Über Kaliumtetracyanoplatinat(II), Kaliumtetracyanopalladat(II) und deren Monohydrate

We have determined the crystal structures of the potassium tetracyanoplatinates(II) and ‐palladates(II), and of their monohydrates, by X‐ray powder diffraction techniques and single crystal structure analysis. K₂[Pt(CN)₄]: orthorhombic; Pccn; a = 1370.11(2); b = 907.09(1); c = 703.91(2) pm; Z = 4; R_F² = 0.0903 (N(hkl) = 415). K₂[Pt(CN)₄] · H₂O: orthorhombic; Pnna; a = 715.79(4); b = 977.91(6); c = 1322.46(8) pm; Z = 4; R(F)_N′ = 0.027 (N′(hkl) = 1066). K₂[Pd(CN)₄]: monoclinic; P2₁/c; a = 433.03(2); b = 782.90(3); c = 1328.17(6) pm; ß = 93.069(3)°; Z = 2; R_p = 0.0583 (N(hkl) = 352). K₂[Pd(CN)₄] · H₂O: orthorhombic; Pnna; a = 721.48(6); b = 976.77(8); c = 1326.4(1) pm; Z = 4; R(F)_N′ = 0.048 (N′(hkl) = 1137). In all examined representatives the anions are stacked one upon the other, even though they are tilted in part. The results are completed by spectroscopic and thermo analytical investigations.     

Ba5[CrN4]N: Das erste Nitridochromat(V)

Ba₅[CrN₄]N: The First Nitridochromate(V) Ba₅[CrN₄]N is prepared by reaction of mixtures of Li₃N, Ba₃N₂ and CrN/Cr₂N (1 : 1) (molar ratio Li : Ba : Cr = 3 : 5 : 1) in tantalum crucibles at 700°C with flowing nitrogen (1 atm) within a period of 48 h. After cooling down to room temperature (60°C/h) black-shining single crystals of the ternary phase with a platy habit are obtained (monoclinic, C2/m; a = 1054.0(2) pm, b = 1170.9(3) pm, c = 937.7(2) pm, b? = 110,79(2)°; Z = 4). The crystal structure contains isolated complex anions [Cr^VN₄]^7? which nearly satisfy the ideal tetrahedral symmetry (Cr? N [pm]: 2 × 175.3(4), 2 × 175.8(5); N? Cr? N [°]: 106.8(2), 109.5(2), 2 × 109.9(2), 2 × 110,3(2)). The coordination sphere for each of the terminal nitride functions of the complex anions is completed by five neighbouring Ba²⁺ ions (distorted CrBa₅ octahedra). The octahedra are connected via common CrBa₂ faces as well as CrBa edges thereby forming condensed tetrameric octahedral groups. The isolated nitride ions which are also present in the crystal structure of Ba₅[CrN₄]N are in an octahedral environment of Ba²⁺ ions. The presence of a d¹-System (Cr(V)) is confirmed by magnetic susceptibility data.     

Strukturelle Vielfalt im pseudo‐ternären System M/Ge/I: α‐[NMe(nBu)3](GeI4)I, β‐[NMe(nBu)3](GeI4)I und [ImMe(nBu)][N(nBu)4](GeI4)3I2

By reaction of GeI₄, [N(nBu)₄]I as iodide donor, and [NMe(nBu)₃][N(Tf)₂] as ionic liquid, reddish‐black, plate‐like shaped crystals are obtained. X‐ray diffraction analysis of single crystals resulted in the compositions ;alpha;‐[NMe(nBu)₃](GeI₄)I (Pbca; a = 1495.4(3) pm; b = 1940.6(4) pm; c = 3643.2(7) pm; Z = 16) and β‐[NMe(nBu)₃](GeI₄)I (Pn; a = 1141.5(2) pm; b = 953.6(2) pm; c = 1208.9(2) pm; β = 100.8(1)°; Z = 2). Depending on the reaction temperature, the one or other compound is formed selectively. In addition, the reaction of GeI₄ and [N(nBu)₄]I, using [ImMe(nBu)][BF₄] (Im = imidazole) as ionic liquid, resulted in the crystallization of [ImMe(nBu)][N(nBu)₄](GeI₄)₃I₂ (P2₁/c; a = 1641.2(3) pm; b = 1903.0(4) pm; c = 1867.7(4) pm; β = 92.0(1)°; Z = 4). The anionic network of all three compounds is established by molecular germanium(IV)iodide, which is bridged by iodide anions. The different connectivity of (GeI₄–I^–) networks is attributed to the flexibility of I^– regarding its coordination and bond length. Here, a [3+1]‐, 4‐ and 5‐fold coordination is first observed in the pseudo‐ternary system M/Ge/I (M: cation).     

