(NH4)4Na2[V10O28]·10H2O

Tetra­ammonium disodium decavanadate decahydrate crystallizes in the triclinic system in space group P. The structure contains typical centrosymmetric OV₆ double octahedra and centrosymmetric pairs of edge‐shared NaO₆ double octahedra forming a layered structure. In contrast to other monovalent cationic decavanadates, the NaO₆ double octahedra are integrated in the layer.     

(Et4N)4[V4O12]·2H2O

The title compound, tetrakis(tetraethylammonium) cyclo‐tetra‐μ‐oxo‐tetrakis[dioxovanadium(V)] dihydrate, (C₈H₂₀N)₄[V₄O₁₂]·2H₂O, was obtained by reacting V₂O₅ with (C₂H₅)₄NOH. It consists of a discrete centrosymmetric molecular anion, [V₄O₁₂]^4?, where four tetrahedral VO₄ units share two vertices with each other to form a ring. A water mol­ecule is attached on each side of the ring through hydrogen bonds.     

[Ni(H2O)6]2[Na(H2O)3]2[V10O28]·4H2O,bis(nickel hexahydrate) bis(sodium trihydrate) decavanadate tetrahydrate

Polyoxometallates are capable of including transition metals in their crystal structures as either discrete cations or heteroatoms. The title compound crystallizes with triclinic symmetry and consists of a centrosymmetric [V₁₀O₂₈]^6? anion, a trimeric {[Na(H₂O)₃][Ni(H₂O)₆][Na(H₂O)₃]}⁴⁺ cation, an [Ni(H₂O)₆]²⁺ cation and four water molecules of crystallization. The compound possesses two Ni atoms (each on independent inversion centres), one as a discrete cation and one in a disodium–nickel trimeric cation involved in the one‐dimensional polycation–polyanion hybrid polymer. The polymers are bound together via hydrogen bonds to the water mol­ecules and the nickel(II) hexahydrate cation. Several structures of decavanadate compounds having transition metal atoms, monovalent cations and [V₁₀O₂₈]^6? anions in the ratio 2:2:1 have been reported previously. However, the present compound differs from these in its arrangement of monovalent cations and transition metal atoms.     

Doppeloktaeder-Cluster [V2O9] in der Kristallstruktur von Vanadium(III)-diphosphat,V4(P2O7)3

Double-Octahedra Clusters [V₂O₉] in the Crystal Structure of Vanadium (III) Diphosphate, V₄(P₂O₇)₃ . As the first example for M^III diphosphates the crystal structure of V₄(P₂O₇)₃ (“ I ”) has been determined by means of X-ray diffraction of single crystals. I – according to [7] obtainable by thermal interaction of V₂O₅, H₃PO₃, and H₃PO₄ – crystallizes orthorhombically (data see above); in the unit cell two kinds of isolated doubleoctahedra (clusters) [V₂O₉], having the symmetry C_s, exist. Due to a mutual face-connection of the octahedra, within these clusters relatively short V–V distances are resulting: 2.774(8) and 3.026(7) Å. The diphosphate anions, O₃POPO₃^4? (three kinds; each having the symmetry C_s and staggered conformation), exhibit POP bond angles of 170°, being remarkably large for non-centrosymmetry. Because of the [M₂^IIIO₉] clusters in I , and also in the isostructural diphosphates Cr₄(P₂O₇)₃ and Fe₄(P₂O₇₃), magnetic investigations seem to be challenged.     

Organic clays. Synthesis and structure of Na5[calix[4] arene sulfonate] · 12 H2O,K5[calix[4]arene sulfonate]·8 H2O,Rb5[calix[4]arene sulfonate]·5 H2O,and Cs5[calix[4] arene sulfonate] ·4 H2O

The title calixarenes all exist in the solid state as bilayers of anionic calixarenes in the cone configuration. These layers alternate with inorganic regions which contain the cations and the water molecules. The overall structures bear a close resemblance to those found for clay minerals. The sodium salt crystallizes in the triclinic space groupP witha = 10.998(6),b = 13.582(5),c = 14.472(5) Å, = 74.01(3), = 89.09(4), = 86.50(4)°, andZ = 2 forD _calc = 1.72 g cm^–3. Refinement based on 4727 observed reflections led to a conventionalR = 0.050. The potassium salt crystallizes in the triclinic space groupP witha = 11.815(9),b = 13.636(6),c = 14.040(9) Å, = 100.24(5), = 111.86(9), = 95,14(9)°, andZ = 2 forD _calc = 1.77 g cm^–3. Refinement based on 2977 observed reflections led toR = 0.15. The rubidium and cesium salts are isostructural and crystallize in the monoclinic space groupP2₁/n with parameters for Rb[Cs]a = 11.603(5) [11.704(3)],b = 28.607(8) [29.747(9)],c = 12.512(5) [12.604(4)] Å, = 91.70(4) [91.63(2)°], andZ = 4 forD _calc = 2.01 [2.24] g cm^–3. Refinement based on 1750 [4257] observed reflections led toR = 0.108 [0.075]. Disorder of the cations was observed for the rubidium and cesium salts. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82074 (95 pages).     

