Ein neuer Strukturtyp bei Oxoiridaten mit quadratisch-planaren [IrO4]4−-Gruppen: K2Na2[IrO4], ein Raumnetz [Na2IrO4] mit Kanälen. (Mit einer Anmerkung zu Rb2Na2[IrO4])

A New Type of Structure in Oxoiridates with Square-planar Groups [IrO₄]^4?: K₂Na₂[IrO₄], a Network [Na₂IrO₄] with Channels (With a Remark on Rb₂Na₂[IrO₄]) For the first time magnificent dark red cuboid single crystals of K₂Na₂[IrO₄] were prepared by annealing intimate mixtures of a) KO_0.51, Na₂O₂, IrO₂ and Ir-powder (molar proportions 3.02 : 1.40 : 1.00 : 1.00; Ag-bomb, 740°C, 54 d) and of b) KO_0.51, Na₂O and IrO₂ (molar proportions K : Na : Ir = 2.20 : 2.20 : 1.00; Ag-bomb, 760°C, 57 d) respectively. The oxide crystallizes mP36, space group P2₁/c with a = 600.35(6) pm, b = 1111.2(1) pm, c = 933.0(1) pm and β = 113.14(1)°. Structure determination via four-circle diffractometer data (Siemens AED 2, Mo-Kα-Radiation) for all 2347 unique reflexions (merged from 9397 I_o(hkl) gave R = 0.0357 and R_w = 0.0340. K₂Na₂[IrO₄] crystallizes in a new type of structure. The oxide is antiferromagnetic as magnetic measurements showed (T_N = 32 K, Θ = ?60.2 K (single crystals) and ?49.2 K (powder) respectively, μ = 3.06 μ_B (single crystals) and 2.93 μ_B (powder) respectively). Effective coordination numbers ECoN, mean fictive ionic radii MEFIR and the Madelung part lattice energy MAPLE as well as the charge distributions CHARDI and CHARDINO are calculated and discussed.     

Pniktogenidostannate(IV) mit isolierten Tetraeder‐Anionen: Neue Vertreter (E1)4(E2)2[Sn(E15)4] (mit E1 = Na,K; E2 = Ca,Sr, Ba; E15 = P,As, Sb,Bi) vom Na6[ZnO4]‐Typ und die Überstrukturvariante von K4Sr2[SnAs4]

Pnictogenidostannates(IV) with Discrete Tetrahedral Anions: New Representatives (E1)₄(E2)₂[Sn(E15)₄] (with E1 = Na, K; E2 = Ca, Sr, Ba; E15 = P, As, Sb, Bi) of the Na₆[ZnO₄] Type and the Superstructure Variant of K₄Sr₂[SnAs₄] The silvery to dark metallic lustrous compounds (E1)₄(E2)₂[Sn(E15)₄] (E1 = Na, K; E2 = Ca, Sr, Ba; E15 = P, As, Sb, Bi) were prepared from melts of stoichiometric mixtures of the elements. They crystallize in the Na₆[ZnO₄]‐type structure (hexagonal, space group: P6₃mc, Z = 2; Na₄Ca₂[SnP₄]: a = 938.94(7), c = 710.09(8) pm; K₄Sr₂[SnAs₄]: a = 1045.0(2), c = 767.0(1) pm; K₄Ba₂[SnP₄]: a = 1029.1(6), c = 780.2(4) pm; K₄Ba₂[SnAs₄]: a = 1051.3(1), c = 795.79(7) pm; K₄Ba₂[SnSb₄]: a = 1116.9(2), c = 829.2(1) pm; K₄Ba₂[SnBi₄]: a = 1139.5(2), c = 832.0(2) pm). The anionic partial structure consists of tetrahedra [Sn(E15)₄]^8– orientated all in the same direction along [001]. In the cationic partial structure one of the two cation positions is occupied statistically by alkali and alkaline earth metal atoms. Up to now only for K₄Sr₂[SnAs₄] a second modification could be isolated, forming a superstructure type with three times the unit cell volume (hexagonal, space group: P6₃cm, Z = 6; a = 1801.3(2), c = 767.00(9) pm) and an ordered cationic partial structure.     

Darstellung,Struktur und magnetische Eigenschaften von Erdalkali-Mangan-Verbindungen AMnX mit A = Mg,Ca, Sr,Ba und X = Si,Ge, Sn

Preparation, Structure, and Magnetic Properties of the Alkaline Earth Manganese Compounds AMnX with A = Mg, Ca, Sr, Ba and X = Si, Ge, Sn The new compounds MgMnGe, MgMnSn, CaMnSi, CaMnSn, and SrMnSn were prepared by reaction of the elements. They crystallize tetragonally with the anti-PbFCl type structure (space group P4/nmm). The lattice constants see ”︁Inhaltsübersicht”︁”︁. Using a Faraday balance, magnetic measurements in the range 4.2 to 800 K were performed with the new substances and with the already known compounds CaMnGe, SrMnGe, and BaMnGe. They indicate metamagnetic behaviour at low temperatures. At high temperatures twodimensional magnetic interactions between the manganese atoms seem to persist. The construction of an unexpensive heating device for the Faraday balance is described.     

