Kristallstruktur von Tetraphenylphosphonium-Monothiocyanatohydro-closo-Decaborat, [P(C6H5)4]2[2-(SCN)B10H9] · CH3CN

Crystal Structure of Tetraphenylphosphonium Monothiocyanatohydro-closo-Decaborate, [P(C₆H₅)₄]₂[2-(SCN)B₁₀H₉] · CH₃CN The X-ray structure determination of [P(C₆H₅)₄]₂[2-(SCN)B₁₀H₉] · CH₃CN (monoclinic, space group P2₁/n, a = 10.6040(10), b = 13.8880(9), c = 33.888(3) Å, β = 94.095(8)°, Z = 4) reveals the S coordination of the SCN substituent with a B? S distance of 1.913(6) Å and a B? S? C angle of 105.3(3)°. The SCN group is nearly linear (178.2(7)°).     

Darstellung und Kristallstrukturen von [P(C6H5)4][1-(NH3)B10H9] und Cs[(NH3)B12H11] · 2CH3OH

Synthesis and Crystal Structures of [P(C₆H₅)₄][1-(NH₃)B₁₀H₉] and Cs[(NH₃)B₁₂H₁₁] · 2CH₃OH The reduction of [1-(NO₂)B₁₀H₉]^2? with aluminum in alkaline solution yields [1-(NH₃)B₁₀H₉]^? and by treatment of [B₁₂H₁₂]^2? with hydroxylamine-O-sulfonic acid [(NH₃)B₁₂H₁₁]^? is formed. The crystal structures of [P(C₆H₅)₄][1-(NH₃)B₁₀H₉] (triclinic, space group P1 , a = 7.491(2), b = 13.341(2), c = 14.235(1) Å, α = 68.127(9), β = 81.85(2), γ = 86.860(3)°, Z = 2) and Cs[(NH₃)B₁₂H₁₁] · 2CH₃OH (monoclinic, space group P2₁/n, a = 14.570(2), b = 7.796(1), c = 15.076(2) Å, β = 111.801(8)°, Z = 4) reveal for both compounds the bonding of an ammine substituent to the cluster anion.     

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 ).     

Kristallstruktur von Dipyridiniomethan-Monohalogenohydro-closo-Decaboraten(2–), [(C5H5N)2CH2][2-XB10H9]; X  Cl,Br, I

Crystal Structures of Dipyridiniomethane Monohalogenohydro-closo-Decaborates(2–), [(C₅H₅N)₂CH₂][2-XB₁₀H₉]; X = Cl, Br, I [B₁₀H₁₀]^2? reacts with chlorine, bromine and iodine or with N-halogenosuccinimide, yielding the monohalogenodecaborates [2-XB₁₀H₉]^2? (X = Cl, Br, I), which are separated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose from the starting compound and higher halogenated products. The X-ray structure determinations of the isotypic chloro and bromo compounds [(C₅H₅N)₂CH₂][2-XB₁₀H₉] (monoclinic, space group C2/c, Z = 8; for X ? Cl: a = 33.174(5), b = 7.2809(4), c = 16.2232(7) Å, β = 113.307(7)°; for X = Br: a = 33.525(11), b = 7.281(2), c = 16.297(4) Å, β = 113.62(2)°) and of the iodo compound [(C₅H₅N)₂CH₂][2-IB₁₀H₉] (monoclinic, space group P2₁, Z = 2, a = 7.143(3), b = 13.568(4), c = 9.479(7) Å, β = 97.57(5)°) show columns of substituted boron clusters [2-XB₁₀H₉]^2?, X = Cl, Br, I and bent dications [(C₅H₅N)₂CH₂]²⁺ along the shortest axis wich are assembled to alternating layers in the crystal lattice.     

