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.     

Das erste Oxocuprat(I) mit hantelförmigem Anion: KNa2[CuO2]

The First Oxocuprate(I) with Dumb-bell-like Anion: KNa₂[CuO₂] For the first time KNa₂[CuO₂] was prepared in transparent, dark yellow single crystals from KO_0.48 NaO_0.50 and Cu₂O (sealed cu-cylinders, 680°C, 30 d). The crystal structure, I 4mm, with a = 432.7(3), c = 1089.1(5) pm, Z = 2, D_x = 2.94 g/cm³, D_pyk = 2.89 g/cm³ was solved (four-circle-diffractometer PW 1100, 347 I₀ (hkl), MoKα; R = 0.073, R_x = 0.069). The structure of KNa₂[CuO₂] may be regarded as a “stuffed derivative” of XeF₂ with dumb-bell-like [CuO₂] units. The C.N. of the two crystallographically independent O^2? are 6 and 9, respectively. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated.     

Ein neues Inoferrat(III): K2 Na4[(FeO3)2]

A New Inoferrate(III): K₂Na₄[(FeO₃)₂] For the first time amber coloured single crystals of K₂Na₄[(FeO₃)₂] were prepared by heating well ground mixtures of KFeO₂ and Na₂O (molar ratio Na₂O:KFeO₂= 1.4:1.0; ?Ag-tube”?, 500 °C/29 d, 400 °C/5 d): Spacegroup Pnma with a = 650.50(6) pm, b = 619.62(5) pm, c = 1020.64(12) pm. K₂Na₄[(FeO₃)₂] is isotypic to K₂Na₄[(GaO₃)₂] [2]. The structure has been determined by four-circle-diffractometer data [Mo—Kα , 982 of 982 unique I₀(hkl), R = 4.56%, R_w = 4.56% (no weight)]; parameters as given in the text. The Madelung Part of Lattice Energy, MAPLE, and the Effective Coordination Number, ECoN, these via Mean Fictive Ionic Radii, MEFIR will be 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.     

Ein neues Oxomanganat(II): K2Mn2O3

A New Oxomanganate(II): K₂Mn₂O₃ For the first time K₂Mn₂O₃ has been prepared from the binary oxides as orangecoloured powder and single crystals. Space group P2₁/c with a = 5.992, b = 6.454, c = 6.374 Å, β = 113.9°, Z = 2; four-circle-diffractometer data, 872 of 897 I₀(hkl), R = 6.09%, R_W = 4.21%, MoKα. K₂Mn₂O₃ is isotypic with K₂Cd₂O₃. The crystal structure, Effective Coordination Numbers, ECoN, as well as the Madelung Part of Lattice Energy, MAPLE, are discussed.     

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.     

Ein neues Periodat Zum Aufbau von K9Li3I2O13 = K9Li3O[IO6]2

A Novel Periodate: On the Structure of K₉Li₃I₂O₁₃ = K₉Li₃O[IO₆]₂ New obtained are weakly dichroitic (pale yellow/bluish) single crystals of K₉Li₃I₂O₁₃ by reaction of KIO₄, K₂O, and Li₂O (KIO₄:K₂O:Li₂O = 1:1:1.5; 800°C, 42 d). Space group P62c, Z = 2, a = 954.9 pm, c = 1172.2 pm, R = 6.2%, Rw = 5.6%, 957 symmetry independend I₀(hkl), MoKα . Characteristic for this structure are ?isolated”? O^2? and octahedral groups [IO₆]. The crystal structure has been determind. The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed.     

Ein neues Oxoiridat(V): KLi6[IrO6]

A New Oxoiridate(V): KLi₆[IrO₆] Hitherto unknown Kli₆[IrO₆] has been prepared by completely pulverized mixtures of K₄[IrO₄] and Li₂O (closed silver cylinder, 30 d, 750°C). The deep dark red single crystals are trigonal-rhombohedral, space group R3 m, a = 819.61(8) pm, c = 709.96(11) pm, Z = 3. It is a “stuffed” variant of the α-Li₆[UO₆]-type; four-circle diffractometer data (PW 1100), R = 1.44% and R_w = 1.41% for 220 I₀(h kl), MoKα. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, the latter derived from mean Fictive Ionic Radii, MEFIR, are calculated and discussed.     