Über Thallium(I)-chlorooxomolybdate: Synthese und Kristallstrukturen von Tl[MoOCl4(NCCH3)], Tl[Mo2O2Cl7] und Tl2[Mo4O4Cl14] und die Struktur von Tl2[MoCl6]

On Thallium(I)-oxochloromolybdates: Synthesis and Crystal Structures of Tl[MoOCl₄(NCCH₃)], Tl[Mo₂O₂Cl₇], and Tl₂[Mo₄O₄Cl₁₄] and the Structure of Tl₂[MoCl₆] Black crystals of Tl₂[MoCl₆] are formed in the reaction of TlCl with MoOCl₃ in a sealed evacuated glass ampoule at 350 °C. The crystal structure analysis shows that Tl₂[MoCl₆] (cubic, Fm 3¯m, a = 986.35(7) pm) adopts the K₂[PtCl₆] structure with a Mo–Cl bond length of 236.6 pm. Tl[MoOCl₄(NCCH₃)] was obtained by the reaction of TlCl with MoOCl₃ in acetonitrile in form of yellow, moisture sensitive crystals. The structure (orthorhombic, Cmcm, a = 746.0(1), b = 1463.8(3), c = 857.3(2) pm) is built of Tl⁺ cations and octahedral [MoOCl₄(NCCH₃)]^– anions in which the acetonitrile ligand is bound in trans position to the oxygen. The reaction of TlCl and MoOCl₃ in dichloromethane yields Tl[Mo₂O₂Cl₇] and Tl₂[Mo₄O₄Cl₁₄] as green moisture sensitive crystals. The structure of Tl[Mo₂O₂Cl₇] (orthorhombic, Pmmn, a = 694.3(1), b = 951.9(2), c = 904.7(1) pm) consists of Tl⁺ cations and dinuclear [Mo₂O₂Cl₇]^– anions, with two equidistant chlorine bridges of 248.2 and one longer chlorine bridge of 265.7 pm. The oxygen atoms are located in the trans positions of the longer chloro bridge. The structure of Tl₂[Mo₄O₄Cl₁₄] (triclinic, P1¯, a = 692.8(1), b = 919.6(1), c = 998.9(1) pm, α = 104.94(1)°, β = 90.31(1)°, γ = 108.14(1)°) is build of Tl⁺ cations and [Mo₄O₄Cl₁₄]^2– anions which form tetramers of distorted octahedral, edgesharing (MoOCl₅) units with chlorine atoms in the bridging positions. The oxygen atoms are located in the trans positions of the longest chlorine bridges.     

Synthese und Kristallstrukturen von (Ph4P)4[Bi8I28], (nBu4N)[Bi2I7] und (Et3PhN)2[Bi3I11] – Iodobismutate mit isolierten bzw. polymeren Anionen

Synthesis and Crystal Structures of (Ph₄P)₄[Bi₈I₂₈], (ⁿBu₄N)[Bi₂I₇], and (Et₃PhN)₂[Bi₃I₁₁] – Bismuth Iodo Complexes with Isolated and Polymeric Anions Solutions of BiI₃ in methanol react with NaI and (ⁿBu₄N)(PF₆) or (Et₃NPh)(PF₆) to form anionic bismuth iodo complexes (ⁿBu₄N)[Bi₂I₇] 1 and (Et₃PhN)₂[Bi₃I₁₁] 2 . In 1 Bi₄I₁₆ units, and in 2 Bi₆I₂₄ units are linked by common I-atoms to onedimensional infinite chains. Reaction of BiI₃ with (Ph₄P)(PF₆) in methanol yields (Ph₄P)₄[Bi₈I₂₈] 3 . The anions of 1–3 consist of edge-sharing BiI₆ octahedra. (ⁿBu₄N)[Bi₂I₇] 1 : Space group I2/m (No. 13), a = 1 082.3(5), b = 2 597.1(13), c = 1 206.1(6) pm, β = 93.17(2)°, V = 3 385(3) · 10⁶ pm³; (Et₃PhN)₂[Bi₃I₁₁] 2 : Space group P1 (No. 2), a = 1 283.5(6), b = 1 345.9(7), c = 1 546.3(8) pm, α = 83.87(2), β = 74.24(2), γ = 68.26(2)°, V = 2 388(2) · 10⁶ pm³; (Ph₄P)₄[Bi₈I₂₈] 3 : Space group P1 (No. 2), a = 1 329.3(4), b = 1 337.0(4), c = 2 193.1(5) pm, α = 104.20(2), β = 99.73(2), γ = 100.44(2)°, V = 3 622(2) · 10⁶ pm³.     

