Polycations Stabilised by Borosulfates: [Au3Cl4][B(S2O7)2] and the One-Dimensional Metal [Au2Cl4][B(S2O7)2](SO3)

(SO₄)-rich silicate analogue borosulfates are able to stabilise cationic cluster-like and chain-like aggregates. Single crystals of [Au₃Cl₄][B(S₂O₇)₂] and [Au₂Cl₄][B(S₂O₇)₂](SO₃) were obtained by solvothermal reaction with SO₃, and the electronic properties were investigated by means of density functional theory–based calculations. [Au₃Cl₄][B(S₂O₇)₂] exhibits a cluster-like cation, and the cationic gold-chloride strands in [Au₂Cl₄][B(S₂O₇)₂](SO₃) are found to resemble one-dimensional metallic wires. This is confirmed by polarisation microscopy.     

The Unprecedented Tetrakis‐(disulfato)‐silicate Anion [Si(S2O7)4]4−, its Germanium Congener [Ge(S2O7)4]4−, and the Tris‐(disulfato)‐metallates [M(S2O7)3]2− (M=Si,Ge, Ti), Stabilized by Divalent Counter Cations B2+ (B=Sr,Ba, Pb)

The reaction of oleum (65 % SO₃) with the tetrachlorides of silicon, germanium, and titanium, respectively, led to the complex disulfates Sr₂[M(S₂O₇)₄] (M=Si, Ge), Ba[M(S₂O₇)₃] (M=Si, Ge, Ti) and Pb[M(S₂O₇)₃] (M=Ge, Ti) if strontium, barium, and lead were used as divalent counter cations. The strontium compounds exhibit the unique tetrakis‐(disulfato)‐metallate anions [M(S₂O₇)₄]^4? with the silicon and germanium atoms in octahedral coordination of two chelating and two monodentate disulfate groups. All of the other compounds display tris‐(disulfato)‐metallate anions [M(S₂O₇)₃]^2? with three chelating disulfate groups surrounding the M atoms. Thermoanalytical investigations on the germanium compounds Sr₂[Ge(S₂O₇)₄] and Ba[Ge(S₂O₇)₃] revealed their decomposition in multi‐step processes leading to a mixture of BSO₄ and BGe₄O₉ (B=Sr, Ba), while the thermal degradation of Pb[Ti(S₂O₇)₃] yields PbTiO₃. For selected examples, IR data are additionally presented.     

Synthesis and Characterization of the Chain Borosulfates (NH4)3[B(SO4)3] and Sr[B2(SO4)4]

Two new borosulfates were obtained either by an open vessel synthesis from sulfuric acid and B(OH)₃, yielding (NH₄)₃[B(SO₄)₃] or from solvothermal synthesis in oleum enriched sulfuric acid and B(OH)₃, yielding Sr[B₂(SO₄)₄]. (NH₄)₃[B(SO₄)₃] crystallizes homeotypic to K₃[B(SO₄)₃] in space group Ibca (Z = 8, a = 728.58(3) pm, b = 1470.84(7) pm, c = 2270.52(11) pm), comprising open branched vierer single chains {¹_∞[B(SO₄)₂(SO₄)_2/2]^3–}. Sr[B₂(SO₄)₄] crystallizes as an ordered variant of Pb[B₂(SO₄)₄] in space group Pnna (Z = 4, a = 1257.4(4) pm, b = 1242.1(4) pm, c = 731.9(2) pm), consisting of loop branched vierer single chains {¹_∞[B(SO₄)_4/2]^2–}. Vibrational spectroscopy confirms both refined structure models. Thermal analysis of the dried powders, showed a decomposition towards the binary and ternary components, whereas a thermal treatment in the presence of the mother liquor promotes a decomposition of Sr[B₂(SO₄)₄] towards Sr[B₂O(SO₄)₃].     

