Strukturen ladungsgestörter oder räumlich überfüllter Moleküle. 15. Tetracyanethen-Natrium-Dimethoxyethan

Structures of Charge-Perturbed or Sterically Overcrowded Molecules. 16. Tetracyanoethylene Sodium Dimethoxyethane The Single crystal structure of [(NC)₂C? C(CN)₂?·Na⊕(H₃CO? CH₂CH₂? OCH₃)]∞ reveals two formula units within the triclinic (P1 ) unit cell. The tetracyanoethylene radical anions are arranged along parallel double layers, which are shifted relative to each other, and in between which are interspersed the sodium counter cations and their dimethoxyethane ligands. The distances within the double layers amount to 300 pm and the ones between them to 385 pm. The six-fold coordinated Na⊕ centers are surrounded by four radical anions with contact distances Na…?N between 250 and 254 pm as well as by a twofold solvent ligand with Na…?O of 238 and 241 pm. Due to the electron transfer to the acceptor molecule, its (NC)₂C-halves twist by 8° and the bond lengths of the N?C? C subunits, bent by each 3°, are shortened up to 2 pm. The structural parameters are compared to those of the analogous potassium salt [TCNE^?K^⊕DME], of the dianion , of the sodium salts [(NC)₃C^?Na^⊕]∞ as well as [(NC)₂C? C(CHCH)₂? C(CN)₂^?Na^⊕]_∞ and, in addition, are discussed based on geometry-optimized MNDO calculations.     

Strukturen und Molekül-Eigenschaften ladungsgestörter Moleküle. 52. Mitteilung. 2, 3-Diphenylchinoxalin-Radikalanionen in Lösung und im Kristall

Structures and Molecular Properties of Charge-Pertubed Molecules. 2, 3-Diphenylquinoxaline Radical Anions in Solution and in Crystals The Na⊕ and K⊕ radical-ion salts of 2, 3-diphenylquinoxaline seem to be (according to a structural database search) among the first ones of N-heterocyclic radical anions in crystals. The one-electron reduction in aprotic 1, 2-dimethoxyethan (DME) solution at metal mirrors and the crystallization under Ar have been preceded by cyclovoltammetric (CV) and ESR/ENDOR measurement. The first electron insertion at ?1.63 V proves to be reversible, whereas the irreversible second step, which is accompanied by an overcrossing of the CV line, can be rationalized by an ‘ECE-DISP’ mechanism via a dianion redox disproportionation. The ENDOR spectrum resolves four ¹H couplings and allows to simulate the ESR spectrum including the ¹⁴N hyperfine splittings. Both dark-blue single crystals of the radical ion salts $[2,3{\rm - diphenylquinoxaline}^{{.} \ominus} {\rm Met}^ \oplus ({\rm DME})]^.$ show unexpected similarities for Met⊕ = Na⊕, K⊕ despite the 36-pm difference in their ionic radii. The largest structural changes inflicted by the one-electron reduction of the N-heterocyclic molecule are observed in the vicinity of the N-centers bearing the highest effective nuclear charge. The DME-chelated metal cations coordinate at the N electron pairs and form Met⊕(DME)-bridged polymer chains of the radical anion, which are differently ondulated in the Na⊕ and K⊕ radical anion salts. The take-home lesson suggests that many more N-heterocyclic molecules might be analogously reduced under optimized conditions and isolated as single crystals.     

Titantetrafluorid – Eine überraschend einfache Kolumnarstruktur

Titanium Tetrafluoride – a Surprising Simple Column Structure For the first time single crystals of TiF₄ have been obtained by solvothermal decomposition of (O₂)₂Ti₇F₃₀ in anhydrous HF. The colourless, transparent needles crystallize orthorhombic in spacegroup Pnma–D (No. 62) with a = 2 281.1, b = 384.8, c = 956.8 pm, Z = 12. The new type of structure is dominated by isolated columns of corner-linked TiF₆-octahedra.     

Photoelektronen-Spektren und Moleküleigenschaften. 133 [1, 2]. Trifluormethyldisulfan und Derivate F3CSSX (X  CF3, F,Cl, Br)

Photoelectron Spectra and Molecular Properties. 133. Trifluoromethyldisulfane and Derivates F₃CSSX (X?CF₃, F, Cl, Br) The He(I) photoelectron spectra of trifluoromethyldisulfane F₃CSSH and its derivatives F₃CSSX (X?CF₃, F, Cl, Br) are assigned by Koopmans correlations, IE = ?ε, with MNDO eigenvalues and by radical cation state comparison. Of special interest are the n/n splittings, which amount to 1.15 eV F₃C? SS? F or 0.87 eV in F₃? SS? Cl, and the dependance of which on the dihedral angle ω(XS? SX), on the SS bond length and on the acceptor effect of the F₃C substituents is discussed.     