Darstellung und Struktur der ersten gemischten Alkalimetallhydrogencarbonate NaA2[H(CO3)2] · 2H2O mit A = K,Rb

Preparation and Crystal Structure of the First Mixed Alkalimetal Hydrogencarbonates NaA₂[H(CO₃)₂] · 2H₂O with A = K, Rb The new hydrogencarbonates NaK₂[H(CO₃)₂] · 2H₂O (Pnma, a = 934.07(13) pm, b = 789.31(10) pm, c = 1142.1(5) pm, V_EZ = 842.0(4) · 10⁶ pm³, Z = 4, R1 (I ? 2σ(I)) = 0.023, wR2 = 0.066 for 989 reflections) and NaRb₂[H(CO₃)₂] · 2H₂O (Pnma, a = 948.24(11) pm, b = 811.37(9) pm, c = 1189.0(2) pm, V_EZ = 914.8(2) · 10⁶ pm³, Z = 4, R1 (I ≤ 2σ(I)) = 0.031, wR2 = 0.077 for 1063 reflections) were prepared from aqueous solutions. The crystal structures were determined. The isostructural compounds contain dimeric, non centrosymmetric [H(CO₃)₂]^3? anions. In NaK₂[H(CO₃)₂] · 2H₂O a short hydrogen bond (d(O … O) = 246.1(2) pm) with an asymmetric potential was detected. In NaRb₂[H(CO₃)₂] · 2H₂O a hydrogen bond with symmetric potential (d(O … O) = 247.8(5) pm) can be assumed. The IR-spectra of NaK₂[H(CO₃)₂] · 2H₂O and Na₃[H(CO₃)₂] · 2H₂O are compared.     

Solvothermal Syntheses and Crystal Structures of Two Novel Borates: [(CH3)3NH][B5O6(OH)4] and Na2[H2TMED][B7O9(OH)5]2

Two novel borates [(CH₃)₃NH][B₅O₆(OH)₄] (I) and Na₂[H₂TMED][B₇O₉(OH)₅]₂ (II) have been synthesized under solvothermal conditions, and characterized by elemental analyses, FT-IR spectroscopy, and single crystal X-ray diffraction. Crystal data for I: monoclinic, P2₁/c, a = 9.3693(11) Å, b = 14.0375(17) Å, c = 10.0495(9) Å, β = 91.815(9)°, Z = 4. Crystal data for II: monoclinic, P2₁/c, a = 11.6329(2) Å, b = 11.9246(3) Å, c = 10.2528(2) Å, β = 100.178(2)°, Z = 4. Their crystal structures both have 3D supramolecular framework with large channels constructed by O–H···O hydrogen-bonding among the polyanions of [B₅O₆(OH)₄]^? or [B₇O₉(OH)₅]^2? clusters. The templating organic amines cations in I and II are both located in the channels of 3D supramolecular frameworks, respectively, and interact with the polyborate frameworks both electrostatically and via hydrogen bonds of N–H···O. Na₂[H₂TMED][B₇O₉(OH)₅]₂ is the first example of heptaborate co-templated by alkali metal and organic base, which is also rare in borates. The photoluminescence property of the synthetic sample of Na₂[H₂TMED][B₇O₉(OH)₅]₂ in the solid state at room temperature was also investigated by fluorescence spectrophotometer.     

Molybdänhalogenidcluster mit sechs terminalen Alkoholatliganden: (C18H36N2O6Na)2[Mo6Cl8(OCH3)6] · 6CH3OH und (C18H36N2O6Na2)2[Mo6Cl8(OC6H5)6]

Molybdenum(II) Halide Clusters with six Alcoholate Ligands: (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OCH₃)₆] · 6CH₃OH and (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OC₆H₅)₆] . The reaction of Na₂[Mo₆Cl₈(OCH₃)₆] and 2,2,2-crypt yields (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OCH₃)₆] · 6 CH₃OH ( 1 ), which is converted to (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OC₆H₅)₆] ( 2 ) by metathesis with phenol. According to single crystal structure determinations ( 1 : P3 1c, a=14.613(3) Å, c=21.036(8) Å; 2 : P3 1c, a=15.624(1) Å, c=19.671(2) Å) the compounds contain anionic clusters [Mo₆Cl₈ⁱ(OR^a)₆]^2? ( 1 : d(Mo—Mo) 2.608(1) Å to 2.611(1) Å, d(Mo—Cl) 2.489(1) Å to 2.503(1) Å, d(Mo—O) 2.046(4) Å; 2 : d(Mo—Mo) 2.602(3) Å to 2.608(3) Å, d(Mo—Cl) 2.471(5) Å to 2.4992(5) Å, d(Mo—O) 2.091(14) Å). Electronic interactions of the halide cluster and the phenolate ligands in [Mo₆Cl₈(OC₆H₅)₆]^2? is investigated by means of UV/VIS spectroscopy and EHMO calculations.     