Das erste Oxoferrat(I): Zur Konstitution von K3[FeO2] und K3[NiO2]

The First Oxoferrate(I): On the Constitution of K₃[FeO₂] and K₃[NiO₂] Garnet-red single crystals of K₃[FeO₂] were obtained for the first time by heating intimate mixtures of K₆[CdO₄] and CdO (molar ratio 1:1.16) in closed Fe-cylinders at 450°C during 40 d. The same way of preparation via “reaction with the cylinder surface” was applied to prepare similarly coloured single crystals of K₃[NiO₂] (K₆CdO₄ in closed Ni-cylinders at 500°C during 49 d). The structure determination by four circle diffractometer data (MoKα , K₃[FeO₂]: 731 out of 731 I_o(hkl), R = 5.76%, R_w = 5.33%, K₃[NiO₂]: 755 out of 755 I_o(hkl), R = 8.70%, R_w = 4.25%) confirms the space groups P 4₁2₁2 and P 4₃2₁2, respectively. K₃[FeO₂]: a = 604.2(2) pm, c = 1 402.7(3) pm, Z = 4 K₃[NiO₂]: a = 603.6(1) pm, c = 1 405.2(2) pm, Z = 4. (powder data, standard deviations in parentheses) Essential feature of the structure are the dumb-bell-like anions [O? M? O]^3? (M = Fe, Ni). Their arrangement corresponds to a stuffed derivative of the KrF₂-type. Magnetic properties of K₃[FeO₂] were determined and cover the monovalence of Fe. MAPLE-calculations reveal the strong coincidence of monovalent VIIIb-cations.     

Oxocuprate(I) mit CO2-analogem Anion: Rb3[CuO2] [1]; (3. Mitteilung)

Inhaltsübersicht. Rb₃[CuO₂] wurde als dunkelgelbes Pulver bzw. erstmals in Form transparenter gelber, blockförmiger Einkristalle durch Tempern der binären Oxide (RbO_0,63/Cu₂O, Rb: Cu = 3,1:1 [Pulver] bzw. 4,2:1 [Einkristalle]) hergestellt (geschlossene Cu-Bömbchen, 600°C/10 d, bzw. 560°C/14 d, dann langsam abgekühlt). Nach Strukturaufklärung (a = 930,9(1); b = 966,8(2); c = 675,5(1) pm, β = 110,1(1)°, P2₁/n–C⁵_2h, Z = 4, Vierkreisdiffraktometer AED2, MoKα, 1409 von 1573 I_o(hkl), R = 14,6%, R_w = 10,0%) liegt ein neuer Strukturtyp vor (Parameter siehe Text). Strukturcharakteristisch sind die CO₂-analogen Hanteln [O–Cu–O] mit d(Cu–O) = 177 pm. Die Struktur wird beschrieben. Der Madelunganteil der Gitterenergie, MAPLE, effektive Koordinationszahlen, ECoN, diese über mittlere fiktive Ionenradien, MEFIR, werden berechnet und diskutiert. Oxocuprates(I) with CO₂-analogues Anions: Rb₃[CuO₂] (3^rd Communication) For the first time Rb₃[CuO₂] was prepared as dark yellow powder resp. yellow single crystals from the binary oxides (RbO_0.63/Cu₂O, Rb: Cu = 3.1:1 [powder] resp. 4.2:1 [single crystals], sealed Cu-cylinders). The crystal structure (a = 930.9(1); b = 966.8(2); c = 675.5(1) pm, β = 110.1(1)°, P2₁/n–C⁵_2h, Z = 4, four circle diffractometer AED2, 1409 out of 1573 I_o(hkl), R = 14.6%, R_w = 10.0%) was solved. The characteristic element is the CO₂-analogues group [O–Cu–O] with d(Cu–O) = 177 pm. The structure is described. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated and discussed.     

