Das erste Oxoaurat(I) mit [O?Au?O]-Hanteln: KNa2[AuO2]

The First Oxoaurate(I) with Dumb-bell-like Anion: KNa₂[AuO₂] By controlled oxidation of NaAu with Na₂O₂ and K₂O_2,2 (sealed Ag-cylinder, 430°C, 6 d; mixtures: K₂O_2,2:Na₂O₂:NaAu = 1:1:2) hitherto unknown KNa₂[AuO₂] is obtained. The single crystals are light yellow, nearly colourless, and transparent. According to single crystal data (space group Pnnm; a = 1025.6(3), b = 547.2(2). c = 400.0(1) pm; Z = 2; (four circle diffractometer PW 1100, MoKα; 376 I₀(h kl); R = 6.2% and R_w = 6.7%)) KNa₂[AuO₂] crystallizes with a new structure type. Characteristic are isolated dumb-bell-like [O Au O] units. The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed.     

Neuartige Mäander mit Co3+ und Au3+: Na4[AuCoO5] = Na8 [(O2/2(CoO)O2AuO2/2)2]

Novel meander with Co³⁺ und Au³⁺: Na₄[AuCoO₅] = Na₈ ¹∞ [(O_2/2 (CoO)O₂AuO_2/2)₂] By “reaction with the wall” we obtained for the first time transparent brown single crystals of Na₄[AuCoO₅] while heating intimate mixtures of Co₃O₄, Na₂O₂, and K₂O₂ (Co: Na: K = 1.00:4.91:2.20; 650°C/44d) in a sealed gold-tube: monoclinic, P2₁/m, with a = 555.69(4) pm, b = 1042.11 (8) pm, c = 555.69(4) pm, β = 117.387(5)°, Z = 2. Characteristic features of Na₄[AuCoO₅] are meandric chains [(O_2/2 (CoO)O₂AuO_2/2)₂]. The structure has been determined by four-circle diffractometer data (Siemens AED 2; Mo? Kα , graphite, 881 I₀(hkl), R = 0.0366, R_w = 0.0316), parameters as given in the text. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, these via Mean Fictive Ionic Radii, and Charge-distribution, CHARDI, are calculated and discussed.     

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.     

Oxydation intermetallischer Phasen: CsK2[AuO2] aus CsAu + K2O2

Oxidation of Intermetallic Phases CsK₂[AuO₂] from CsAu+K₂O₂ We prepared the hitherto unknown CsK₂[AuO₂] [Heating mixtures of CsAu and K₂O_2,2; 1:1; gives single crystals (Ag-cylinder, 430°C, 6d)]. The single crystals are light blue, nearly colourless, and transparent. A new type of structure is found. The single crystal data are: Pnma; a = 1256.5(5), b = 727.3(2), c = 627.9(2)pm, Z = 4; four-circle diffractometer PW 1100, MoKα;849 out of 871 I₀(hkl), R = 7.3% and R_w = 6.3%. The Madelung Part of Lattice Energy, MAPLE, is calculated.     

Ein neues Oxoindat K2Na3[InO4]

A New Oxoindate K₂Na₃[InO₄] We prepared the hitherto unknown K₂Na₃[InO₄] on two different ways as single crystals

• a) by heating mixtures of In₂O₃, NaO_0.48 and KO_0.60 (In:Na:K = 1:3.3:2.2) [Ag-cylinder, 580°C, 42 d].
• b) by the oxidation of NaIn with Na₂O₂ and KO_0.87 (In:Na:K = 1:2:6) [Ag-cylinder, 480°C, 8 d].

The single crystals of K₂Na₃[InO₄] are colourless, all transparent and rough. The type of structure was elucidated by 4-circle diffractometer (Siemens AED 2) data: Pnnm; a = 955.5(4), b = 927.6(4), c = 753.4(2) pm; Z = 4; MoKα; 909 of 1031 I₀(hkl); R = 9.7%, R_w = 3.9%. The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed.     

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.     