2‐Imino‐3‐allyl‐benzothiazole as a π‐Ligand: Synthesis and Crystal Structure of [(CuCl)C10H10SN2], [C10H11SN2+]2[Cu2Cl4]2−, and [C10H11SN2+]2[Cu2Br4]2− π‐Compounds

The reaction of 2‐amino‐benzothiazole with allyl bromide resulted in a mixture of 2‐imino‐3‐allyl‐benzothiazole and 2‐imino‐3‐allyl‐benzothiazolium bromide.Using such a mixture and copper(II) chloride in acetonitrile solution in alternating‐current electrochemical synthesis crystals of the [(CuCl)C₁₀H₁₀SN₂] ( I ) have been obtained. The same procedure, performed in ethanol solution, has led to formation of [C₁₀H₁₁SN₂⁺]₂[Cu₂Cl₄]^2? ( II ). In the same manner the bromine derivative [C₁₀H₁₁SN₂⁺]₂[Cu₂Br₄]^2? ( III ) has been synthesized. All three compounds were X‐ray structurally investigated. I :monoclinic space group P2₁/n, a = 13.789(6), b = 6.297(3), c = 13.830(6) Å, β = 112.975(4)°, V = 1105.6 (9) ų, Z = 4 for CuCl·C₁₀H₁₀ SN₂ composition. Compounds II and III are isomorphous and crystallize in triclinic space group. II a = 7.377(3), b = 8.506(3), c = 9.998(4) Å, α = 79.892(10)°, β = 82.704(13)°, γ = 78.206(12)°, V = 601.9(4) ų, Z = 1. III a = 7.329(2), b = 8.766(3), c = 10.265(3) Å, α = 79.253(9)°, β = 82.625(9)°, γ = 77.963(9)°, V = 630.9(3) ų, Z = 1. In the structure I [(CuCl)C₁₀H₁₀SN₂] building blocks are bound into infinitive spiral‐like chains via strong N‐H..Cl hydrogen bonds. In the zwitter‐ionic II and III compounds copper and halide atoms form centrosymmetric [Cu₂X₄]^2? anions, which are interconnected via N‐H..X hydrogen bonds into infinite butterfly‐like chains. The strongest Cu‐(C=C) π‐interaction has been observed in structure I , where copper possesses coordination number 3. Increasing copper coordination number to 4 in II as well as replacing chlorine atoms by bromine ones in III suppresses markedly this interaction.     

Neue Halogenochalkogen(IV)‐Säuren: [H3O(Benzo‐18‐Krone‐6)]2[Te2Br10] und [H5O2(Dibenzo‐24‐Krone‐8)]2[Te2Br10]

Novel Halogenochalcogeno(IV) Acids: [H₃O(Benzo‐18‐Crown‐6)]₂[Te₂Br₁₀] and [H₅O₂(Dibenzo‐24‐Crown‐8)]₂[Te₂Br₁₀] Systematic studies on halogenochalcogeno(IV) acids containing tellurium and bromine led to the new crystalline phases [H₃O(Benzo‐18‐Crown‐6)]₂[Te₂Br₁₀] ( 1 ) and [H₅O₂(Dibenzo‐24‐Crown‐8)]₂[Te₂Br₁₀] ( 2 ). The [Te₂Br₁₀]^2‐ anions consists of two edge‐sharing distorted TeBr₆ octahedra, the oxonium cations are stabilized by crownether. ( 1 ) crystallizes in the monoclinic space group P2₁/n with a = 14.520(5) Å, b = 22.259(6) Å, c = 16.053(5) Å, β = 97.76(3)° and Z = 4, whereas ( 2 ) crystallizes in the triclinic space group with a = 11.005(4) Å, b = 12.103(5) Å, c = 14.951(6) Å, α = 71.61(3)°, β = 69.17(3)°, γ = 68.40(3)° and Z = 1.     

