Das neue Orthotitanat CsNa3[TiO4]

The New Orthotitanate CsNa₃[TiO₄] Colourless, square stonelike single crystals of CsNa₃[TiO₄] [1], isostructural with CsNa₃[PbO₄] [2], are obtained by heating a well grounded mixture of the binary oxides CsO_0,56, NaO_0,52 and TiO₂ (Cs : Na : Ti = 1,1:3,1:1,0) in Nitubes (9d, 400°C). The structure determination by using four-circle diffactometer data (Siemens AED2, 5541 I_o(hkl), MoK) leads to the residual-values R = 8.8% and R_w = 4.7%. Lattice constants (triclinic, Cmca, P1 , Z = 4, four-circle diffactometer data, MoK: a = 1161.2(6) pm, b = 854.9(3) pm, c = 651.1(3) pm, α = 100.52(2)°, β = 108.84(3)°, γ = 91.61(3)°; additional data see text). The Madelung Part of Lattice Energy (MAPLE), Effective Coordination Numbers (ECoN), Mean Fictive Ionic Radii (MEFIR) and the Charge Distribution in Solids (CHARDI) are calculated and discussed.     

Unerwartete Strukturverwandtschaft: Das neue Orthotitanat Rb3Na[TiO4]

On Unexpected Structural Relations: The New Orthotitanate Rb₃Na[TiO₄] [1] The new oxide Rb₃Na[TiO₄], platelike colourless crystals, was obtained by heating a well grounded mixture of the binary oxides in Ni-tubes. Therewith the oxides RbO_0.52, NaO_1.03, Ti₂O₃ (Rb:Na:Ti = 2.8:2.5:1.0) were heated for 26 d at 1000°C. Rb₃Na[TiO₄] (monoclinic, P2₁/c) is “isostructural” with Rb₃Na[PbO₄] [2] (lattice constants: a = 1076.3(3) pm, b = 638.8(4) pm, c = 1088.9(7) pm, β = 112.83(12)°; four-circle diffractometer data, Z = 4). The structure was determinated by using four-circle diffractometer data (Siemens AED2, 6683 I₀(hkl), MoKα , R = 6.2%, R_w = 3.8%, additional data see text). The Madelung Part of Lattice Energy (MAPLE), Effective Coordination Numbers (ECoN), Mean Fictive Ionic Radii (MEFIR) and the Charge Distribution in Solids are calculated and 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 einfaches Titanat: KNaTiO3

A New Simple Titanate: KNaTiO₃ KNaTiO₃, the first titanate containing different alkaline metals, was prepared by annealing mixtures of Na₂O, K₂O, and TiO₂ (Na: K: Ti = 1.0: 1.0: 1.0) in closed Ni cylinders for 10 days at 900°C. The compound forms colourless crystals of monoclinic symmetry (C2/c) with a = 5.7960(16), b = 10.9608(20), c = 5.4735(15) Å, β = 97.36(2)°, Z = 4, which are sensitive to moisture. The compound adopts a new type of structure (data were collected on a four-circle diffractometer, R = 5.15%, R_w = 4.69%) in which Ti⁴⁺ as well as Na⁺ form infinite chains of square pyramids TiO₅ and NaO₅, resp. K⁺ has the coordination number 8. Structural characteristics are discussed in connection with calculations of the Madelung part of lattice energy, MAPLE, Effective Coordination numbers, ECoN, and Mean Fictive Ionic Radii, MEFIR.     

Darstellung,Kristallstruktur und Eigenschaften von Cäsiumozonid

Synthesis, Crystal Structure and Properties of Cesium Ozonide By reaction between CsO₂ and mixtures of O₂ and O₃ in the temperature range from 25°C to ?70°C and subsequent extraction with liquid ammonia pure CsO₃ was obtained in grammeamounts. By X-ray powder and thermal techniques a reversible, structural phase transition was detected at +8°C, and decomposition into CsO₂ and O₂ at +53°C. The low-temperature form (T? CsO₃) is isostructural to RbO₃ (P2₁/c; a = 675.1(2), c = 901.5(3) pm, β = 120.74(3)°l Z = 4), the crystal structure of H? CsO₃, which shows orientational disorder with respect to the ozonide ion, corresponds to the CsCl-type of structure (a = 436.06(3) pm). Using the geometry as determined for KO₃ and RbO₃, and the vibrational frequencies of different isotopomeres, the force constants of O₃^? have been redetermined.     