Ni[B2(SO4)4] and Co[B2(SO4)4]: Unveiling Systematic Trends in Phyllosilicate Analogue Borosulfates

Borosulfates are compounds analogous to silicates, with heteropolyanionic subunits of vertex-linked (SO₄)- and (BO₄)-tetrahedra. In contrast to the immense structural diversity of silicates, the number of borosulfates is yet very limited and the extent of their properties is still unknown. This is particularly true for representatives with phyllosilicate and tectosilicate analogue anionic substructures. Herein, we present Ni[B₂(SO₄)₄] and Co[B₂(SO₄)₄], two new borosulfates with phyllosilicate analogue topology. While the anionic subunits of both structures are homeotypic, the positions of the charge compensating cations differ significantly: Ni^II is located between the borosulfate layers, while Co^II—in contrast—is embedded within the layer. Detailed analysis of these two structures based on single-crystal X-ray diffraction, magnetochemical investigations, X-ray photoelectron spectroscopy, and quantum chemical calculations, unveiled the reasons for this finding. By in silico comparison with other divalent borosulfates, we uncovered systematic trends for phyllosilicate analogues leading to the prediction of new species.     

Coordination Chemistry of [Nb2(S2)2]4+ Clusters: Preparation and Crystal Structures of K4[Nb2(S2)2(C2O4)4] · 6 H2O and (NH4)6[Nb2(S2)2(C2O4)4](C2O4)

Bis(disulfido)bridged Nb^IV cluster oxalate complexes [Nb₂(S₂)₂(C₂O₄)₄]^4– were prepared by ligand substitution reaction from the aqua ion [Nb₂(μ‐S₂)₂(H₂O)₈]⁴⁺ and isolated as K₄[Nb₂(S₂)₂(C₂O₄)₄] · 6 H₂O ( 1 ), (NH₄)₆[Nb₂(S₂)₂(C₂O₄)₄](C₂O₄) ( 2 ) and Cs₄[Nb₂(S₂)₂(C₂O₄)₄] · 4 H₂O ( 3 ). The crystal structures of 1 and 2 were determined. The crystals of 1 belong to the space group P1, a = 720.94(7) pm, b = 983.64(10) pm, c = 1071.45(10) pm, α = 109.812(1)°, β = 91.586(2)°, γ = 105.257(2)°. The crystals of 2 are monoclinic, space group C2/c, a = 1567.9(2) pm, b = 1906.6(3) pm, c = 3000.9(4) pm, β = 95.502(2)°. The packing in 2 shows alternating layers of cluster anions and of ammonium/uncoordinated oxalates perpendicular to the [1 0 1] direction. Vibration spectra, electrochemistry and thermogravimetric properties of the complexes are also discussed.     

Cu[B2(SO4)4] and Cu[B(SO4)2(HSO4)]—Two Silicate Analogue Borosulfates Differing in their Dimensionality: A Comparative Study of Stability and Acidity

Borosulfates are an ever‐expanding class of compounds and the extent of their properties is still elusive. Herein, the first two copper borosulfates Cu[B₂(SO₄)₄] and Cu[B(SO₄)₂(HSO₄)] are presented, which are structurally related but show different dimensionalities in their substructure: While Cu[B₂(SO₄)₄] reveals an anionic chain, [B(SO₄)_4/2]^?, with both a twisted and a unique chair conformation of the B(SO₄)₂B subunits, Cu[B(SO₄)₂(HSO₄)] reveals isolated [B₂(SO₄)₄(HSO₄)₂]^4? anions showing exclusively a twisted conformation. The complex anion can figuratively be obtained as a cut‐out from the anionic chain by protons. Comparative DFT calculations based on magnetochemical measurements complement the experimental studies. Calculation of the pK_a values of the two conformers of the [B₂(SO₄)₄(HSO₄)₂]^4? anion revealed them to be more similar to silicic than to sulfuric acid, highlighting the close relationship to silicates.     