Novel Barium Beryllates Ba[Be2N2] and Ba3[Be5O8]: Syntheses,Crystal Structures and Bonding Properties

Ba[Be₂N₂] was prepared as a yellow‐green microcrystalline powder by reaction of Ba₂N with Be₃N₂ under nitrogen atmosphere. The crystal structure Rietfeld refinements (space group I4/mcm, a = 566.46(5) pm, c = 839.42(9) pm, R_int = 4.73 %, R_prof = 9.16 %) reveal the compound to crystallize as an isotype of the nitridoberyllates A[Be₂N₂] (A = Ca, Sr) consisting of planar 4.8² nets of mutually trigonal planar coordinated Be and N species. Averaged magnetic susceptibility values for the anion [(Be₂N₂)^2?] determined from measurements on A[Be₂N₂] with A = Mg, Ca, Ba allow to derive a diamagnetic increment for N^3? χ_dia = (?13±1stat.) · 10^?6emu mol^?1. Colorless Ba₃[Be₅O₈] was first obtained as an oxidation product of Ba[Be₂N₂] in air. The crystal structure was solved and refined from single crystal X‐ray diffaction data (space group Pnma, a = 942.9(1) pm, b = 1163.47(7) pm, c = 742.1(1) pm, R1 = 2.99 %, wR2 = 7.15 %) and contains infinite rods of Be in trigonal planar, tetrahedral and 3 + 1 coordination by O. The crystal structure is discussed in context with other known oxoberyllates. Electronic structure calculations and electron localization function diagrams for both compounds support the classification as nitrido‐ and oxoberyllate, respectively.     

Ein neues cis‐[Bi3I12]3−‐Anion in Tri(n‐butyl)methylammonium Dodecaiodotribismutat

The Novel cis‐[Bi₃I₁₂]^3?‐Anion in Tri(n‐butyl)methylammoniumdodecaiodo‐tribismutate By reaction of equivalent amounts of BiI₃, KI and I₂ in [N(CH₃) (n‐C₄H₉)₃][N(SO₂CF₃)₂] as Ionic Liquid, transparent reddish crystals with the composition [N(CH₃)(n‐C₄H₉)₃]₃[Bi₃I₁₂] are formed. Concerning to X‐ray diffraction investigations based on single crystals as well as powders, [N(CH₃)(n‐C₄H₉)₃]₃[Bi₃I₁₂] crystallizes monoclinic (P2₁/c; a = 2383.0(5); b = 1241.0(3); c = 2493.0(5) pm; β = 97.50(3)°; Z = 4). The anion consists of distorted (BiI₆)‐octahedra, which are face‐shared via cis‐oriented octahedral faces. With the cis‐[Bi₃I₁₂]^3?‐anion such a connectivity is firstly described.     

Zur Oxydation intermetallischer Phasen: Die Oxoplumbate(II) K6[Pb2O5] [1] und K4[PbO3] [2]