Ein „Lithosilicat”︁ mit Kolumnareinheiten: RbLi5{Li[SiO4]}2

A “Lithosilicate” with Columnar Units: RbLi₅{Li[SiO₄]}₂ In order to prepare RbLi₃[SiO₄] single crystals of RbLi₅{Li[SiO₄]}₂ have been obtained for the first time by heating of a well ground mixture of the binary oxides RbO_0.68, LiO_0.5 and SiO₂ [Rb:Li:Si = 1.1:3.0:1.0; 600°C; 21 d] in tightly closed Ni tubes. The new “lithosilicate” crystallizes monoclinic (space group C2/m with a = 1563.1(2) pm, b = 635.4(1) pm, c = 776.3(1) pm, β = 90.53(1)°, Guinier-Simon powder data). The crystal structure was determined by four-cycle diffractometer data [Philips PW 1100, 1237 from 1609 I_o(hkl), Z = 4, R = 9.2%, R_w = 8.3%], parameters see text. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, have been calculated.     

Was heißt eigentlich Festkörper??. Neue molekulare Aspekte am Beispiel Rb2[TiO3] [1], [2]

What does Solid State Mean?. New Molecular Aspects on the Example of Rb₂[TiO₃] [1], [2] Rb₂TiO₃ [3], parent type of the oxides K₂CoO₃, Rb₂CoO₃ and Cs₂CoO₃ [4], colourless crystals, needles, was newly obtained by heating a well grounded mixture of the binary oxides RbO_0.98, RbO_0.52, Ti₂O₃ (molar ratio = 2.4:6.2:1.0) 41 d at 780°C in Ni-Tubes. The first structure determination by using four-circle diffractometer data (Siemens AED2, 5366 I_o(hkl), MoKα ) leads to the residual-values R = 7.9% and Rw = 3.7%. Lattice constants (orthorhombic, Cmca, Z = 8, Guinier-Simon-data, CuKα₁): a = 596.5(1) pm, b = 1185.2(1) pm, c = 1326.6(1) pm (additional data see text). The structure determination 1974 by filmdata is confirmed. The Madelung Part of Lattice Energy (MAPLE), Effective Coordination Numbers (ECoN), Mean Fictive Ionic Radii (MEFIR) and the Charge Distribution in Solids (CHARDI) are calculated and discussed.     

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.     

Oxometallate neuen Typs: Über Ba3NaNbO6 und Ba3NaTaO6

Oxometallates of a new Type: On Ba₃NaNbO₆ and Ba₃NaTaO₆ For the first time in form of colourless, transparent single crystals of Ba₃NaNbO₆ [annealed mixtures of BaO, Na₂O and Nb₂O₅, Ba : Na : Nb = 3.3 : 1.1 : 1, Ni-cylinder, 1100°C, 3d] as well as Ba₃NaTaO₆ [annealed mixtures of BaO, Na₂O and Ta₂O₅, Ba : Na : Ta = 3.3 : 1.1 : 1, Ni-cylinder, 1100°C, 3d] have been prepared. The crystal structure was solved by fourcycle-diffractometer data [Ba₃NaNbO₆: Mo? Kα , 356 out 356 I₀ (hkl), space group R3 c with a = 1026.6(1)pm, c = 1195.3(2)pm (Guinier-Simon powder data), Z = 6, R = 2.4%, R_w = 2.0% and Ba₃NaTaO₆: Ag? Kα , 498 out of 498 I₀ (hkl), space group R3 c with a = 1027.6(1)pm, c = 1196.0(2)pm (Guinier-Simon powder data), Z = 6, R = 4.9%, R_w = 4.4%], parameters see text. The Ba₃M part of structure (M = Nb, Ta) corresponds to a slightly (hexagonal) deformed Nb₃Al arrangement with Na inserted along [001] between adjacent M^v, which are nearly perfectly octahedrally surrounded by 6 O. The structural relations are deduced by Schlegel Diagrams. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, the latter derived from Mean Effective Ionic Radii, MEFIR, as well as Charge Distribution, CHARDI, are calculated.     