From Infinite Chains according to 1∞[Zr(S2O7)4/2] in Zr(S2O7)2 to the unprecedented [Zr(S2O7)4]4– Anion in Ag4[Zr(S2O7)4]

The reaction of ZrCl₄ with oleum (65 % SO₃) in the presence of Ag₂SO₄ at 250 °C yielded colorless single crystals of Zr(S₂O₇)₂ [orthorhombic, Pccn, Z = 4, a = 709.08(6) pm, b = 1442.2(2) pm, c = 942.23(9) pm, V = 963.5(2) × 10⁶ pm³]. Zr(S₂O₇)₂ shows Zr⁴⁺ ions in an eightfold distorted square antiprismatic coordination of oxygen atoms belonging to four chelating disulfate units. Each S₂O₇^2– ion is connected to a further Zr⁴⁺ ion leading to chains according to ¹_∞[Zr(S₂O₇)_4/2]. The same reaction at a temperature of 150 °C resulted in the formation of Ag₄[Zr(S₂O₇)₄] [monoclinic, C2/c, Z = 4, a = 1829.35(9) pm, b = 704.37(3) pm, c = 1999.1(1) pm, β = 117.844(2)°, V = 2277.6(2) × 10⁶ pm³]. Ag₄[Zr(S₂O₇)₄] exhibits the unprecedented [Zr(S₂O₇)₄]^4– anion, in which the central Zr⁴⁺ cation is coordinated by four chelating disulfate units. Thus, in Ag₄[Zr(S₂O₇)₄] the ¹_∞[[Zr(S₂O₇)_4/2] chains observed in Zr(S₂O₇)₂ are formally cut into pieces by the implementation of Ag⁺ ions.     

Sm4S3[Si2O7] und NaSm9S2[SiO4]6: Zwei Sulfidsilicate mit dreiwertigem Samarium

Sm₄S₃[Si₂O₇] and NaSm₉S₂[SiO₄]₆: Two Sulfide Silicates with Trivalent Samarium The sulfide silicates Sm₄S₃[Si₂O₇] and NaSm₉S₂[SiO₄]₆ are obtained as light yellow transparent crystals by the reaction of Sm, Sm₂O₃, S, and SiO₂ with fluxing SmCl₃ or NaCl, respectively, in suitable molar ratios in fused evacuated silica tubes (850 °C, 7 d). Tetragonal crystals of Sm₄S₃[Si₂O₇] (I4₁/amd; Z = 8; a = 1186.4(1); c = 1387.0(2) pm) with ecliptically conformed [Si₂O₇]^6–‐groups of corner sharing [SiO₄]‐tetrahedra are formed. These double tetrahedra as well the sulfide anions (S^2–) coordinate two crystallographically independent metal cations. They provide coordination numbers of 8 + 1 (5 S^2– and 3 + 1 O^2–) for Sm1 and 9 (3 S^2– and 6 O^2–) for Sm2. NaSm₉S₂[SiO₄]₆ crystallizes hexagonally (P6₃/m; Z = 1; a = 975.32(9); c = 676.46(7) pm) in a modified bromapatite‐type structure. The coordination spheres about the two crystallographically different Sm³⁺ cations are built up by oxygen atoms of the orthosilicate units ([SiO₄]^4–) and sulfide anions (S^2–). As a result, Sm1 and Sm2 have coordination numbers of 9 and 8, respectively. Na⁺ and (Sm1)³⁺ occupy the position 4 f in a molar ratio of 1 : 3 whereas the lower coordinated (Sm2)³⁺ occupies the 6 h position.     

Synthesis and Characterization of Gd2[Pt2(SO4)4(HSO4)2](HSO4)2

Red single crystals of Gd₂[Pt₂(SO₄)₄(HSO₄)₂](HSO₄)₂ (triclinic, , Z = 1, a = 844.02(9), b = 908.50(9), c = 939.49(8) pm, α = 107.73(1)°, β = 112.10(1)°, γ = 103.53(1)°) were obtained by the reaction of [Gd(NO₃)(H₂O)₇][PtCl₆]·4H₂O with sulfuric acid at 320 °C in a sealed glass ampoule. In the crystal structure, Pt₂ dumbbells are coordinated by four chelating sulfate groups and two monodentate hydrogensulfate ions. Two further HSO₄^? ions are not bonded to the Pt₂ dumbbell. The Gd³⁺ ions are eightfold coordinated by oxygen atoms. The IR data of Gd₂[Pt₂(SO₄)₄(HSO₄)₂](HSO₄)₂ are typical for these type of compounds. The thermal decomposition of the compound leads to elemental platinum and Gd₂O₃.     