On the Oxidation of Intermetallic Phases: The Oxoplumbates(II) K₆[Pb₂O₅] [1] and K₄[PbO₃] [2] Very pale yellow crystals of K₆[Pb₂O₅] were obtained by heating a wellground mixture of LiPb und K₂O₂ (K₂O₂: LiPb = 2.5:1) in Ag-tubes (550°C; 40 d). The crystal structure, triclinic, space group P1 , a = 1 326.7(6); b = 758.8(4); c = 637.0(3) pm; α = 92.17(3)°; β = 94.41(3)°; γ = 112.85(4)°; Z = 2 was determined (four-circle diffractometer data, Mo? K, 3 270 I_o(hkl), R = 8.0%, R_w = 3.5%, parameters see text). The pale yellow crystals of K₄[PbO3] were received by heating KPb and K₂O₂ (K₂O₂: KPb = 3.3:2) in Ni-tubes (450°C; 17 d). The crystal structure (orthorhombic, space group Pbca with a = 658.2(1); b = 1 131.8(4); c = 1 872.2(6) pm; Z = 8) was refined (four-circle diffractometer data, Mo? K, 2 003 I_o(hkl), R = 4.9%, R_w = 2.8%). The Madelung Part of Lattice Energy (MAPLE), Effective Coordination Numbers (ECoN), the Mean Fictive Ionic Radii (MEFIR) and the Charge Distribution (CHARDI) are being calculated for both oxides.     

Synthesis and Structure of Ba[ZrN2] and Ba2[NbN3]

Ba₃N₂ reacts at 950°C under pure N₂ with Zr to yield dark red, air-sensitive Ba[ZrN₂]. This new compound crystallizes in the tetragonal space group P4/nmm with a = 416.10(2), c = 839.2(1) pm and Z = 2. The crystal structure was solved and refined using X-ray and neutron powder diffraction data. In the nitrido zirconate [ZrN₂]^2? the Zr atoms exhibit a square-pyramidal coordination by five N atoms at distances of 201(3) and 220.2(2) pm. The pyramids share all the edges in the basal plane to form layers parallel to (001) with their apices alternately pointing up and down. The Ba²⁺ cations are integrated into these layers at the levels of the pyramidal apices. The structure can be interpreted as a stuffed PbFCl type. Ba₂[NbN₃] is formed by the reaction of Ba₃N₂ and NbN or of Ba and Nb at 1 000°C under N₂. Isostructural to Ba₂[TaN₃] it crystallizes in the monoclinic space group C2/c with a = 613.2(3), b = 1 176.8(3), c = 1 322.9(4) pm, β = 91.65(2)°, Z = 8. The nitrido niobate anions form chains of corner sharing NbN₄ tetrahedra with distances Nb? N between 188(1) and 199.9(9) pm.     

Two New Modifications of [P(C6H5)4]2[Cu2I4]

Single crystals of two new modifications of [P(C₆H₅)₄]₂[Cu₂I₄] were obtained by reaction of granulated copper with iodine and [P(C₆H₅)₄]I in dry acetone under nitrogen atmosphere. They crystallise monoclinically, space group P2₁/n (No. 14), a = 11.550(6), b = 7.236(2), c = 27.232(13) Å, β = 98.13(3)°, V = 2253(2) ų, and Z = 2 ([P(C₆H₅)₄]₂[Cu₂I₄]-C), and space group Cc (No. 9), a = 17.133(5), b = 15.941(5), c = 18.762 (6) Å, β = 114.02(1)°, V = 4681(3) ų, and Z = 4 ([P(C₆H₅)₄]₂[Cu₂I₄]-D), respectively. In these compounds the [CuI₂]^? anions form dimers di-μ-iodo-diiodocuprate(I), which are either planar ( C ) or folded ( D ).     

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.     

Ein Erdalkalimetallpolyphosphid ungewöhnlicher Zusammensetzung: Die Kristallstruktur von Ba5P9

A Polyphosphide of Unusual Composition: The Crystal Structure of Ba₅P₉ The metallic grey compound Ba₅P₉ can be synthesised from the elements in stoichiometric amounts. It reacts easily with moist air. In the crystal structure (orthorhombic, Fdd2 , a = 1562.6(1) pm, b = 1896.8(2) pm, c = 1027.2(2) pm; Z = 8) anionic P₉ chain fragments are separated by Ba cations. With respect to the stoichiometry a charge of 10‐ results for the polyphosphide anion, but 11 electrons are needed following the (8‐N) rule. According to magnetic measurements the anionic unit is no radical, so a stabilisation by double bonds is discussed.     