Kristall- und Molekülstruktur von SbI3 · 9S3 (9S3 = 1,4,7-Trithiacyclononan)

Crystal and Molecular Structure of SbI₃ · 9S3 (9S3 = 1.4.7-Trithiacyclononane) . SbI₃ forms a 1:1 adduct with 1.4.7-trithiacyclononane. The crystal structure exhibits discrete complexes with a distorted octahedral coordination of antimony(III). In comparison with molecular SbI₃ the Sb? I distances are elongated from 271.9 to 290.4 pm (mean). The mean value of the Sb? S distances is 287.5 pm. The planes through iodine and sulfur atoms, respectively, are nearly coplanar. There is no significant stereochemical influence of the Sb(III) lone pair.     

有机-无机自由基盐(DBTTF)6PMo12O40·2H2O的合成、性质和晶体结构

用电解法制备了有机-无机自由基盐(DBTTF)6PMo12O40·2H2O.用红外光谱、电子光谱和电子自旋共振谱进行了表征,测定了其磁化率、导电性和单晶的晶体结构,该晶体属三斜晶系,P1空间群,晶胞参数为a=1.378 7(7)nm,b=1.420 4(2)nm,c=1.570 2(2)nm,α=104.570(8)°,β=103.41(2)°,γ=95.80(2)°,V=2.853(2)nm3,Z=1,Dc=2.142 Mg·m-3,R=0.072 7.     

Ti9Se2 – Eine Verbindung mit kolumnaren [Ti9]-Baueinheiten

The Metal-Rich Titanium Selenide Ti₉Se₂ The new compound Ti₉Se₂ has been prepared as hitherto most metal-rich phase in the system titanium-selenium. It crystallizes in the orthorhombic space group Pbam (No. 55) with a = 691.7(2), b = 1 550.5(9), c = 345.4(2) pm. The structure consists of [Ti₉]-strings which are described within the concept of condensed clusters. The Se atoms are coordinated by tricapped trigonal prisms of Ti atoms.     

Untersuchungen über Zinn(IV)-alkoxide. I Kristall- und Molekülstruktur des Zinn(IV)-isopropanolat-Isopropanolsolvats,Sn(OiPr)4 · i-PrOH

Investigations into Tin(IV) Alkoxides. I. Crystal and Molecular Structure of Tin(IV)-isopropoxide-Isopropanol Solvate, Sn(OⁱPr)₄ · i-PrOH The isopropanol complex of tin(IV)-isopropoxide has been prepared by the reaction of tin tetrachloride with sodium isopropoxide. The compound forms colourless, moisture sensitive crystals, which in dry air easily release the coordinated solvent molecules. The crystal and molecular structure of Sn(OⁱPr)₄ · i-PrOH has been determinated by single crystal X-ray diffraction. The compound crystallizes in the monoclinic space group P2₁/c with a = 1174.2(5), b = 1428.5(3), c = 1234.1(3) pm, β = 95.37(1)° and Z = 4. The crystal structure consists of discrete, dimeric molecules in which the two tin atoms are bridged by two alkoxide groups. The octahedral coordination sphere of each tin atom is completed by one solvent molecule which, in addition, forms one hydrogen bridge to an alkoxide group of the neighboring tin atom.     

Über Neue Oxoruthenate vom Typ der 6 L-Perowskite: Ba3SrRu2−xTaxO9 (x = 0,8 und 1,4) mit einem Beitrag über Ba3CaRu2O9

On Novel Oxoruthenates of the 6 L-Perovskite Type: Ba₃SrRu_2?xTa_xO₉ (x = 0.8 and 1.4) with a Comment on Ba₃CaRu₂O₉ Single crystals of the phases Ba₃SrRu_2?xTa_xO₉ [(I): x = 0.8 and (II): x = 1.4] and the compound (III): Ba₃CaRu₂O₉ were prepared by a BaCl₂ flux and investigated by X-ray methods. (I)–(III) crystallizes with hexagonal symmetry space group P6 2c with lattice constants: (I) a = 6.003 Å; c = 15.227 Å; (II) a = 5.988 Å; c = 15.220 Å and (III) a = 5.891 Å; c = 14.571 Å. The crystal structures of these substances corresponds to the 6 layer perovskites with the stacking sequence (hcc)₂. All of them show a so far not described slightly distorted oxygen framework caused by the Sr²⁺ and Ca²⁺ ions.     