Na2[Pr4O2]Cl9 und K2[Pr4O2]Cl9, die ersten reduzierten quaternären Praseodymchloride mit anti-SiS2-analogen [Pr4/2O]-Ketten

Na₂[Pr₄O₂]Cl₉ and K₂[Pr₄O₂]Cl₉, the First Reduced Quaternary Praseodymium Chlorides with Anti-SiS₂ Analogous [Pr_4/2O] Chains The compounds A₂[Pr₄O₂]Cl₉ (A = Na, K) are the first reduced quaternary praseodymium chlorides with anti-SiS₂ analogous [Pr_4/2O] chains. Synthesis took place in the temperature range from 900 to 600°C in silica-jacketed niobium containers from Pr metal, PrCl₃, PrOCl and NaCl (KCl) as starting materials. The X-ray structure analysis of a single crystal of Na₂[Pr₄O₂]Cl₉ (monoclinic, P2₁/m (No. 11), Z = 2, a = 812.2(2) pm, b = 1 134.1(2) pm, c = 937.6(2) pm, β = 106.51(2)°, R = 0.048, R_w = 0.037) exhibits trans-edge connected chains of [Pr_4/2O] tetrahedra running along [001] which are connected by surrounding common chloride ions forming layers parallel to (001). These layers are connected by further chloride ions to a three-dimensional network. The sodium ions surrounded by a heavily distorted octahedron of chloride ions are placed between the layers. The X-ray structure analysis of a single crystal of the otherwise isotypic K₂[Pr₄O₂]Cl₉ (monoclinic, P2₁/m (No. 11), Z = 2, a = 820.6(2) pm, b = 1 133.2(4) pm, c = 949.2(3) pm, β = 103.94(2)°, R = 0.073, R_w = 0.054) shows that potassium is coordinated by nine chloride ions.     

Ein neues Oxoberyllat: K2Na4[O2BeOBeO2]

On K₂Na₄[O₂BeOBeO₂] For the first time colourless single crystals of K₂Na₄[Be₂O₅] which are isotypic with K₂Na₄[Co₂O₅] [2] and Rb₂Na₄[Co₂O₅] have been prepared by heating e.g. a well ground mixture of K₂O, Na₂O and BeO (K:Na:Be = 2.2:4.4:2; 750°C; 21 d; Ni-tube). The crystal structure was solved by four-circle diffractometer data [Siemens AED 2; 389 I_o(hkl); space group P4₂/mnm; Z = 2; a = 595.17(4) pm, c = 1 002.66(9) pm; R = 4.1%; R_w = 2.3%]. Mean Fictive Ionic Radii, MEFIR, Effective Coordination Numbers, ECoN, the Madelung Part of Lattice Energy, MAPLE, and the charge distribution are calculated.     

硒钼钒杂多配合物的合成与表征

由钒原子取代杂多阴离子中的钼或钨原子后,形成的多元配合物具有与原来杂多配合物显著不同的催化性质,有关钼钒的同多阴离子,近年报道的有[V2Mo6O26]^6-、[V5Mo8O40]^7-、[V8Mo4O36]^8-等,而三元硒钼钒杂多分配物仅见于[Se2Mo2V6O28]^6-。本文合成了两种硒钼钒三元杂多配合物,并对其进行了表征。     

Die ersten Oxocobaltate(II) mit zweikernigem Anion: Rb2Na4[Co2O5] und K2Na4[Co2O5]

The First Oxocobaltate(II) with Dinuclear Anion: Rb₂Na₄[Co₂O₅] and K₂Na₄[Co₂O₅] By heating of well ground mixtures of the binary oxides [A₂O, Na₂O, ?CoO”?, A:Na:Co = 1.00:2.00:1, (A = K, Rb); Ag-tube, 600°C, 14 d] we obtained Rb₂Na₄[Co₂O₅] and K₂Na₄[Co₂O₅] rough, transparent, red single crystals. We find a new type of structure with the anion [O₂CoOCoO₂]^6?. Space group P4₂/mnm; a = 634.4 pm, c = 1030.3 pm, Z = 2 (A = K) a = 647.6 pm, c = 1021.1 pm, Z = 2 (A = Rb); four-circle diffractometer data; MoKα -radiation; 360 from 364 I₀(hkl), R = 4.34%, R_w = 3.54% (A = K); 361 from 366 I₀(hkl), R = 6.54%, R_w = 2.70% (A = Rb). The anion is planar, the CN of Co is 3. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, are calculated and discussed.     