Chloroselenate(IV): Darstellung,Struktur und Eigenschaften von [As(C6H5)4]2Se2Cl10 und [As(C6H5)4]Se2Cl9

Chloroselenates(IV): Synthesis, Structure, and Properties of [As(C₆H₅)₄]₂Se₂Cl₁₀ and [As(C₆H₅)₄]Se₂Cl₉ The Se₂Cl₁₀^2? and Se₂Cl₉^? anions were prepared, as the first dinuclear haloselenates(IV), from the reaction of (SeCl₄)₄ with stoichiometric quantities of chloride ions in POCl₃ solutions; they were isolated as yellow crystalline As(C₆H₅)₄⁺ salts. Complete X-ray structural analyses at ?130°C of [As(C₆H₅)₄]₂Se₂Cl₁₀ ( 1 ) (space group P1 , a = 10.296(7), b = 11.271(6), c = 12.375(8) Å, = 74.17(5)°, α = 81.38(5)°, β = 67.69(4)°, V = 1276 ų) and of [As(C₆H₅)₄]Se₂Cl₉ ( 2 ) (space group P2₁/n, a = 12.397(5), b = 17.492(6), c = 14.235(4) Å, α 93.25(3)°, V = 3082 ų) show in both cases two distorted octahedral SeCl₆ groups connected through a common edge in 1 and a common face in 2 . The terminal Se? Cl bonds (average 2.317 Å in 1 , 2.223 Å in 2 ) are much shorter than the Se? Cl bridges (av. 2.661 Å in 1 , 2.652 Å in 2 ). The stereochemical activity of the Se^IV lone electron pair causes severe distortion of the central Se₂Cl₂ ring in the centrosymmetric Se₂Cl₁₀^2? ion. The vibrational spectra of the anions are reported.     

Crystal structure of tris(ethylenediamine)cobalt(III) (aqua)hexachloromercurate(II) chloride [Co(En)3]2[Hg2(H2O)Cl6]Cl4

The compound [Co(En)₃]₂[Hg₂(H₂O)Cl₆]Cl₄ (I, En is ethylenediamine) has been synthesized and studied by X-ray diffraction. The crystals of I (a = 21.8745(14) Å, b = 10.6008(6) Å, c=15.4465(12) Å, space group Pna2₁) consist of tris(ethylenediamine)cobalt(III) complexes (the unit cell contains two [Co(En)₃]³⁺ cations of opposite chirality). [Hg₂(H₂O)Cl₆]^2? anions, and isolated chloride ions. The complex anion consists of the tetrahedral [HgCl₄]^2? group (Hg-Cl, 2.44–2.56 Å) and the hydrated molecule [Hg(H₂O)Cl₂] (Hg-Cl, 2.301 and 2.308 Å; Hg-O, 2.788 Å) combined by weak Hg-Cl interactions (2.915 and 3.220 Å).     

Darstellung, 11B-NMR-, Schwingungsspektren und Kristallstruktur von [(C5H5N)2CH2][1-(O2N)B10H9]

Preparation, ¹¹B NMR, Vibrational Spectra, and Crystal Structure of [(C₅H₅N)₂CH₂][1-(O₂N)B₁₀H₉] By reaction of [B₁₀H₁₀]^2? in aqueous acetonitrile with a saturated solution of NO₂ in dichloromethane [1-(O₂N) · B₁₀H₉]^2? and [B₁₀H₉(NO)B₁₀H₉]^3? are formed which can be separated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose from the starting compound. The X-ray structure determination of [(C₅H₅N)₂CH₂][1-(O₂N)B₁₀H₉] (triclinic, space group P1 , a = 7.1530(9), b = 8.3753(8), c = 15.198(2) Å, α = 96.00(1), β = 95.48(1), γ = 95.60(1)°, Z = 2) reveals the coordination of the NO₂ group via N with a B1? N distance of 1.535(5) Å and an O2? N? O1 angle of 119.3(3)°. The ¹¹B NMR spectrum exhibits the characteristic feature (1 : 1 : 4 : 4) of an apical monosubstituted B₁₀ cluster with a strong downfield shift of the ipso-B atom at +13.4 ppm. The IR and Raman spectra show strong NO stretching vibrations at 1381 und 1420 cm^?1.     