A structural study of Si6‐ring‐containing [Si6Cl14]2− chlorosilicates

The crystal structures of four substituted‐ammonium dichloride dodecachlorohexasilanes are presented. Each is crystallized with a different cation and one of the structures contains a benzene solvent molecule: bis(tetraethylammonium) dichloride dodecachlorohexasilane, 2C₈H₂₀N⁺·2Cl⁻·Cl₁₂Si₆, (I), tetrabutylammonium tributylmethylammonium dichloride dodecachlorohexasilane, C₁₆H₃₆N⁺·C₁₃H₃₀N⁺·2Cl⁻·Cl₁₂Si₆, (II), bis(tetrabutylammonium) dichloride dodecachlorohexasilane benzene disolvate, 2C₁₆H₃₆N⁺·2Cl⁻·Cl₁₂Si₆·2C₆H₆, (III), and bis(benzyltriphenylphosphonium) dichloride dodecachlorohexasilane, 2C₂₅H₂₂P⁺·2Cl⁻·Cl₁₂Si₆, (IV). In all four structures, the dodecachlorohexasilane ring is located on a crystallographic centre of inversion. The geometry of the dichloride dodecachlorohexasilanes in the different structures is almost the same, irrespective of the cocrystallized cation and solvent. However, the crystal structure of the parent dodecachlorohexasilane molecule shows that this molecule adopts a chair conformation. In (IV), the P atom and the benzyl group of the cation are disordered over two sites, with a site‐occupation factor of 0.560 (5) for the major‐occupied site.     

Compounds with Cluster Cations together with Cluster Anions [(M6X12)(EtOH)6]2+ besides [(Mo6Cl8)Cl4X2]2– (M = Nb,Ta; X = Cl,Br) – Synthesis and Crystal Structures

Compounds consisting of both cluster cations and cluster anions of the composition [(M₆X₁₂)(EtOH)₆][(Mo₆Cl₈)Cl₄X₂] · n EtOH · m Et₂O (M = Nb, Ta; X = Cl, Br) have been prepared by the reaction of (M₆X₁₂)X₂ · 6 EtOH with (Mo₆Cl₈)Cl₄. IR data are given for three compounds. The structures of [(Nb₆Cl₁₂)(EtOH)₆][(Mo₆Cl₈)Cl₆] · 3 EtOH · 3 Et₂O 1 and [(Ta₆Cl₁₂)(EtOH)₆][(Mo₆Cl₈)Cl₆] · 6 EtOH 2 have been solved in the triclinic space group P1 (No. 2). Crystal data: 1 , a = 10.641(2) Å, b = 13.947(2) Å, c = 15.460(3) Å, α = 65.71(2)°, β = 73.61(2)°, γ = 85.11(2)°, V = 2005.1(8) ų and Z = 1; 2 , a = 11.218(2) Å, b = 12.723(3) Å, c = 14.134(3) Å, α = 108.06(2)°, β = 101.13(2)°, γ = 91.18(2)°, V = 1874.8(7) ų and Z = 1. Both structures are built of octahedral [(M₆Cl₁₂)(EtOH)₆]²⁺ cluster cations and [(Mo₆Cl₈)Cl₆]^2– cluster anions, forming distorted CsCl structure types. The Nb–Nb and Ta–Ta bond lengths of 2.904 Å and 2.872 Å (mean values), respectively, are rather short, indicating weak M–O bonds. All O atoms of coordinated EtOH molecules are involved in H bridges. The Mo–Mo distances of 2.603 Å and 2.609 Å (on average) are characteristic for the [(Mo₆Cl₈)Cl₆]^2– anion, but there is a clear correlation between the number of hydrogen bridges to the terminal Cl and the corresponding Mo–Cl distances.     

