁺ and [C₂(COO)₂]^2? ions. Ba²⁺ has coordination number 9 and is bound to two water molecules and seven oxygen atoms belonging to carboxylate groups of the dianion. The [C₂(COO)₂]^2? ion does not merely act like a multiple monodentate ligand, but coordinates Ba²⁺ in a chelate-like manner as well. The carboxylate groups of the dianion are inclined to each other by 65°.     

Zu den Kristallstrukturen der Übergangsmetall(II)‐Dodekahydro‐closo‐Dodekaborat‐Hydrate Cu(H2O)5,5[B12H12]·2,5 H2O und Zn(H2O)6[B12H12]·6 H2O

On the Crystal Structures of the Transition‐Metal(II) Dodecahydro‐closo‐Dodecaborate Hydrates Cu(H₂O)_5.5[B₁₂H₁₂]·2.5 H₂O and Zn(H₂O)₆[B₁₂H₁₂]·6 H₂O By neutralization of an aqueous solution of the free acid (H₃O)₂[B₁₂H₁₂] with basic copper(II) carbonate or zinc carbonate, blue lath‐shaped single crystals of the octahydrate Cu[B₁₂H₁₂]·8 H₂O (≡ Cu(H₂O)_5.5[B₁₂H₁₂]·2.5 H₂O) and colourless face‐rich single crystals of the dodecahydrate Zn[B₁₂H₁₂]·12 H₂O (≡ Zn(H₂O)₆[B₁₂H₁₂]·6 H₂O) could be isolated after isothermic evaporation. Copper(II) dodecahydro‐closo‐dodecaborate octahydrate crystallizes at room temperature in the monoclinic system with the non‐centrosymmetric space group Pm (Cu(H₂O)_5.5[B₁₂H₁₂]·2.5 H₂O: a = 768.23(5), b = 1434.48(9), c = 777.31(5) pm, β = 90.894(6)°; Z = 2), whereas zinc dodecahydro‐closo‐dodecaborate dodecahydrate crystallizes cubic in the likewise non‐centrosymmetric space group F23 (Zn(H₂O)₆[B₁₂H₁₂]·6 H₂O: a = 1637.43(9) pm; Z = 8). The crystal structure of Cu(H₂O)_5.5[B₁₂H₁₂]·2.5 H₂O can be described as a monoclinic distortion variant of the CsCl‐type arrangement. As characteristic feature the formation of isolated [Cu₂(H₂O)₁₁]⁴⁺ units as a condensate of two corner‐linked Jahn‐Teller distorted [Cu(H₂O)₆]²⁺ octahedra via an oxygen atom of crystal water can be considered. Since “zeolitic” water of hydratation is also present, obviously both classical H–O^δ?···^+δH–O and non‐classical B–H^δ?···^+δH–O hydrogen bonds play a significant role for the stabilization of the structure. A direct coordinative influence of the quasi‐icosahedral [B₁₂H₁₂]^2? anions on the Cu²⁺ cations has not been determined. The zinc compound Zn(H₂O)₆[B₁₂H₁₂]·6 H₂O crystallizes in a NaTl‐type related structure. Two crystallographically different [Zn(H₂O)₆]²⁺ octahedra are present, which only differ in their relative orientation within the packing of the [B₁₂H₁₂]^2? anions. The stabilization of the crystal structure takes place mainly via H–O^δ?···^+δH–O hydrogen bonds, since again the hydrogen atoms of the [B₁₂H₁₂]^2? anions have no direct coordinative influence on the Zn²⁺ cations.     

Zur Kenntnis von Kaliumarseniten im Dreistoffsystem K2O?As2O3?H2O. Darstellung und Kristallstruktur von K3(HAs2O4)(As2O4) · 3/2 H2O

Concerning Potassium Arsenites in the Three-Component System K₂O? As₂O₃? H₂O. Preparation and Crystal Structure of K₃(HAs₂O₄) (As₂O₄) · 3/2 H₂O The phase K₃(HAs₂O₄)(As₂O₄) · 3/2 H₂O has been identified in the system K₂O? As₂O₃? H₂O at 40°C and characterized by X-ray structural analysis. In the crystal lattice independent polymetaarsenite anions, [HAs₂O₄^?]_n and [As₂O₄^2?]_n, adopt parallel zweier single chains.     

Zur Koordination des Aluminiums in den Calciumaluminathydraten 2 CaO · Al2O3 · 8 H2O und CaO · Al2O3 · 10 H2O

On the Coordination of Al in the Calcium Aluminate Hydrates 2 CaO · Al₂O₃ · 8 H₂O and CaO · Al₂O₃ · 10 H₂O By investigations with high-resolution ²⁷Al-NMR in solids it is shown that in the compound 2 CaO · Al₂O₃ · 8 H₂O the Al merely exist in octahedral coordination. According to this and considering its structural relationship with 4 CaO · Al₂O₃ · 19 H₂O the dicalcium aluminate hydrate is proposed to be formulated as [Ca₂Al(OH)₆][Al(OH)₃ (H₂O)₃]OH. Likewise for the compound CaO · Al₂O₃ · 10 H₂O the octahedral coordination of the Al is proved by ²⁷Al-NMR. This result corresponds with literature according to which a constitution as cyclohexaaluminate Ca₃[Al₆(OH)₂₄] · 18 H₂O is proposed.     

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.