The [Sn5]2– Cluster Compound [K‐(2,2,2‐crypt)]2Sn5 – Synthesis,Crystal Structure,Raman Spectrum,and Hierarchical Relationship to CaIn2

Dark red crystals of [K‐(2,2,2)‐crypt)]₂Sn₅ precipitate after the reaction of (2,2,2)‐crypt with a solution of K_1.33Sn in liquid ammonia at room temperature. The compound is sensitive to oxidation and hydrolysis. The sequence of Raman bands (104, 120, 133 and 180 cm^–1) is characteristic for the trigonal bipyramidal closo‐[Sn₅]^2– cluster anion. The wave numbers correspond with the data from Hartree‐Fock calculations (114, 128, 142 and 187 cm^–1). The compound crystallizes trigonally (a = 11.736 Å, c = 22.117 Å, Z = 2, space group P3c1 (No. 165); Pearson code hP262), isotypic with [Na‐(2,2,2)‐crypt)]₂Pb₅. The atoms of the cluster show strange anisotropic displacements, which are perfectly reducible to a helical rigid‐body motion around and along [001] (libration: ± 9.5°; translation ± 0.29 Å). The structure can be described as a hierarchical derivative of the initiator CaIn₂ (P6₃/mmc, hP6), generated by an atom‐to‐aggregate replacement: [Ca][In]₂ = [Sn₅][K @ C₃₆H₇₂N₄O₁₂]₂. Thus, the distribution of the [Sn₅]^2– Zintl anions is hexagonal primitive, and the cation complexes are located close to the centers of trigonal superprisms formed by Sn₅ clusters.     

Das Addukt von BiCl3 mit Mo6Cl12: [BiCl]-Hanteln in der Struktur von [BiCl][Mo6Cl14]

The Adduct of BiCl₃ and Mo₆Cl₁₂: [BiCl] Dumbbells in the Structure of [BiCl][Mo₆Cl₁₄] MoCl₃ reacts under decomposition to MoCl₂ and Cl₂ with BiCl₃ in a sealed evacuated glass ampoule at 550 °C to form light red crystals of [BiCl][Mo₆Cl₁₄]. The crystal structure determination (monoclinic, C 2/c, a = 1268.1(4) pm, b = 1304.6(3) pm, c = 2571.9(8) pm, β = 91.79(3)°, Z = 8) shows that the structure is built of [(Mo₆Cl₈)Cl₆] units containing nearly regular octahedral Mo₆ clusters. These units are arranged in the motiv of a cubic closest packing. The octahedral interstices contain [BiCl] dumbbells with a Bi–Cl bond length of 249 pm. The coordination sphere of the Bi atom is completed by six weaker Bi–Cl-contacts of 275 to 308 pm length to a distorted monocapped trigonal prism. Neglecting the secondary Bi–Cl bonds, the title compound can be formulated as [(BiCl)²⁺][(Mo₆Cl₁₄)^2–].     

ChemInform Abstract: [Ta3O3]A (A: Li,Na, K) and [Ta3O3]B[Ta3O3] (B: Ca,Sr, Ba): Sandwich‐Type Complexes Containing Ta3O3‐ δ and π Double Aromatic Ligands.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

[Na · Triglyme]2[S(BH3)4]: Ein Salz des neuen Anions Tetrakis(boran)sulfat(2—) Kristallstruktur und theoretische Untersuchung der Molekülstruktur

[Na · Triglyme]₂[S(BH₃)₄]: a Salt of the New Anion Tetrakis(borane)sulfate(2? ). Crystal Structure and Theoretical Investigation of the Structure Na[H₃B-m?₂-S(B₂H₅)] 1 is produced by the reaction between NaSH and THF · BH₃, under dehydrogenation. 1 is also formed as the first ¹¹B-NMR-spectroscopically detectable reaction product by the reaction between anhydrous Na₂S and THF · BH₃. Adducts of BH₃ with the S^2? ion are not detectable in THF. The anion [S(BH₃)₄]^2? can however be obtained, by the addition of NaBH₄ to 1 in diglyme or triglyme respectively: [Na — Triglyme]₂[S(BH₃)₄] 2. 2 crystallizes in the monoclinic space group P2₁/n (Nr. 14). Structural data of 1 and 2 have been calculated by SCF methods. The anion of 2 may be viewed either as an adduct of B₂H₆ with S^2?, or as a bridge substituted thia derivative of B₂H₇^?; furthermore the anion of 2 is isoelectronic and isostructural with the SO ion.