Ternäre Hydroxide. I. Synthese,Struktur und Eigenschaften von Li2[Sn(OH)6] · 2 H2O

Ternary Hydroxides. I. Synthesis, Structure, and Properties of Li₂[Sn(OH)₆] · 2 H₂O Colourless crystals of Li₂[Sn(OH)₆] · 2 H₂O were synthesized by reaction of SnCl₄ with LiOH in aqueous solution. The crystal structure was determined from single crystal data. Li₂[Sn(OH)₆] · 2 H₂O: monoclinic, P2₁/n (Nr. 14), a = 502.3(1), b = 692.3(1), c = 1020.2(3) pm, β = 99.78(1)°, V = 349.6(2) · 10⁶ pm³, Z = 2, R/Rw = 0.0192/0.0472, N(I) > 2σ(I) = 1527, N(Par.) = 54. Within the crystal structure only slightly distorted octahedrally [Sn(OH)₆]^2? ions are bonded via hydrogen bonds with water molecules forming layers, which themselve are linked by tetrahedrally coordinated Li ions; the structure is in accordance with the IR-data and the results of the ¹¹⁹Sn solid state NMR-spectroscopy; the hydrat water is eliminated at 117.1°C, the condensation reaction – forming the ternary oxide – takes place at 257.7°C.     

Darstellung und Strukturen neuartiger Triphenylsilylund Triphenylgermyl‐substituierter Gallane und Oligogallane – [Ga3(GePh3)6]–, das erste lineare Trigallan

Chemistry of Gallium. 20. Synthesis and Structures of Novel Triphenylsilyl and Triphenylgermyl Substituted Gallanes and Oligogallanes – [Ga₃(GePh₃)₆]^–, the First Linear Trigallane From the raction of sonochemically prepared “GaI” with LiEPh₃ (E = Si, Ge) the compounds [Li(THF)₂][GaI(EPh₃)₃] (E = Si: 22 , E = Ge: 24 ), [Li(THF)₄][GaI(SiPh₃)₃] ( 23 ), [Li(THF)₄][Ga₂(SiPh₃)₅] ( 21 ) and [Li(THF)₄][Ga₃(GePh₃)₆] ( 25 ) as well as polymeric Li(THF)I ( 20 ) were obtained and structurally characterized. 21 is a monoanionic digallane, exhibiting a trigonal planar and a tetrahedrally coordinated gallium centre. 25 has a linear Ga₃ core, where the terminal gallium atoms bear three GePh₃‐groups, each. The central Ga atom is only 2‐coordinated. Thus, 25 may be a valuable hint to the formation of larger gallium clusters with “naked” gallium atoms. Derivatives of 21 and 25 have been studied by DFT methods.     

Ternäre Halogenide vom Typ A3MX6. II. Das System Ag3−xNaxYCl6: Synthese,Strukturen, Ionenleitfähigkeit

Ternary Halides of the A₃MX₆ Type. II. The System Ag_3?xNa_xYCl₆: Synthesis, Structures, Ionic Conductivity . The influence of the substitution of Ag⁺ by Na⁺ ions on the crystal structure and the ionic conductivity of Ag₃YCl₆ (stuffed LiSbF₆-type structure) has been investigated. The system Ag_3?xNa_xYCl₆ forms a complete solid solution. The stuffed LiSbF₆-type structure is stable for all compositions. For compounds with Na⁺ contents of x > 1.67, the cryolite-type structure is observed as the high-temperature form. The transition temperature decreases steadily with increasing Na⁺ content. The “end member” phase Na₃YCl₆ transforms at 243 K from the monoclinic cryolite-type structure to the stuffed LiSbF₆-type structure (trigonal, R3 ; a = 697.3(1), c = 1 868.4(14) pm, Z = 3; R = 0.094; R_w = 0.069). The crystal structures of Ag_1.3Na_1.7YCl₆ (trigonal, R3 ; a = 691.5(2), c = 1 853.7(6) pm, Z = 3; R = 0.099, R_w = 0.081) and AgNa₂YCl₆ (trigonal, R3 ; a = 691.7(1), c = 1 853.9(5) pm, Z = 3; R = 0.099, R_w = 0.064) have also been determined. Both chlorides crystallize like Ag₃YCl₆ and Na₃YCl₆-I in the stuffed LiSbF₆-type structure. The monovalent cations, Ag⁺ and Na⁺, are distributed over the five octahedral voids that are occupied by the Ag⁺ ions alone in Ag₃YCl₆. The ionic conductivity for compounds within the solid solution Ag_3?xNa_xYCl₆ decreases with increasing Na⁺ content. The values for Na₃YCl₆ (σ = 1 · 10^?6 Ω^?1 cm^?1 at T = 500 K) are by 2.5 to 3.5 orders of magnitude smaller than those for Ag₃YCl₆ (σ = 6 · 10^?4 Ω^?1 cm^?1 at T = 500 K).     