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.     

Studies on synthesis, characterization and thermochemistry of Mg2[B2O4(OH)2]·H2O

A new magnesium borate Mg₂[B₂O₄(OH)₂]·H₂O has been synthesized by the method of phase transformation of double salt at hydrothermal condition and characterized by XRD, IR, TG and DSC. The enthalpy of solution of Mg₂[B₂O₄(OH)₂]·H₂O in 0.9764 mol L^–1 HCl was determined. With the incorporation of the enthalpies of solution of H₃BO₃ in HCl (aq), of MgO in (HCl+H₃BO₃) (aq), and the standard molar enthalpies of formation of MgO(s), H₃BO₃(s), and H₂O(l), the standard molar enthalpy of formation of –(3185.78±1.91) kJ mol^–1 of Mg₂[B₂O₄(OH)₂]·H₂O was obtained.This revised version was published online in November 2005 with corrections to the Cover Date.     

Reaktionen von Zinnchloriden mit Polysulfiden. Die Kristallstrukturen von (PPh4)2[SnCl2(S6)2], (PPh4)2[Sn4Cl4S5(S3)O] und (PPh4)2[SnCl6] · S8 · 2CH3CN

Reaction of Tin Chlorides with Polysulfides. Crystal Structures of (PPh₄)₂[SnCl₂(S₆)₂], (PPh₄)₂[Sn₄Cl₄S₅(S₃)O], and (PPh₄)₂[SnCl₆] · S₈ · 2CH₃CN . The reaction of PPh₄[SnCl₃] with Na₂S₄ in acetonitrile in the presence of small amounts of water yields (PPh₄)₂[Sn₄Cl₄S₅(S₃)O] and minor amounts of (PPh₄)₂[SnCl₂(S₆)₂], PPh₄Cl · 2S₈ and (PPh₄)₂[SnCl₆]. SnCl₄ is partially reduced by (PPh₄)₂S_x, PPh₄[SnCl₃] and (PPh₄)₂[SnCl₆] · S₈ · 2CH₃CN being produced. According to the X-ray crystal structure determination the [Sn₄Cl₄S₅(S₃)O]^2?-ion consists of an O atom that is coordinated by four Sn atoms which in turn are liked with one another by five single S atoms and one S₃ group. In the [SnCl₂(S₆)₂]^2?-ion the Sn atom is octahedrally coordinated by two Cl atoms in trans arrangement and by two chelating S₆ groups. Octahedral [SnCl₆]^2? ions and S₈ molecules in the crown conformation are present in (PPh₄)₄[SnCl₆] · S₈ · 2CH₃CN.     

Die Kristallstruktur des Tetragermanats K2Ba[Ge4O9]2

The crystal structure of the compound K₂Ba[Ge₄O₉]₂ has been determined by means of three-dimensional X-ray data resulting a finalR-value of 0.034. The lattice constants of the trigonal unit cell ( ) are:a=11.729 (I) andc=19.278 (3) Å. There is a close structural relationship to the tetragermanates K₂Ge₄O₉ and BaGe₄O₉. The new compound also consists of three-membered rings built up by [GeO₄] tetrahedra, which are linked by [GeO₆] octahedra forming a three-dimensional network.According to their powder diagrams the following compounds are isostructural to K₂Ba[Ge₄O₉]₂: Na₂Ba[Ge₄O₉]₂, Rb₂Ba[Ge₄O₉]₂, Na₂Sr[Ge₄O₉]₂ and K₂Sr[Ge₄O₉]₂.     