Darstellung und Kristallstruktur von [P(C6H5)4][2,9-{N,N′-(2-NH?(C5H4N))}B10H8]

Synthesis and Crystal Structure of [P(C₆H₅)₄][2,9-{N,N′-(2-NH? (C₅H₄N))}B₁₀H₈] [N(C₄H₉)₄]₂[B₁₀H₁₀] reacts with 2-aminopyridine forming a product mixture from which [2,9-{N,N′-(2-NH? (C₅H₄N))}B₁₀H₈]^? can be isolated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose. The crystal structure of [P(C₆H₅)₄][2,9-{N,N′-(2-NH? (C₅H₄N))}B₁₀H₈] (triclinic, space group P1 , a = 10.1103(9), b = 11.5665(9), c = 14.877(2) Å, α = 102.600(8), β = 107.567(8) und γ = 96.487(7)°, Z = 2) reveals the bonding of 2-NH₂-(C₅H₄N) via both N atoms to vicinal B atoms of the two square planes of the B₁₀ cluster (B2? N1 = 1,541(7) und B9? N2 = 1.505(7) Å) forming a five-membered ring.     

Synthese,Kristallstruktur und thermischer Abbau von Fluoroaluminaten der Zusammensetzung (NH4)[M(H2O)6][AlF6] (M = Zn,Ni), [Zn(H2O)6][AlF5(H2O)] und (PyH)4[Al2F10] · 4 H2O

Synthesis, Crystal Structure and Thermal Behaviour of Fluoroaluminates of the Composition (NH₄)[M(H₂O)₆](AlF₆) (M = Zn, Ni), [Zn(H₂O)₆][AlF₅(H₂O)], and (PyH)₄[Al₂F₁₀] · 4 H₂O Four new fluoroaluminates were obtained from fluoroacidic solutions of respective metal salts. The compounds of zinc ( I a : P2₁/c, a = 12.688(3), b = 6.554(1), c = 12.697(3) Å, β = 95.21(3)°, V = 1051.5(4) ų, Z = 4) and nickel ( I b : P2₁/c, a = 12.685(3), b = 6.517(1), c = 12.664(2)Å, β = 94.55(2)°, V = 1043.6(4) ų, Z = 4) are isotypic and represent a new structure type consisting of two different cations, NH₄⁺ and [M(H₂O)₆]²⁺ and [AlF₆]^3–‐anions. [Zn(H₂O)₆][AlF₅(H₂O)] ( II : C2/m, a = 10.769(2), b = 13.747(3), c = 6.487(1)Å, β = 100.02(3)°, V = 945.7(3) ų, Z = 4) is characterized by a H₂O/F‐disorder in the [AlF₅(H₂O)]‐octahedra in two trans positions. In (PyH)₄[Al₂F₁₀] · 4 H₂O ( III : Cmc2₁, a = 15.035(3), b = 20.098(4), c = 12.750(4) Å, V = 5364(2) ų, Z = 8), bioctahedral [Al₂F₁₀]^4– anions have been found for the first time. The structures are described and discussed in comparison. The new compounds were used as precursors in order to obtain new AlF₃‐phases. However, the thermal decomposition did not result in the formation of any new metastable AlF₃‐phase. Instead, phase mixtures of either α‐AlF₃ and β‐AlF₃ or AlF₃ and MF₂ were obtained.     