Iodoplumbate mit polymeren Anionen – Synthese und Kristallstrukturen von [Na3(OCMe2)12][Pb4I11(OCMe2)], (Ph4P)2[Pb5I12] und (Ph4P)4[Pb15I34(dmf)6]

Iodoplumbates with Polymeric Anions – Synthesis and Crystal Structures of [Na₃(OCMe₂)₁₂][Pb₄I₁₁(OCMe₂)], (Ph₄P)₂[Pb₅I₁₂], and (Ph₄P)₄[Pb₁₅I₃₄(dmf)₆] Reactions of PbI₂ with NaI in polar organic solvents followed by crystallization with large cations yield iodoplumbate complexes with various compositions and structures. [Na₃(OCMe₂)₁₂][Pb₄I₁₁(OCMe₂)] 3 , (Ph₄P)₂[Pb₅I₁₂] 4 and (Ph₄P)₄[Pb₁₅I₃₄(dmf)₆] 7 contain one-dimensional infinite anionic chains of face- or edge-sharing PbI₆ or PbI₅L (L = acetone, DMF) octahedra. [Na₃(OCMe₂)₁₂][Pb₄I₁₁(OCMe₂)] 3 : Space group P1 (No. 1), a = 1120.3(5), b = 1265.3(6), c = 1608.3(8) pm, α = 74.64(4), β = 70.40(4), γ = 85.24(4)°, V = 2071(2) · 10⁶ pm³; (Ph₄P)₂[Pb₅I₁₂] 4 : Space group C2/c (No. 15), a = 787.00(10), b = 2812.0(5), c = 3115.9(5) pm, β = 96.240(13)°, V = 6885(2) · 10⁶ pm³; (Ph₄P)₄[Pb₁₅I₃₄(dmf)₆] 7 : Space group P2₁/n (No. 14), a = 2278.8(4), b = 1782.6(3), c = 2616.8(4) pm, β = 114.432(13)°, V = 9678(3) · 10⁶ pm³.     

Drei Alkalimetall‐Erbium‐Thiophosphate: Von der Schichtstruktur bei KEr[P2S7] zur dreidimensionalen Vernetzung in NaEr[P2S6] und Cs3Er5[PS4]6

Three Alkali‐Metal Erbium Thiophosphates: From the Layered Structure of KEr[P₂S₇] to the Three‐Dimensional Cross‐Linkage in NaEr[P₂S₆] and Cs₃Er₅[PS₄]₆ The three alkali‐metal erbium thiophosphates NaEr[P₂S₆], KEr[P₂S₇], and Cs₃Er₅[PS₄] show a small selection of the broad variety of thiophosphate units: from ortho‐thiophosphate [PS₄]^3? and pyro‐thiophosphate [S₃P–S–PS₃]^4? with phosphorus in the oxidation state +V to the [S₃P–PS₃]^3? anion with a phosphorus‐phosphorus bond (d(P–P) = 221 pm) and tetravalent phosphorus. In spite of all differences, a whole string of structural communities can be shown, in particular for coordination and three‐dimensional linkage as well as for the phosphorus‐sulfur distances (d(P–S) = 200 – 213 pm). So all three compounds exhibit eightfold coordinated Er³⁺ cations and comparably high‐coordinated alkali‐metal cations (CN(Na⁺) = 8, CN(K⁺) = 9+1, and CN(Cs⁺) ≈ 10). NaEr[P₂S₆] crystallizes triclinically ( ; a = 685.72(5), b = 707.86(5), c = 910.98(7) pm, α = 87.423(4), β = 87.635(4), γ = 88.157(4)°; Z = 2) in the shape of rods, as well as monoclinic KEr[P₂S₇] (P2₁/c; a = 950.48(7), b = 1223.06(9), c = 894.21(6) pm, β = 90.132(4)°; Z = 4). The crystal structure of Cs₃Er₅[PS₄] can also be described monoclinically (C2/c; a = 1597.74(11), b = 1295.03(9), c = 2065.26(15) pm, β = 103.278(4)°; Z = 4), but it emerges as irregular bricks. All crystals show the common pale pink colour typical for transparent erbium(III) compounds.     