Ein Oxostannat neuen Strukturtyps: Cs4[SnO4]

An Oxostannate of a New Structure Type: Cs₄[SnO₄] In order to prepare Cs₃LiSnO₄ by heating of a well ground mixture of the binary oxides [CsO_0.67, Li₂O, SnO₂; Cs:Li:Sn = 3.3:1.0:1.0; 450°C; 28 d; Ni-tube] colourless, monoclinic single crystals of Cs₄[SnO₄] have been yielded for the first time: space group P2₁/c with a = 1180.8 pm. b = 728.2 pm, c = 1166,7 pm, β = 111.79°, Z = 4. The crystal structure was solved by fourcycle-diffractometer data [Siemens AED2, 2299 from 2708 I₀(hkl), R = 7.0%, R_w = 5.6%], parameters see text. Characteristic for the complicated structure are “isolated” [SnO₄]^4? tetrahedra. Mean Fictive Ionic Radii, MEFIR, Effective Coordination Numbers, ECoN and the Madelung Part of Lattice Energy, MAPLE, have been calculated.     

Synthese und Kristallstruktur von Cs3AuO2

Synthesis and Crystal Structure of Cs₃AuO₂ Bright orange single crystals of Cs₃AuO₂, sensitive to moisture and atmosphere, are obtained by reacting CsAu with a 1 : 1 molar mixture of Cs₂O and CsO₂ (CsAu : Cs₂O : CsO₂ = 3 : 2 : 2) in sealed silver crucibles under argon atmosphere at 380 °C for a period of 6 days. The crystal structure (Pearsoncode mP72, P2₁/n, a = 1019.6(3), b = 1984.3(7), c = 1028.5(4) pm, β = 93.96(1)°, Z = 12, 2562 reflections mit I_o > 2σ(I), R₁ = 0.0662, wR₂ = 0.1660) is characterized by the presence of dumb‐bell‐shaped [O–Au–O]‐moieties (d(Au–O) = 200,8(2) pm), a common feature of oxoaurates(I).     

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.     

Neue Silicate mit „Stuffed Pyrgoms”︁: CsKNaLi9{Li[SiO4]}4, CsKNa2Li8{Li[SiO4]}4, RbNa3Li8{Li[SiO4]}4 [1] und RbNaLi4{Li[SiO4]}2 [2]

More Silicates with ?Stuffed Pyrgoms”?: CsKNaLi₉{Li[SiO₄]}₄, CsKNa₂Li₈{Li[SiO₄]}₄, RbNa₃Li₈{Li[SiO₄]}₄ [1] and RbNaLi₄{Li[SiO₄]}₂ [2] Single crystals of the new silicates CsKNaLi₉{Li[SiO₄]}₄, CsKNa₂Li₈{Li[SiO₄]}₄, RbNa₃Li₈{Li[SiO₄]}₄ and RbNaLi₄{Li[SiO₄]}₂ as well as powder (Rb-containing compounds only) were obtained for the first time. The samples were prepared by heating well ground mixtures of the binary oxides in Ni and Ag tubes, respectively. The structure determination was carried out by four-circle diffractometer data (MoKα radiation; Siemens AED 2): CsKNaLi₉{Li[SiO₄]}₄: tetragonally prismatic crystals, light yellow; 726 I₀(hkl), R = 4.4%, R_w = 2.8%; a = 1 102.0(6), c = 637.9(5) pm; Z = 2; space group I4/m; 2 CsO_0.55 + Li₄TlO₄ + glas (560°C, 15 d). CsKNa₂Li₈{Li[SiO₄]}₄: tetragonally prismatic crystals, light yellow; 727 I₀(hkl), R = 4.4%, R_w = 2.6%; a = 1 103.5(7), c = 637.7(4) pm; Z = 2; space group I4/m; 1.1 CsO_0.61 + 1.1 KO_0.55 + 1.4 NaO_0.52 + 6.5 Li₂O + 4 SiO₂ (600°C, 60 d). RbNa₃Li₈{Li[SiO₄]}₄: tetragonally prismatic crystals, colourless; 600 I₀(hkl), R = 2.3%, R_w = 2.0%; a = 1 092.08(6), c = 632.76(4) pm; Z = 2; space group I4/m; 4 RbO_0.57 + 3 NaO_0.52 + 6.5 Li₂O + 4 SiO₂ (650°C, 63 d). RbNaLi₄{Li[SiO₄]}₂: monoclinic, ball-shaped, colourless; 1 224 I₀(hkl), R = 3.1%, R_w = 3.1%; a = 1 573.10(13), b = 630.48(5), c = 781.25(8) pm, b = 90.566(8)°; Z = 4; space group C2/m; 1.1 RbO_0.52 + 1.2 NaO_0.45 + 5 Li₂O + 4 SiO₂ (700°C, 40 d).     