Synthesis,Crystal Structure,and Thermal Properties of Na5[SnS4]Cl·13H2O

Reaction of Na₂S with SnCl₄ · 5H₂O in aqueous alkaline sodium hydroxide solution leads to the formation of Na₅[SnS₄]Cl · 13H₂O ( 1 ). The compound crystallizes monoclinic in space group P2₁/m with two formula units in the unit cell. In the crystal structure the Na⁺ cations are octahedrally coordinated and are linked into layers by bridging water molecules, μ₃ bridging Cl^– anions and μ_1,1 bridging S atoms of [SnS₄]^4– anions. Extended hydrogen bonding interactions generate a three‐dimensional network. Investigations using differential thermoanalysis, thermogravimetry, and differential scanning calorimetry shows that upon heating in open crucibles the water can be removed leading to the formation of the anhydrate that is stable at room temperature and does not transform back into compound 1 . Storage of the anhydrate in a desiccator over a water atmosphere leads first to formation of Na₄SnS₄ · 14H₂O followed by crystallization of the title compound. After longer storage times NaCl appears as a second crystalline phase. If the thermal measurements are performed in a self‐produced atmosphere, compound 1 transforms partly into Na₄SnS₄ · 14H₂O with an increasing amount of this phase with increasing temperature. Synthetic investigations reveal that crystallization of compound 1 sensitively depends on the water content of acetone, which is used for precipitation of 1 . Reacting Na₄SnS₄ · 14H₂O directly with NaCl afforded formation of complex mixtures.     

Synthesis and Characterization of Na5[VO4][O] and Na4[VO4][OH]

Na₅[VO₄][O] and Na₄[VO₄][OH] were obtained from reactions of V₂O₅ with Na₂O and additional NaOH in the latter case, respectively, at 600‐700 °C in sealed Ag containers under Ar atmosphere. The crystal structures have been determined from X‐ray single crystal data. The structures contain isolated [VO₄]^3? complexes and non‐coordinating oxide and hydroxide anions, respectively. Raman and infrared data is compared for both compounds and hydrogen bonding is discussed for Na₄[VO₄][OH].     

The Mixed Valence Tungsten(IV,V) Compound Na[W2O2Br6]

The reaction of W₆Br₁₂, NaBr, and WO₂Br₂ in the presence of Br₂ in a sealed silica tube yields Na[W₂O₂Br₆] together with WOBr₄ and WO₂Br₂ in the low temperature zone (temperature gradient 1030/870 K). Na[W₂O₂Br₆] crystallizes orthorhombically in the space group Immm (no. 71) with a = 3.775 Å, b = 10.400 Å, c = 13.005 Å and Z = 2. Pairs of condensed trans-[WO₂Br₄] octahedra with a common Br₂ edge form along [100] double chains [W₂O_4/2Br₆]^1– via the oxygen atoms. The mixed valent tungsten atoms are bonded to W₂ pairs with a 2 c–3 e bond (d(W–W) = 2.946 Å, d(W–O) = 1.888 Å, d(W–Br^b) = 2.537 Å, d(W–Br^t) = 2.535 Å, ∢O–W–O = 177.4°, ∢Br^b–W–Br^b (endocyclic) = 109.0°). The Na⁺ cations connect the anionic double chains to form two-dimensional layers parallel (001), which interact by van der Waals forces. The cations are eightfold coordinated by a cube of the terminal Br^t ligands of the polymeric anions (d(Na–Br) = 3.138 Å). Na[W₂O₂Br₆] may be discussed as an intercalation compound of the oxide bromide WOBr₃.     

Ein neues Orthovanadat(V): Cs2Na[VO4]

A New Orthovanadate (V): Cs₂Na[VO₄] Colourless single-crystals of Cs₂Na[VO₄] resulted by heating intimate mixtures of CsO_0.52, NaO_0.52 and V₂O₅ (Cs: Na: V = 2.2:1.1:1.0) in tightly closed Ni-tubes. The crystal structure was determined (four-circle diffractometer data), 1341 I_o(hkl), R = 6.23%, R_w = 4.23%, parameters see text. The new orthovanadate(V) crystallizes monoclinic (space group P2₁/m) with a = 839.9(1), b = 624.7(1), c = 614.8(1) pm, β = 92.66(1)° (Guinier-Simon powder data), Z = 2. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, these calculated via Mean Fictive Ionic Radii, MEFIR, are discussed.