Über ein neues Oxoferrat mit „Butterfly-Motiv”︁: K2Na4[Fe2O5]

A New Oxoferrate with “Butterfly-Motiv”: K₂Na₄[Fe₂O₅] Dark red-brown single-crystals of K₂Na₄[Fe₂O₅] were obtained for the first time by heating “K₃Na₃CdO₄” at 500°C in closed Fe-cylinders. Determination and refinement of the crystal structure confirms the space group P4₂/mnm (No. 136). Four-circle diffractometer data: MoKα , 373 out of 373 I_o(hkl); R = 5.3%; R_w = 4.6%; a = 645.94(5), c = 1 039.2(1) pm. In contrast to the already known oxoferrates(II) with the “Butterfly-Motiv”, Rb₆[Fe₂O₅] and K₆[Fe₂O₅] [1], we now found an isotypic structure for K₂Na₄[Fe₂O₅] with the oxocobaltates of Rb₂Na₄[Co₂O₅] and K₂Na₄[Co₂O₅] [2].     

Das erste Oligo-Oxo-Aluminat: Na14[Al4O13]

The First Oligo-Oxo-Aluminate: Na₁₄[Al₄O₁₃] Colourless single crystals of Na₁₄[Al₄O₁₃] are formed by reaction of Na₂O and Al₂O₃ in a closed Ni-cylinder at 980 K. The compound is very sensitive against moisture. Na₁₄[Al₄O₁₃] crystalizes in the monoclinic space group P2₁/c with 2 formula units (a = 599.7, b = 2704.0, c = 596.9 pm, β = 120.1°). The characteristic feature of the structure, the anion [Al₄O₁₃]^14?, is built of four AlO₄-tetrahedra, sharing vertices. The connection of these groups by the counter-cations is discussed.     

Na3[BN2] and Na2K[BN2]: A Known and a Novel Alkali Metal Dinitridoborate Obtained via Mild Thermal Dehydrogenation

Na₃[BN₂] and Na₂K[BN₂] were obtained as white polycrystalline powders from the reaction of the respective binary mixtures NaNH₂:NaBH₄ and NaNH₂:KBH₄ in molar ratio 2:1 at 873 K and 683 K, respectively, in an argon stream. According to the results of thermal analysis measurements, both compounds are thermally stable only up to 954 K (Na₃[BN₂]) and 712 K (Na₂K[BN₂]), respectively, decomposing under evolution of alkali metal and nitrogen to yield hexagonal BN as final residue, which was identified from powder patterns. The crystal structure of Na₃[BN₂] {β‐Li₃[BN₂] type; P2₁/c (No. 14); Z = 4} was confirmed and the unit cell parameters redetermined: a = 5.724(1) Å, b = 7.944(1) Å, c = 7.893(1) Å, β = 111.31(1)°. According to X‐ray powder data, Na₂K[BN₂] crystallizes isotypic to Na₂KCuO₂ in the tetragonal space group I4/mmm (No. 139) with a = 4.2359(1) Å, c = 10.3014(2) Å and Z = 2. The crystal structure of Na₂K[BN₂] is composed of linear [N–B–N]^3– anions centering elongated M₁₄ rhombic dodecahedra, which are formed by 8 sodium and 6 potassium atoms. The [BN₂]@Na_8/4K_6/6 polyhedra are stacked along [001] and condensed via common tetragonal faces to generate a space‐filling 3D arrangement. The B–N bond lengths for the strictly linear [N–B–N]^3– units are 1.357(4) Å. Vibrational spectra of the title compounds were measured and analyzed based on D_∞h symmetry of the relevant [N–B–N]^3– groups taking into account the site symmetry effects for Na₃[BN₂]. Both the wavenumbers, as well as the calculated valence force constants f(B–N) = 7.29 N · cm^–1 (Na₃[BN₂]) and 7.33 N · cm^–1 (Na₂K[BN₂]), respectively, are in good agreement with those of the known alkali and alkaline earth dinitridoborates.     

Oxydation intermetallischer Phasen: K4{Na2[Tl2O6]} aus NaTl und K2O2

Oxidation of Intermetallic Phases: K₄{Na₂[Tl₂O₆]} from NaTl and K₂O₂ The hitherto unknown K₄{Na₂[Tl₂O₆]} was prepared in form of transparent, yellow single crystals from NaTl and KO_1,08 (molar ratio 1:1.3; sealed Ag-cylinder; 450°C, 30 d). The structure determination (four-circle diffractometer, MoKα, 1 280 out of 1 523 I_o(hkl), R = 5.75%, R_w = 4.58%) confirms the space group P2₁/c with a = 641.3 pm, b = 691.1 pm, c = 1188.5 pm, β = 95.69° and Z = 2. As characteristic building units of the structure there are doubles of tetrahedra of [Tl₂O₆] and [Na₂O₆]. The compound is isotypic with Cs₆[In₂O₆] and Rb₆[Tl₂O₆]. The Madelung Part of Lattice Energy, MAPLE, the Mean Fictive Ionic Radii, MEFIR, Effective Coordination Numbers, ECoN, and Charge Distribution, CHARDI, are calculated.     