Synthese und Struktur von Ba10[Ti4N12], ein ternäres Nitrid mit vierkernigen cyclischen Nitridotitanat-Ionen

Synthesis and Structure of Ba₁₀[Ti₄N₁₂], a Ternary Nitride with Tetranuclear Cyclic Nitridotitanate Ions Ba₁₀[Ti₄N₁₂] results from the reaction of Ba₃N₂, TiN, and N₂ at 980°C. It crystallizes in the triclinic space group P1 with the lattice parameters a = 644.3(4); b = 942.9(7); c = 966.9(7) pm, α = 106.37(4)°; β = 102.22(4)°; γ = 108.56(4)°, Z = 1. The crystal structure is built up by Ba²⁺ cations and tetranuclear cyclic nitridotitanate(IV) anions. In the anions four TiN₄ tetrahedra are each connected by two corners to form centrosymmetrical rings, which are stacked along [100] forming tubes. The Ti? N distances range from 192 to 199 pm.     

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.     

Synthese und Kristallstrukturen von [Li(thf)4]2[Bi4I14(thf)2], [Li(thf)4]4[Bi5I19] und (Ph4P)4[Bi6I22]

Synthesis and Crystal Structure of [Li(thf)₄]₂[Bi₄I₁₄(thf)₂], [Li(thf)₄]₄[Bi₅I₁₉], and (Ph₄P)₄[Bi₆I₂₂] Solutions of BiI₃ in THF or methanol react with MI (M = Li, Na) to form polynuclear iodo complexes of bismuth. The syntheses and results of X-ray structure analyses of compounds [Li(thf)₄]₂[Bi₄I₁₄(thf)₂], [Li(thf)₄]₄[Bi₅I₁₉], [Na(thf)₆]₄[Bi₆I₂₂] and (Ph₄P)₄[Bi₆I₂₂] are described. The anions of these compounds consist of edge-sharing BiI₆ and BiI₅(thf) octahedra. The Bi atoms lie in a plane and are coordinated by bridging and terminal I atoms and by THF ligands in a distorted octahedral fashion. [Li(thf)₄]₂[Bi₄I₁₄(thf)₂]: Space group P1 (No. 2), a = 1 159.9(6), b = 1 364.6(7), c = 1 426.5(7) pm, α = 114.05(3), β = 90.01(3), γ = 100.62(3)°. [Li(thf)₄]₄[Bi₅I₁₉]: Space group P2₁/n (No. 14), a = 1 653.0(9), b = 4 350(4), c = 1 836.3(13) pm, β = 114.70(4)°. [Na(thf)₆]₄[Bi₆I₂₂]: Space group P2₁/n (No. 14), a = 1 636.4(3), b = 2 926.7(7), c = 1 845.8(4) pm, β = 111.42(2)°. (Ph₄P)₄[Bi₆I₂₂]: Space group P1 (No. 2), a = 1 368.6(7), b = 1 508.1(9), c = 1 684.9(8) pm, α = 98.28(4), β = 95.13(4), γ = 109.48(4)°.     

Synthese und Kristallstrukturen von α‐ und β‐Ba3(PS4)2 sowie von Ba3(PSe4)2

Synthesis and Crystal Structures of α‐, β‐Ba₃(PS₄)₂ and Ba₃(PSe₄)₂ Ba₃(PS₄)₂ and Ba₃(PSe₄)₂ were prepared by heating mixtures of the elements at 800 °C for 25 h. Both compounds were investigated by single crystal X‐ray methods. The thiophosphate is dimorphic and undergoes a displacive phase transition at about 75 °C. Both modifications crystallize in new structure types. In the room temperature phase (α‐Ba₃(PS₄)₂: P2₁/a; a = 11.649(3), b = 6.610(1), c = 17.299(2) Å, β = 90.26(3)°; Z = 4) three crystallographically independent Ba atoms are surrounded by ten sulfur atoms forming distorted polyhedra. The arrangement of the PS₄ tetrahedra, isolated from each other, is comparable with the formation of the SO₄^2? ions of β‐K₂SO₄. In β‐Ba₃(PS₄)₂ (C2/m; a = 11.597(2), b = 6.727(1), c = 8.704(2) Å; β = 90.00(3)°; Z = 2) the PS₄ tetrahedra are no more tilted along [001], but oriented parallel to each other inducing less distorted tetrahedra and polyhedra around the Ba atoms, respectively. Ba₃(PSe₄)₂ (P2₁/a; a = 12.282(2), b = 6.906(1), c = 18.061(4) Å; β = 90.23(3)°; Z = 4) is isotypic to α‐Ba₃(PS₄)₂ and no phase transition could be detected up to about 550 °C.     