Darstellung, 11B-NMR-, Schwingungsspektren und Kristallstruktur von (PPh4)[1-(NO)B10H9]

Synthesis, ¹¹B NMR, Vibrational Spectra, and Crystal Structure of (PPh₄)[1-(NO)B₁₀H₉] By reaction of (n-Bu₄N)₂[B₁₀H₁₀] in aqueous acetonitrile with NO₂ a reaction mixture is formed from which [1-(NO)B₁₀H₉]^– has been isolated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose. The X-ray structure determination of (PPh₄)[1-(NO)B₁₀H₉] (triclinic, space group P1, a = 7.6553(11), b = 13.179(2), c = 14.122(3) Å, α = 69.853(13), β = 82.445(14), γ = 87.230(13)°, Z = 2) reveals the coordination of the NO group via N in an apical position of the B₁₀ cluster with B1–N = 1.457(5) and N–O = 1.101(4) Å. The ¹¹B NMR spectrum exhibits the characteristic feature (1 : 1 : 4 : 4) of a in 1 position substituted B₁₀ cluster with a strong downfield shift of the ipso-B atom at +6.5 ppm. The IR and Raman spectra show a strong NO stretching vibration at 2219 cm^–1.     

Molybdänhalogenidcluster mit zwei terminalen Alkoholatliganden: Synthese und Kristallstrukturen von (C18H36N2O6Na)2[Mo6Cl12(OCH3)2] und (C18H36N2O6Na)2[Mo6Cl12(OC15H11)2] · 2C4H6O3

Molybdenum(II) Halide Clusters with two Alcoholate Ligands: Syntheses and Crystal Structures of (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₁₂(OCH₃)₂] and (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₁₂(OC₁₅H₁₁)₂] · 2C₄H₆O₃ . Reaction of Mo₆Cl₁₂ with two equivalents of sodium methoxide in the presence of 2,2,2-crypt yields (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₁₂(OCH₃)₂] ( 1 ), which can be converted to (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₁₂(OC₁₅H₁₁)₂] · 2C₄H₆O₃ ( 2 ) by metathesis with 9-Anthracenemethanole in propylene carbonate. As confirmed by X-ray single crystal structure determination ( 1 : C2/m, a=25.513(8) Å, b=13.001(3) Å, c=10.128(3) Å, β=100.204(12)°; : C2/c, a=15.580(5) Å, b=22.337(5) Å, c=27.143(8) Å, β=98.756(10)°) the compounds contain anionic cluster units [Mo₆ClCl(OR^a)₂]^2? with two alcoholate ligands in terminal trans positions ( 1 : d(Mo—Mo) 2.597(2) Å to 2.610(2) Å, d(Mo—Clⁱ) 2.471(3) Å to 2.493(4) Å, d(Mo—Cl^a) 2.417(8) Å and 2.427(8) Å, d(Mo—O) 2.006(13) Å; 2 : d(Mo—Mo) 2.599(3) Å to 2.628(3), d(Mo—Clⁱ) 2.468(8) Å to 2.506(7) Å, d(Mo—Cl^a) 2.444(8) Å and 2.445(7) Å, d(Mo—O) 2.012(19) Å).     

Evidence for the Solid State Structural Transformation of the Network-Type Decavanadate (NC7H14)4[H2V10O28] into a Lamellar Topology (NC7H14)[V4O10]

The hydrothermal synthesis and the structural determinations of two vanadium oxides interleaved by quinuclidinium cations are described; (NC₇H₁₄)₄[H₂V₁₀O₂₈] is an anhydrous diprotonated decavanadate (triclinic, P 1 (n° 2), a = 9.701(1) Å, b = 10.839(1) Å, c = 12.7566(2) Å, α = 109.13(1)°, β = 112.09(1)°, γ = 92.17(2)°) and (NC₇H₁₄)[V₄O₁₀] a layered compound (orthorhombic, C mcm (n° 63), a = 18.4461(5) Å, b = 6.6619(2) Å, c = 11.7967(2) Å). Thermodiffractometry shows that the decavanadate irreversibly transforms at 230 °C into the layered compound without any amorphous intermediate state.     