Zur Kenntnis des Natrium-tetrahydroxoaluminat-chlorids Na2[Al(OH)4]Cl

On the Sodium Tetrahydroxoaluminate Chloride Na₂[Al(OH)₄]Cl The hitherto unknown compound Na₂[Al(OH)₄]Cl was prepared by crystallisation from a NaCl containing sodium aluminate solution. According to the X-ray single crystal investigation (tetragonal, space group P4/nmm, a = 7.541 Å, c = 5.059 Å, Z = 2) the compound represents the first example of a crystalline hydroxoaluminate with monomeric [Al(OH)₄]^? anions. Cl^? shows a quadratic anti prismatic coordination to 4 Na⁺ and over hydrogen bonds to 4 O^2? while Na⁺ is octahedrally coordinated by 4 O^2? and 2 Cl^? (axial). The results of the crystal structure analysis are confirmed by ²⁷Al and ²³Na MAS NMR investigations. Na₂[Al(OH)₄]Cl decomposes at about 200°C without intermediates under formation of β-NaAlO₂ and NaCl.     

Zur Überwindung von Vorurteilen: Das erste basische Oxoindat,Na26O3[InO4]4

The First Basic Oxoindate: Na₂₆O₃[InO₄]₄ For the first time Na₂₆O₃[InO₄]₄ was obtained by annealing intimate mixtures of Na₂O, CdO and elemental In (molar ratio 3.5:1.0:2.0) in closed Ni-cylinders (30 days, 600°C) in form of yellow single crystals. The structure determination by four circle diffractometer data (MoKα, 921 out of 921 I_o(hkl), R = 2.53, R_w = 2.18%) confirms the space group 143d (cubic) with a = 1 427.37 pm and Z = 4. All kation are surrounded by tetrahedron of O^2?. In³⁺ is coordinated with O(1) and O(2) (without O(3)) only. There are ?isolated”? [InO₄]-tetrahedra. The Madelung Part of Lattice Energy, MAPLE, the Mean Fictive Ionic Radii, MEFIR, Effective Coordination Numbers, ECoN, and Charge Distribution, CHARDI, are calculated.     

Über quaternäre Oxowolframate (VI) Na6Li2[W2O10] - ein Diwolframat

On Quaternary Oxotungstates (VI). Na₆Li₂[W₂O₁₀] — a Ditungstate For the first time, Na₆Li₂[W₂O₁₀] has been prepared by annealing mixtures of WO₃, Na₂O and Li₂O with W:Na:Li = 1:3:1 [closed Pt-tube in quartz-glass ampoule, 840°C, 60 d (single crystals)]. The colourless crystals are of squatted shape. The structure determination [1813/I₀(h kl), four-cycle diffractometer PW 1100 (Fa. Philips), ω-scan, AgK_α, R = 8.32%, absorption not considered] confirms the space group P1 with a = 784.66(11), b = 602.53(7) c, = 563.81(11) pm α = 106.784(14)°, β = 114.548(14)°, γ = 91.082(13)°, Z = 2, d_x = 4.92 g · cm^?3, d^pyk = 4.85 g · cm^?3. The structure may be described as a distorted derivative of the NaCl-type. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated and discussed.     

Na4[PbO4] — Darstellung neuer Plumbate(IV) durch Oxydation intermetallischer Phasen

Na₄[PbO₄] — Preparation of new Plumbates(IV) by Oxidizing Intermetallic Phases By oxidizing NaPb with Na₂O₂ (molar ratio Na₂O₂:NaPb = 2.04:1; Ag-tubes; 600°C/50d) we obtained for the first time small orange coloured single crystals of Na₄[PbO₄]: Na₄[SiO₄]-type [2], P? 1 (I.T. No. 2) with a = 898.5(3); b = 675.6(3); c = 592.2(2) pm; α = 124.75(1)°; β = 96.75(1)°; γ = 100.18(2)°; Z = 2; (four circle diffractometer data (MoK; 3 251 I_o(hkl); R = 3.4%; R_w = 3.0%), parameters see text. Furthermore the Madelung part of lattice energy (MAPLE), effective coordination numbers (ECoN), mean fictive ionic radii (MEFIR) and the charge distribution (CHARDI) are being calculated.     