Zum Aufbau von RbNa5Be8O11

On RbNa₅Be₈O₁₁ For the first time RbNa₅Be₈O₁₁ was obtained by annealing intimate mixtures of the binary oxides (Rb:Na:Be = 1.1:5.5:8, Ni-cylinder, 650°C, 21d). The compound crystallizes triclinic (P 1 ) with a = 1 063.4 pm, b = 645.6 pm, c = 948.8 pm, α = 110.2º, β = 114.9º, γ = 90.8º, Z = 2. The crystal structure was solved by four-circle-diffractometer data [Siemens AED2, 3099 I₀ (hkl), R = 5.1%, R_w = 3.8%]. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, are calculated.     

Die Kryolithstruktur von Na3ScF6 und die Oktaederkippung in isostrukturellen Natriumhexafluorometallaten Na3MF6

The Cryolite Structure of Na₃ScF₆ and the Tilting of Octahedra in Isostructural Sodium Hexafluorometallates Na₃MF₆ X-ray studies at single crystals of Na₃ScF₆ confirmed the monoclinic cryolite type structure of this compound: a = 559.5, b = 580.2, c = 811.6 pm, β = 90.72°, Z = 2, space group P2₁/n; R1 = 0.021 for 512 symmetry independent reflections. The octahedra of [ScF₆] (average Sc? F = 200.7 pm), as well as those of [NaF₆] (Na1? F = 229.1 pm) linked to them, are titled by about 20° with respect to the axes of the perovskite-like pseudocell. This tilting of octahedra is discussed in comparison with other cryolites and with orthorhombic perovskites NaMF₃; there results a correlation between tilt angle and tolerance factor t ? 0.88 of these compounds, the [NaF₈] coordination of which invariably exhibits a constant mean value of Na2? F = 231.5 ± 1 pm for the four shortest distances.     

Das erste „Lithovanadat”︁: K2{LiVO4}.

The First ?Lithovanadate”?: K₂{LiVO₄} By heating of well ground mixtures of the binary oxides [K₂O, Li₂O, V₂O₅, K:Li: V = 2.2:1.1:1.0; Ni-tube, 900°C, 46 d] colourless monoclinic single crystals of K₂[LiVO₄] have been prepared for the first time: space group C2/m; a = 835.7(1) pm, b = 774.5(1) pm, c = 753,3(1) pm, β = 90.23(1)°. The structure was determined by four-circle diffractometer data [MoKα, 1018 form 1262 I₀ (hkl), R = 8.65%, R_w = 5.67%], parameters see text. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, have been calculated.     

Über Cs2Li2[GeO4]

About Cs₂Li₂[GeO₄] By heating of a well-ground mixture of the binary oxides CsO_0.55, Li₂O and GeO₂ (Cs:Li:Ge=2,6:2,2:1; Ni-tube; 600 °C; 49d) we got single crystals of Cs₂Li₂[GeO₄] for the first time. Cs₂Li₂[GeO₄] is isotypic to Rb₂Li₂[MO₄] [M = Si, Ti, Ge] [2] and Cs₂Li₂[MO₄] (M = Si, Ti) [3]: according to this Cs₂Li₂[GeO₄] crystallizes triclinic, in the spacegroup P1 with a = 968.7(4) pm, b = 586.0(2) pm, c = 571.4(2) pm, α = 92.71(4)°, β = 110.95(3)° and γ = 94.34(4)° (Guinier-Simon data), Z = 2. The structure was determined by four-circle diffractometer data (Ag? K_α ; 2381 I_o(hkl); R = 8,4%; R_w = 5.0%), parameters see text. Further the Madelung Part of Lattice Energy (MAPLE), Effective Coordination Numbers (ECoN) and the Mean Fictive Ionic Radii (MEFIR), have been calculated.     