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。     

Bariumstannat‐Pulver durch hydrothermale Synthese und durch Thermolyse von Bariumzinn(IV)‐glykolaten. Synthese und Struktur von [Ba(C2H6O2)4][Sn(C2H4O2)3] und [Ba(C2H6O2)2][Sn(C2H4O2)3]·CH3OH

Barium Stannate Powders from Hydrothermal Synthesis and by Thermolysis of Barium‐Tin(IV)‐Glycolates. Synthesis and Structure of [Ba(C₂H₆O₂)₄][Sn(C₂H₄O₂)₃] and [Ba(C₂H₆O₂)₂][Sn(C₂H₄O₂)₃]·CH₃OH The hydrothermal reaction as well as the microwave assisted hydrothermal reaction of SnO₂·aq with barium hydroxide gives Ba[Sn(OH)₆] ( 1 ) as powder with bar like particles. Compound 1 of the same morphology can also be isolated from a hydrothermal reaction of [Ba(C₂H₆O₂)₄][Sn(C₂H₄O₂)₃] ( 3 ). The reaction of SnO₂·aq with Ba(OH)₂·8H₂O in ethylene glycol yields the glycolate [Ba(C₂H₆O₂)₄][Sn(C₂H₄O₂)₃] ( 3 ), which forms in methanol the solvate [Ba(C₂H₆O₂)₂][Sn(C₂H₄O₂)₃]·CH₃OH ( 4 ). Compounds 1 , 3 and 4 react at different temperatures to BaSnO₃ ( 2 ) consisting of powders with different morphologies; because of the grain size of the resulting powders compounds 3 and 4 are suitable as precursor for the fabrication of corresponding ceramics.     

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.     

Die kristallstruktur des kaliumtetragermanats K2[Ge4O9]

Zusammenfassung Die Kristallstruktur des Kaliumtetragermanats, K₂[Ge₄O₉], wurde mit Hilfe dreidimensionaler Röntgendaten bestimmt. K₂[Ge₄O₉] kristallisiert trigonal mit der Raumgruppe P033034c1 (Nr. 165) und den Gitterparametern:a=11.84 undc=9.80 Å. Die vorgeschlagene strukturchemische Beziehung zum Wadeit, K₂Zr[Si₃O₉], wird durch die Existenz tetraedrischer [Ge₃O₉]-Ringe, die über [GeO₆]-Oktaeder zu einem dreidimensionalen Gerüst verknüpft sind, bestätigt. Es wurden folgende mittlere Ge–O-Abstände gefunden: 1.762 (Tetraeder) und 1.886 Å (Oktaeder).

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The crystal structure of potassium tetragermanate K₂[Ge₄O₉]

The crystal structure of potassium tetragermanate K₂[Ge₄O₉] has been determined by means of three-dimensional x-ray data. K₂[Ge₄O₉] crystallizes trigonal with space group P033034c1 (No. 165) and lattice parametersa=11.84 andc=9.80 Å. The proposed structural relationship to wadeite K₂Zr[Si₃O₉] is confirmed by the existence of [Ge₃O₉] rings built by tetrahedra, which are linked by [GeO₆] octahedra forming a three-dimensional network. The mean Ge–O distances are found to be: 1.762 (tetrahedra) and 1.886 Å (octahedra).

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Mit 2 Abbildungen

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Herrn Prof. Dr.H. Nowotny in Verehrung gewidmet.     

Synthesis and X-ray and Spectral Study of the Compounds [Q4N]2[Fe2(S2O3)2(NO)4] (Q = Me,Et, n-Pr,n-Bu)