Stable N,N’-Diarylated Dihydrodiazaacene Radical Cations

Three stable N,N’-diarylated dihydroazaacene radical cations were prepared by oxidation of neutral N,N’-diarylated dihydroazaacenes synthesized via palladium-catalyzed Buchwald-Hartwig aminations of aryl iodides with N,N’-dihydroazaacenes. Both neutral as well as oxidized species were investigated via UV-vis spectroscopy, single crystal analysis, and DFT calculations. All the radical cations are surprisingly stable—their absorption spectra in dichloromethane remain unchanged in ambient conditions for at least 24 hours.     

Magnetic properties of a new cobalt hydrogen vanadate with a dumortierite‐like structure: Co13.5(OH)6(H0.5VO3.5)2(VO4)6

The magnetic properties of a novel cobalt‐based hydrogen vanadate, Co_13.5(OH)₆(H_0.5VO_3.5)₂(VO₄)₆, are reported. This new magnetic material was synthesized in single‐crystal form using a conventional hydrothermal method. Its crystal structure was determined from single‐crystal X‐ray diffraction data and was also characterized by scanning electron microscopy. Its crystal framework has a dumortierite‐like structure consisting of large hexagonal and trigonal channels; the large hexagonal channels contain one‐dimensional chains of face‐sharing CoO₆ octahedra linked to the framework by rings of VO₄ tetrahedra, while the trigonal channels are occupied by chains of disordered V₂O₄ pyramidal groups. The magnetic properties of this material were investigated by DC magnetic measurements, which indicate the occurrence of antiferromagnetic interactions.     

Organoruthenaborane Chemistry. X. The SM2-catalysed formation of [ l-(η6-C6Me6)-isocloso-RuB9H9], and some B-phenylamino derivatives. NMR and X-ray diffraction studies

The action of SMe₂ on the ten-vertex nido-ruthenaborane [6-(η⁶-C₆Me₆)RuB₉H_l3] ( 1 ) provides a high-yield route to the unsubstituted isocloso-ruthenaborane [1-(η⁶-C₆Me₆)RuB₉H₉] (2). The benzene analogue [1-(η⁶-C₆Me₆)RuB₉H₉] is prepared similarly. By contrast, reaction of (1) with PhNH₂ gives a variety of B-phenylamino isocloso derivatives, including orange crystals of [1-(η⁶-C₆Me₆)-2-(PhNH)-isocloso-1-RuB 9 H₈] ( 3 ), red-orange [1-(η⁶-C₆Me₆)-2,3-(PhNH)₂-isocloso-1-RuB₉H₇] ( 4 ) and dark-red [1-(η⁶-C₆Me₆)-5,6,7-(PhNH)₃-isocloso-1-RuB₉H₆] ( 5 ). Detailed ¹H and ¹¹B nmr properties of these various compounds are described. The structure of ( 3 ) has been established by a single-crystal X-ray diffraction study of the solvate [1-(η⁶-C₆Me₆)-2-(PhNH)-isocloso-1-RuB₉H₈] · 1/2 CH₂Cl₂; the crystals were monoclinic, space group C2/c, with a = 1895.1(3), b = 1556.6(3), c = 1716.4(3) pm, β = 104.37(1)° and z = 8.     

Zur Chemie des Dimesityleisens. VIII. Lösungsverhalten von Tetramesityldieisen und die Kristallstruktur eines Dimethoxyethan-Addukts

Chemistry of Dimesityl Iron. VIII Solution Behaviour of Tetramesityldiiron and Crystal Structure of Dimesityl(dimethoxyethane)iron The dimer dimesityliron yields in polar solvents solvated monomers. The adduct with dimethoxyethane was isolated and characterized by X-ray structure determination.     

Beiträge zur Kristallchemie der Urantelluride. I. Die Kristallstruktur des α-Urantritellurids

Contributions to the Crystal Chemistry of Uranium Tellurides. I. The Crystal Structure of α-Uranium Tritelluride Single crystals of the title compound up to a size of 8 mm were available via chemical transport reactions with TeBr₄ as transporting agent starting from the elements. The analysis by atomic emission spectrometry gave UTe_3.0(1). By X-ray single crystal structure analysis we found that UTe₃ crystallizes monoclinic (space group P 2₁/m, Z = 2) with a = 609.7(1) pm, b = 422.06(4) pm, c = 1031.2(1) pm and β = 97.87(1)º in the ZrSe₃-structure type. The layer structure is built up by bicapped trigonal prisms.