Hydroxoverbindungen. 10. Über die Natriumoxohydroxostannate(II) Na4[Sn4O(OH)10] und Na2[Sn2O(OH)4]

Hydroxo Compounds. 10. The Sodium Oxohydroxostannates(II) Na₄[Sn₄O(OH)₁₀] and Na₂[Sn₂O(OH)₄] Na₄[Sn₄O(OH)₁₀] = Na₄[Sn(OH)₃]₂[Sn₂O(OH)₄] ( I ) and Na₂[Sn₂O(OH)₄] ( II ) have now been doubtlessly characterized as the first Na-hydroxostannates(II). I crystallizes monoclinic in P2₁/n (a = 1522.4(5) pm, b = 830.0(2) pm, c = 1276.0(3) pm, β = 104.8(2)°, Z = 4, R = 0.047, 1137 I_hkl); II crystallizes orthorhombic in P2₁2₁2₁ (a = 1450(2) pm, b = 1665(2) pm, c = 590.7(8) pm, Z = 8, R = 0.042, 1208 I_hkl). II is identical with the compound which was described up to now as “Na[Sn(OH)₃]”. The new compounds contain the complex anions [Sn(OH)₃]^? and [Sn₂O(OH)₄]^2?, whose structures are now proved. The oxotetrahydroxo-distannate(II) anion [Sn₂O(OH)₄]^2? exhibits a syn-conformation with respect to the projection along the (Sn? Sn) vector. The two compounds crystallize with pronounced layer structures, which show direct topotactical relations with one another as well as with SnO. This relates closely to the fast formation of SnO from crystals of I and II .     

Neue Oxoferrate(III). Na2Li3[FeO4] und K2Li3[FeO4]

New Oxoferrates (III). Na₂Li₃[FeO₄] and K₂Li₃[FeO₄] . Na₂Li₃[FeO₄] and K₂Li₃[FeO₄] (transparent, pink or light yellow single crystals) have been prepared by heating mixtures of the oxides (Na:Li:Fe = 2.2:3.3:1; Ag-tube, 720°C, 27 d or K:Li:Fe = 2.2:3.3:1; analogous, 700°C, 40 d). Na₂Li₃[FeO₄] is isotypic with Na₂Li₃[GaO₄] (a = 832.2(1), b = 796.0(1), c = 656.3(1)pm, Pnnm) and K₂Li₃[FeO₄] with K₂Li₃[GaO₄] (a = 557.7(1), b = 880.6(1), c = 1101.8(2)pm, β = 111.51(2)°, P2₁/c). Four cycle diffractometer data: MoK_α, 525 out of 686 I₀(hkl), R = 9.36%, R_w = 5.97% or 1424 out of 1424 I₀(hkl), R = 8.45%, R_w = 5.66%. Parameters see text. The structures are characterized by calculations of the Madelung Part of Lattice Energy, MAPLE. The Effective Coordination Numbers, ECoN, which are calculated by means of Mean Fictive Ionic Radii, MEFIR, are compared with the analogous gallates.     

Synthesis,Crystal Structure,and Spectroscopic Characterization of Na5[NiO2][CO3], containing the Linear [NiO2]3– Group with Monovalent Nickel

For the first time ruby‐red single crystals and powder samples of Na₅[NiO₂][CO₃] were obtained via a redox reaction between nickel metal and CdO in the presence of Na₂O and Na₂CO₃ (molar ratios of CdO : Na₂O : Na₂CO₃ equal 1 : 3 : 2). The crystal structure has been refined from single crystal X‐ray diffraction data at 170 K (tetragonal, P4/mmm, a = 462.7(1) pm, c = 830.5(2) pm) and at 293 K (a = 462.35(7) pm, c = 830.9(1) pm). Na₅[NiO₂][CO₃] is the first example of an alkaline‐rich transition metal oxide with two different oxoanions, [NiO₂]^3– and [CO₃]^2–, coexisting in one compound. The electronic spectrum of Na₅[NiO₂][CO₃] has been measured between 4000 and 25000 cm^–1. Two d‐d‐transitions of the linear [NiO₂]^3– complex (d⁹) are observed at 5870 cm^–1 and 11850 cm^–1 and analysed using the angular overlap model. MIR and FIR spectra give evidence for the [CO₃]^2– anion present in the structure.     