Iron nitrosyl complexes with general formula [Q₄N]₂[Fe₂(S₂O₃)₂(NO)₄] (Q = Me, Et, n-Pr, n-Bu) were synthesized by the exchange reaction of K₂[Fe₂(S₂O₃)₂(NO)₄] with tetraalkylammonium bromides. The molecular and crystal structure of [(CH₃)₄N]₂[Fe₂(S₂O₃)₂(NO)₄] were studied by X-ray diffraction analysis. The iron atom in the four-membered cycle of the [2Fe–2S] anion is bound to another Fe atom and to two sulfur atoms and is coordinated by two nonequivalent NO groups, each bridging sulfur atom being bound to the SO₃group. The structurally equivalent iron atoms are in the state Fe^1–(S= 1/2). The Mössbauer spectroscopy method shows that the complexes are diamagnetic due to the strong Fe–Fe bond. It is found that the SO₃group provides higher stability of the thiosulfate anion than the anion in Roussin's red salt [Fe₂S₂(NO)₄]^2–.     

Pr4S3[Si2O7] und Pr3Cl3[Si2O7]: Durch weiche Fremdanionen modifizierte Derivate von Praseodymdisilicat

Pr₄S₃[Si₂O₇] and Pr₃Cl₃[Si₂O₇]: Derivatives of Praseodymium Disilicate Modified by Soft Foreign Anions For synthesizing both the disilicate derivatives Pr₄S₃[Si₂O₇] and Pr₃Cl₃[Si₂O₇], Pr, Pr₆O₁₁ and SiO₂ are brought to reaction with S and PrCl₃, respectively, in suitable molar ratios (850 °C, 7 d) in evacuated silica tubes. By using NaCl as a flux, Pr₄S₃[Si₂O₇] crystallizes as pale green, transparent single crystals (tetragonal, I4₁/amd, a = 1201.6(1), c = 1412.0(2) pm, Z = 8) with the appearance of slightly compressed octahedra. On the other hand, Pr₃Cl₃[Si₂O₇] emerges as pale green, transparent platelets and crystallizes monoclinically (space group: P2₁, a = 530.96(6), b = 1200.2(1), c = 783.11(8) pm, β = 109.07(1)°, Z = 2). In both crystal structures ecliptically conformed [Si₂O₇]^6– units of two corner‐linked [SiO₄] tetrahedra with Si–O–Si bridging angles of 131° in the sulfide and 148° in the chloride disilicate are present. In Pr₄S₃[Si₂O₇] both crystallographically independent Pr³⁺ cations show coordination numbers of 8 + 1 (5 S^2– and 3 + 1 O^2–) and 9 (3 S^2– and 6 O^2–). For Pr1, Pr2 and Pr3 in Pr₃Cl₃[Si₂O₇] coordination numbers of 10 (5 Cl^– and 5 O^2–) and 9 (2 ×; 4 Cl^– and 5 O^2– or 3 Cl^– and 6 O^2–, respectively) occur.     

Das gemischtvalente ternäre Oxoferrat(II,III) K3[Fe2O4] – eine aufgefüllte Variante des K2[Fe2O4]‐Typs

The Mixed‐Valent Oxoferrate(II,III) K₃[Fe₂O₄] – A Stuffed Variant of the K₂[Fe₂O₄] Type of Structure K₃[Fe₂O₄] has been obtained by tempering “Cs₃K₃CdO₄” in sealed Fe containers (36 d at 450–480 °C) as dark red transparent single crystals of rectangular shape. The structure determination (IPDS diffractometer data, MoKα, 1891 collected reflections, 234 symmetry independent, R1 = 0.033, wR2 = 0.088) confirms the space group Fddd; a = 596.11(9), b = 1140.3(1), c = 1717.9(3) pm; Z = 8. K₃[Fe₂O₄] exhibits a structure with [FeO₄] tetrahedra connected via corners leading to a three‐dimensional network closely related to the KFeO₂ type of structure. From the oxidation at 520 °C of iron metal with KO₂ in the presence of Na₂O black single crystal of K₂[Fe₂O₄] have been obtained. K₂[Fe₂O₄] crystallizes in the space group Pbca with Z = 8 and a = 559.18(7), b = 1122.1(1), c = 1592.8(2) pm (IPDS diffractometer data, MoKα, collected refelctions: 9543, 1213 symmetry independent, R1 = 0.043, wR2 = 0.102).