Zur Konstitution von Ba2WO3F4 und Ba2MoO3F4

On the Structure of Ba₂Wo₃F₄ and Ba₂MoO₃F₄ Ba₂[WO_2/2O₂F₂]F₂ has been prepared for the first time as colourless single crystals (from powder, Au-tube, 680°C, 90 d). It crystallizes in the monoclinic (C c) crystal system with a = 1151.1, b = 938.2, c = 718.8 pm, ß = 126.17°, Z = 4. d_x = 6.17, d_pyk = 6.13 g · cm^?3. (Fourcirclediffractometer PW 1100, Fa. Philips, MoKα-, ω-2Θ-scan, 1832 I₀(hkl) R = 8.3, R_w = 7.4%). Parameters see in the text. The isotypic Ba₂MoO₃F₄ has been prepared as powder (a = 1147.5, b = 937.0, c = 725.1 pm, ß = 126.42°). The structure shows chains of (WO_2/2O₂F₂) groups along [001]. To establish O^2? and F^? on the positions IR and Raman Spectra are employed. The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed.     

Ortho‐Chalcogenotetrelate Anions as Chelating Ligands: Syntheses and Characterization of [K6(MeOH)9][Sn2Se6][Cr(en)2(SnSe4)]2, [Na(H2O)4][Cr(en)3]2[GeS3OH]2[Cr(en)2(GeS4)], and [Ba(H2O)10][{Cr(en)}2(GeSe4)2]

Reactions of K₄[SnSe₄], Na₄[GeS₄] or Ba₂[GeSe₄] with different 1,2‐diaminoethane (= en) coordinated complexes of CrCl₃ ([Cr(en)₂Cl₂]Cl or [Cr(en)₃]Cl₃) in MeOH or aqueous solution yielded three novel compounds that contain complexes of Cr³⁺ with ortho‐chalcogenotetrelate anions [E′E₄]^4? (E′ = Ge, Sn; E = S; Se): the crystal structures of [K₆(MeOH)₉][Sn₂Se₆][Cr(en)₂(SnSe₄)]₂ ( 1 ), [Na(H₂O)₄][Cr(en)₃]₂[GeS₃OH]₂[Cr(en)₂(GeS₄)] ( 2 ), and [Ba(H₂O)₁₀][{Cr(en)}₂(GeSe₄)₂] ( 4 ) have been determined by means of single crystal X‐ray diffraction ( 1 : triclinic space group ; lattice dimensions at 203 K: a = 1175.7(2), b = 1315.3(3), c = 1326.7(3) pm, α = 61.99(3)°, β = 64.05(3)°, γ = 83.57(3)°, V = 1617.4(6)·10⁶ pm³; R₁ [I > 2σ(I)] = 0.0788; wR₂ = 0.1306; 2 : monoclinic space group C2/c; lattice dimensions at 203 K: a = 2445.3(5), b = 1442.5(3), c = 1579.3(3) pm, β = 94.61(3)°, V = 5552.9(19)·10⁶ pm³; R₁ [I > 2σ(I)] = 0.0801; wR₂ = 0.2046; 4 : triclinic space group ; lattice dimension at 203 K: a = 1198.4(2), b = 1236.8(3), c = 1297.5(3) pm, α = 65.69(3)°, β = 63.35(3)°, γ = 81.21(3)°, V = 1565.2(5)·10⁶ pm³; R₁ [I > 2σ(I)] = 0.0732; wR₂ = 0.1855). 1 and 2 show the yet unprecedented complexation of transition metal ions by non‐bridging, single chalcogenotetrelate ligands to produce dinuclear, heterobimetallic complexes. Compound 2 contains the first structurally characterized complex with an ortho‐thiogermanate ligand. The formation of these compounds, and of a by‐product of 2 , [Cr(en)₃][GeS₃OH]·6H₂O ( 3 : monoclinic space group C2/c; lattice dimensions at 203 K: a = 2396.8(5), b = 1463.4(3), c = 1740.1(4) pm, β = 132.99(3)°, V = 4463.8(15)·10⁶ pm³; R₁ [I > 2σ(I)] = 0.0462; wR₂ = 0.1058), provides some insight in fundamental differences between the reaction behavior of [SnE₄]^4? anions one the one hand and [GeE₄]^4? anions on the other hand. The crucial role of the counterion charge becomes evident when comparing the structure motifs of the ternary anions in 1 and 2 with that observed in the Ba²⁺ compound 4 .     