Zum Magnetischen Verhalten der Alkalimetallozonide KO3, RbO3 und CsO3

Magnetic Properties of the Alkali Metal Ozonides KO₃, RbO₃, and CsO₃ The magnetic susceptibilities of KO₃, RbO₃ and CsO₃ have been determined between 3.6 and 250 K. Above 50 K Curie-Weiss behaviour is observed. Magnetic moments of 1.74 μ_B (KO₃, CsO₃) and 1.80 μ_B (RbO₃) calculated from the Curie-Weiss straight lines correspond with spin-only moments expected for isolated O₃- species with one unpaired electron. The Weiss constants θ are — 34 K (KO₃), — 23 K (RbO)₃ and — 10 K (CsO₃). The low temperature behaviour of KO₃ and RbO₃ (broad maxima in susceptibility at 20 and 17 K, respectively, and minima at 6 K) is typical of systems which show with decreasing temperature low-dimensional antiferromagnetic and three-dimensional magnetic ordering. Inspecting the intermolecular distances between oxygen atoms the pathways of exchange interactions are discussed.     

Neue Beryllate der Alkalimetalle: Na6Be8O11

Novel Beryllates of the Alkali Metals: Na₆Be₈O₁₁ For the first time transparent, colourless single crystals of Na₆Be₈O₁₁ have been prepared (Na₂O/BeO; Na:Be = 6:8, Ni-tube; 650°, 14 d). The compound crystallizes triclinic (P1 ) with a = 532.1(1) pm, b = 642.4(2) pm, c = 839.1(2) pm, α = 101.7°, γ = 105.8°, Z = 2, d_x = 2.42 g/cm³, d_pyk=2.51 g/cm³. The crystal structure was solved by four-circle diffractometer data [Siemens AED 2, MoKα , R = 7.9%, R_w = 6.2%, 1429 I₀(hkl)]. Effektive Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated.     

Quaternäre Chloride des zweiwertigen Europiums mit dreiwertigen Übergangsmetallen: Synthese und Kristallstruktur von Na6Eu3M4Cl24 (M = Ti,V, Cr)

Quaternary Chlorides of Divalent Europium and Trivalent Transition Metal Ions: Synthesis and Crystal Structure of Na₆Eu₃M₄Cl₂₄ (M = Ti, V, Cr) The reaction of EuCl₂, NaCl and MCl₃ (M = Ti, V, Cr) yields the chlorides Na₆Eu₃M₄Cl₂₄. According to X‐ray single crystal investigations, their crystal structure is a variant of the monoclinic cryolite‐type structure. One crystallographic site is occupied by Na1 and Eu simultaneously. For charge compensation the Na2 site is not fully occupied. In Na₆Eu₃Ti₄Cl₂₄ (P2₁/n, Z = 1/2, a = 663.8(1) pm, b = 718.3(1) pm, c = 953.3(2) pm, β = 91.55(2)°, R_all = 0.0314), Na₆Eu₃V₄Cl₂₄ (P2₁/n, Z = 1/2, a = 660.4(1) pm, b = 715.8(1) pm, c = 946.5(2) pm, β = 91.41(2)°, R_all = 0.0313) and Na₆Eu₃Cr₄Cl₂₄ (P2₁/n, Z = 1/2, a = 654.8(1) pm, b = 706.5(1) pm, c = 945.4(2) pm, β = 91.07(2)°, R_all = 0.0368) the ratio of Na1 : Eu amounts to 5 : 3. The colours of the compounds, orange yellow for M = Ti, orange red for M = V and dark red for M = Cr, indicate electronic interactions between Eu²⁺ and M³⁺.