Neue dimere Goldselenolate: Darstellung und strukturelle Charakterisierung von [(n-C4H9)4N]2[AuSSeCC(CN)2]2 und [(n-C4H9)4N]2[AuSe2CC(CN)2]2

New Dimeric Gold Selenolates: Preparation and Characterization of [(n-C₄H₉)₄N]₂[AuSSeC ? C(CN)₂]₂ and [(n-C₄H₉)₄N]₂[AuSe₂C ? C(CN)₂]₂ The preparation and structural characterization of the dimeric Au^I complexes of 1,1-dicyanoethene-2,2-thioseleonlate (i-mnts) and 1,1-dicyanoethene-2,2-diselenolate (i-mns), isolated as Bu₄N salts, are described. They are isotype (monoclinic, space group P2₁/c, Z = 2) with lattice parameters: (Bu₄N)₂[Au(i-mnts)]₂; a = 14.078(3) Å, b = 8.912(3) Å, c = 20.142(4) Å, β = 106.32(5)°; (Bu₄N)₂[Au(i-mns)]₂; a = 13.998(3) Å, b = 9.125(3) Å, c = 20.039(2) Å, β = 105.12(5)°. Ab initio Hartree-Fock calculations based on the experimentally determined structure yield a positive value of the Au? Au bonding order suggesting weak bonding interactions between the d¹⁰ metal centres.     

Li6+2x[B10Se18]Sex (x ≈ 2), ein ionenleitendes Doppelsalz

Li_6+2x[B₁₀Se₁₈]Se_x (x ≈ 2), an Ion‐conducting Double Salt Li_6+2x[B₁₀Se₁₈]Se_x (x ≈ 2) was prepared in a solid state reaction from lithium selenide, amorphous boron and selenium in evacuated carbon coated silica tubes at a temperature of 800 °C. Subsequent cooling from 600 °C to 300 °C gave amber colored crystals with the following lattice parameters: space group I2/a (at 173 K); a = 17.411(1) Å, b = 21.900(1) Å, c = 17.820(1) Å, β = 101.6(1)°. The crystal structure contains a well‐defined polymeric selenoborate network of composition ([B₁₀Se₁₆Se_4/2]^6?)_n consisting of a system of edge‐sharing [B₁₀Se₁₆Se_4/2] adamantanoid macro‐tetrahedra forming large channels in which a strongly disorderd system of partial occupied Li⁺ cations and additional disordered Se^2? anions is observed. The crystal structure of the novel selenoborate is isotypic to Li_6+2x[B₁₀S₁₈]S_x (x ≈ 2) [1]. X‐ray and ⁷Li magic‐angle spinning NMR data suggest that the site occupancies of the three crystallographically distinct lithium ions exhibit a significant temperature dependence. The lithium ion mobility has been characterized by detailed temperature dependent NMR lineshape and spin‐lattice relaxation measurements.     

Darstellung und Kristallstrukturen von Dipyridiniomethan-Monohalogenohydro-closo-Dodecaboraten(2−), [(C5H5N)2CH2][B12H11X]; X = Cl,Br, I

Preparation and Crystal Structures of Dipyridiniomethane Monohalogenohydro-closo-Dodecaborates(2?), [(C₅H₅N)₂CH₂][B₁₂H₁₁X]; X = Cl, Br, I [B₁₂H₁₂]^2? reacts with dihalogenomethanes CH₂X₂ in presence of trifluoro acetic acid, yielding the monohalogenododecaborates [B₁₂H₁₁X]^2? (X = Cl, Br, I), which are separated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose from the starting compound and higher halogenated products. The X-ray structure determinations of [(C₅H₅N)₂CH₂][B₁₂H₁₁Cl] · 2(CH₃)₂SO (orthorhombic, space group Pnma, a = 17.351(6), b = 16.034(5), c = 9.659(2) Å, Z = 4) and of the isotypic bromo and iodo compounds [(C₅H₅N)₂CH₂][B₁₂H₁₁X] (monoclinic, space group P2₁/n, Z = 4; for X = Br: a = 7.339(2), b = 15.275(3), c = 16.761(4) Å, β = 96.80(2)°; for X = I: a = 7.4436(8), b = 15.3510(8), c = 16.9213(16) Å, ß = 97.326(7)°) exhibit crystal lattices build up by columns of substituted boron clusters and angular dications [(C₅H₅N)₂CH₂]²⁺ orientated along the shortest axis which are assembled to alternating layers.