[Cl3Cu(I)-As(III)O3]: Ein kristallchemisch neues Bauelement in der Struktur des Pb6Cu(AsO3)2Cl7

The synthetic compound Pb₆Cu(AsO₃)₂Cl₇ crystallizes in space group R witha ₀=9.8614(4),c ₀=17.089(2)Å,Z=3. The crystal structure, determined by single crystal X-ray work, is a typical layer structure. Complex Pb₆(AsO₃)₂Cl₆ layers are combined via monovalent Cu and Cl atoms. A novel element within the structure is a [Cl₃Cu(I)-As(III)O₃] group with the interatomic distances (Å): Cu-Cl=2.44 (3×), As-O=1.76 (3×), Cu-As=2.34 (1×).

     

Ein neues Oxozincat: Li6[ZnO4] [1]

A New Oxozincate: Li₆[ZnO₄] Colourless single crystals of Li₆[ZnO₄] are formed by reaction of Li₂O and ZnO [(Li₂O:ZnO = 3.3:1, 700°C 50 d), Space group P4₂/nmc, Z = 2, a = 652.76 pm, c = 465.09 pm R = 2.6%, Rw = 2.1%, 173 symmetry independend I₀(hkl), MoK]. The crystal structure has been determined.     

Ein neues Oxotantalat(V): Über KLi6[TaO6] [1]

A New Oxotantalate(V): On KLi₆[TaO₆] [1] For the first time hitherto unknown KLi₆[TaO₆] was obtained by intimately pulverized mixtures of K₂O, Li₂O and Ta₂O₅ (molar ratio K:Li:Ta = 1.1:6.6:1) in a closed Ni-cylinder (800°C, 30 d) in form of colourless single crystals; trigonal-rhomboedral (space group R3 m) with a = 822.6(1) pm, c = 721.2(1) pm (Guinier-Simonpowder data), Z = 3. The determination of the crystal structure (four cycle diffractometer data, 224 out of 224 I₀ (hkl), R = 1.80%, R_w = 1.79%, absorption not considered) proves that KLi₆[TaO₆] is isotypic with KLi₆[IrO₆], a stuffed derivative of the α-Li₆[UO₆] structure type. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, the latter derived from Mean Effective Ionic Radii, MEFIR, as well as the Charge Distribution, CHARDI, are calculated and discussed.     

Ein neues Oxomanganat(II): KLiMnO2

A New Oxomanganate (II): KLiMnO₂ For the first time, KLiMnO₂ has been prepared from the binary oxides (640°C, 17 d, Ni? or Ag-cylinders) in form of orange-coloured single crystals. The crystal structure (a = 11.085, b = 3.389, c = 8.357 Å, β = 120.67°, Space-Group C2/m, 4-circlediffractometer, MoK_α, 458 I₀ (hkl), R = 4.87%) corresponds to that of KLiZnO₂. Both oxides represent a new formula type A[(TO)_n] with n = 2 and K^[7] Li^[4] Mn^[4] O₂. Effective Coordination Numbers, ECoN, and the Madelung Part of Lattice Energy, MAPLE, are calculated and discussed.     

Potassium thiocyanate argentates: K3[Ag(SCN)4], K4[Ag2(SCN)6] and K[Ag(SCN)2]

The anions of the title compounds contain [Ag(SCN)₄] units, with the S atoms coordinating to Ag⁺ in a tetrahedral arrangement. Whereas in the isolated anions of tripotassium tetra­thio­cyanatoargentate(I), K₃[Ag(SCN)₄], (I), all SCN^? groups are bonded as terminal ligands, in tetrapotassium di‐μ‐thio­cyanato‐S:S‐bis­[dithio­cyanato­argentate(I)], K₄[Ag₂(SCN)₆], (II), two AgS₄ tetrahedra share one common edge. In poly[potassium [argentate(I)‐di‐μ‐thio­cyanato‐S:S]], K[Ag(SCN)₂], (III), edge‐ and vertex‐sharing of AgS₄ tetrahedra results in infinite [Ag(SCN)₂]^? layers.     

Die IR-Spektren von [Cr(O2)2(NH3)3] und K3[Cr(O2)2(CN)3]

The infrared spectra of the title compounds are reported and discussed. The influence of the peroxide groups on the bond properties of the other ligands and some characteristics of the metal—peroxide interactions are analyzed.