SeBr3[AlBr4] und TeI3[AlI4] – zwei weitere Vertreter des SCl3[AlCl4]-Strukturtyps

SeBr₃[AlBr₄] and TeI₃[AlI₄] – two further Compounds in the SCl₃[AlCl₄] Structure Type The reaction of SeBr₄ and AlBr₃ in a closed glass ampoule at 150°C yields quantitatively SeBr₃[AlBr₄] in form of yellow moisture sensitive crystals. From Te, two equivalents of I₂, and AlI₃ one obtains TeI₃[AlI₄] in form of dark red, moisture sensitive crystals. Both compounds crystallize monoclinic in the space group Pc (SeBr₃[AlBr₄]: a = 670.7(7) pm, b = 663.9(5) pm, c = 1 428.6(2) pm, β = 101.21(9)°, TeI₃[AlI₄]: a = 731.9(1) pm, b = 730.8(1) pm, c = 1 565.5(3) pm, β = 102.01(2)°). They are isotypic and have the SCl₃[AlCl₄] structure type. The structures are built of tetrahedral AlX₄^? ions and of pyramidal EX₃⁺ ions (E = S, Se, Te; X = Cl, Br, I). The chalcogen atoms are additionally coordinated by halogen atoms of surrounding AlX₄^? ions, corresponding to a strongly distorted octahedral coordination EX₃₊₃.     

Über die Kronenetherkomplexe [K(15-Krone-5)2]3[Sb3I12], [TeCl3(15-Krone-5)][TeCl5] und [TeCl3(15-Krone-5)]2[TeCl6]

On the Crown Ether Complexes [K(15-Crown-5)₂]₃[Sb₃I₁₂], [TeCl₃(15-Crown-5)][TeCl₅], and [TeCl₃(15-Crown-5)]₂[TeCl₆] Orange-coloured crystals of [K(15-crown-5)₂]₃[Sb₃I₁₂] are formed in the reaction of potassium iodide with antimony triiodide and 15-crown-5 in acetonitrile solution. An X-ray structure determination reveals severe disorder of the crown ether molecules, which coordinate to the potassium atoms in a sandwich array; so only the [Sb₃I₁₂]^3? ion and the potassium positions were ascertained. The anion is a centrosymmetric trimer (symmetry C_2h), which can be understood as central SbI₆^3? ion, coordinated by two SbI₃ molecules. (Space group C2/m), Z = 2, 3263 observed, independent reflections, R = 0.06, lattice dimensions at 20°C: a = 2541.1 pm, b = 1441.7 pm, c = 1588.4 pm, β = 113.33°. The tellurium complexes [TeCl₃(15-crown-5)] [TeCl₅] and [TeCl₃(15-crown-5)]₂[TeCl₆] are prepared by reaction of TeCl₄ with 15-crown-5 in acetonitrile solution, forming yellow-green crystals sensitive to moisture. They are characterized by their i.r. spectra.