Preparation,Structure and Properties of the One-Dimensional Polymeric Complex Na2[AlW3O4(O2CEt)8]2

Abstract

The heterometallic polymeric cluster Na₂[AlW₃O₄ (O₂CEt)₈]₂ (1) has been prepared by reaction of W(CO)₆ and NaWO₄·2H₂O with AlCl₃ at 120°C in propionic anhydride and characterized by X-ray crystallography, with the following crystal data: triclinic, space group P1, a = 12.205(5), b = 13.032(4), c = 13.925(3) Å, α = 90.21(3)°, β = 109.53(5)°, γ = 117.26(6)°, V = 1822.8(1)ų, Z = 1, R = 0.038 and R_w = 0.101. The structure consists of two triangular [W₃O₄(O₂CEt)₈]^4? cluster unit, which act as polydenate ligands to link Al³⁺ and Na⁺ ions forming a one–dimensional chain structure. IR spectra show characteristic [W₃O₄]⁴⁺ bands at 746–815 cm^?1. Thermal analysis reveals that the complex is air stable up to 250°C. Cluster 1 decomposes in hot aqueous 2 M HCl solution to produce discrete [W₃O₄]⁴⁺ units.     

Synthesis,characterization and X-ray structure of one-dimensional polymeric complexes with triangular molybdenum clusters as building blocks: Na2Ga2[Mo3O4(O2CEt)8]2 and Na2AlGa[Mo3O4(O2CEt)8]2

The heterometallic polymeric cluster complexes Na₂Ga₂[Mo₃O₄(O₂CEt)₈]₂ (1) and Na₂AlGa[Mo₃O₄(O₂CEt)₈]₂ (2) have been prepared by reaction of Mo(CO)₆, NaMoO₄·2H₂O with GaCl₃ and a mixture of AlCl₃ and GaCl₃ (1:1 molar ratio), respectively, in heated propionic anhydride and characterized by X-ray crystallography. The structures are isostructural and each consists of two triangular propionate cluster units [Mo₃O₄(O₂CEt)₈]⁴⁻, which act as polydentate ligands to link trivalent heterometal and sodium ions forming one-dimensional chain structures. Both clusters decompose in 2 M HCl at room temperature to produce discrete [Mo₃O₄]⁴⁺ cluster units. Thermal analysis of 1 reveals that the complex is air stable up to 250°C. IR spectra show the characteristic bands of [Mo₃O₄]⁴⁺ cores at 745–812 cm⁻¹.     

Ein neuer Perowskit mit Lücken im Anionenteil: Ba4[Na2W2O11]

A New Perowskite with Deficiencies in the Oxygen Part: Ba₄[Na₂W₂O₁₁] For the first time colourless single crystals of Ba₂NaWO_5.5 were prepared by reaction of Na₄WO₅ [2] and ?BaO₂”? [Ba:Na:W = 4:4:1, Ni-cylinder, 725°C, 35 d]. Single crystal data [432 of 505 I₀ (hkl), Four-circle-diffractometer Siemens AED2, MoKα , R = 6.1%, R_w = 5,6%] verify the space group P mmm with a = 579.16(8), b = 580.85(8), c = 859.4(1) pm, Z = 1. The structure is based upon the CaTiO₃-type of structure. Ba²⁺ take the place of Ca²⁺ meanwhile Ti⁴⁺ is substituted alternately by W⁶⁺ and Na⁺. Complete occupation of all lattice positions would lead to a deficite of positive charge. This is compensate by deficiencies in the oxygen part of the lattice. Related to [Na(1)₁Na(2)₁W(1)₁W(2)₁O(1)₄O(2)₂O(3)₂O(4)₃] these deficiencies are statistically distributed on O(4). Structural relations are deduced by Schlegel-Diagrams. The Madelung Part of Lattice Energie, MAPLE, Effektive Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated and discussed.