Chloroaqua Complexes [M3S4(H2O)9?xClx](4?x)+ (M = Mo, W; x = 4, 6, 7) and Their Supramolecular Compounds with Cucur[8]uril

Compounds of trigonal cluster chloroaqua complexes with cucurbit[8]uril were synthesized by slowly evaporating HCl solutions of chalcogenides heterometallic cubane cluster complexes of molybdenum and tungsten with cucurbit[8]uril in air; the complexes were characterized by X-ray diffraction analysis: (H₃O)₈[Mo₃S₄(H₂O)_2.5Cl_6.5]₂Cl(PdCl₄)·(C₄₈H₄₈N₃₂O₁₆)· 29H₂O (a = 13.3183(17) Å, b = 13.7104(18) Å, c = 18.225(3) Å; α = 80.263(3)°, β = 77. 958(3)°, γ = 87.149(4)°, V = 3207.4(7) ų, space group P , Z = 1, ρ(calc) = 1.900 g/cm³), (H₃O)₄ [Mo₃S₄(H₂O)₃Cl₆]₂·(C₄₈H₄₈N₃₂O₁₆)₃·68H₂O (a = 21.413(6) Å, c = 49.832(10) Å; γ = 120°, V = 19788(8) ų, space group R , Z = 3, ρ(calc) = 1.695 g/cm³), (H₃O)₆ [Mo₃S₄(H₂O)₃Cl₆]₂Cl₂·(C₄₈H₄₈N₃₂O₁₆)·12H₂O (a = 15.881(2) Å, b = 17.191(2) Å, c = 23.276(4) Å; β = 98.865(15)°, V = 6278.7(15) ų, space group P2₁/c, Z = 2, ρ(calc) = 1.638 g/cm³), [W₃S₄(H₂O)₅Cl₄]₂·(C₄₈H₄₈N₃₂O₁₆)₃·35H₂O (a = 21.038(3) Å; α = 61.20(1)°, V = 6762.0(14) ų, space group R , Z = 1, ρ(calc) = 1.582 g/cm³). The [Mo₃S₄(H₂O)₃Cl₆]²⁻ anion complex was isolated as three geometrical isomers.Original Russian Text Copyright © 2004 by E. V. Chubarova, D. G. Samsonenko, H. G. Platas, F. M. Dolgushin, A. V. Gerasimenko, M. N. Sokolov, Z. A. Starikova, M. Yu. Antipin, and V. P. Fedin__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 1049–1058, November–December, 2004.     

Metabolites of the marine fungus <Emphasis Type="Italic">Humicola fuscoatra</Emphasis> KMM 4629

A new sesquiterpene of the caryophyllene series, fuscoatrol A (1), and known compounds, 11-epiterpestacin (2) and -nitropropionic acid (3), were isolated from the marine fungus Humicola fuscoatra (Traaen) KMM 4629 associated with the Kuril colonial ascidium. The structure of 1 was established on the basis of X-ray diffraction data and 2D NMR spectroscopy. The antimicrobial and cytotoxic activities of compounds 1–3 were studied.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2534–2537, November, 2004.     

Tetraphenylbismuth 2,4-Dimethylbenzenesulfonate: Synthesis and Structure

Tetraphenylbismuth 2,4-dimethylbenzenesulfonate was synthesized by reacting pentaphenylbismuth or bromine with diphenylbismuth 2,4-dimethylbenzenesulfonate and its structure was established using X-ray diffraction analysis. The Bi atom has a distorted trigonal bipyramidal coordination. The Bi–C bond lengths are equal to 2.199(4)–2.227(4) Å the Bi–O distance and axial CBiO angle are equal to 2.665(3) Å and 174.2(1)°, respectively.     

Triphenylbismuth Bis(2,4,6-Tribromophenoxide): Synthesis and Structure

A reaction of triphenylbismuth with 2,4,6-tribromophenol and hydrogen peroxide (molar ratio 1 : 2 : 1) in ether affords triphenylbismuth bis(2,4,6-tribromophenoxide). The complex obtained was structurally characterized by X-ray diffraction analysis. The coordination polyhedron of the Bi atom is a trigonal bipyramid with axial aroxy groups. The Bi–C and Bi–O bond lengths are 2.202(4), 2.203(4), 2.212(4) and 2.241(3), 2.245(3) Å, respectively. The intramolecular Bi···Br(1,4) contacts are 3.629(1) and 4.077(1) Å, respectively.     

Synthesis and Structure of Tetraphenylantimony Phenoxyacetate and Ethylmalonate Ph4SbOC(O)R (R = CH2OPh and CH2C(O)OC2H5)

Tetraphenylantimony phenoxyacetate (I) was synthesized by reacting pentaphenylantimony with phenoxyacetic acid (at a molar ratio of 1 : 1) in toluene. Tetraphenylantimony ethylmalonate (II) was synthesized from triphenylantimony and malonic ether in the presence of hydrogen peroxide (1 : 1 : 1) in diethyl ether. According to X-ray diffraction data, Sb atoms in compounds I and II have a distorted trigonal bipyramidal coordination to the axial oxygen atoms. The axial OSbC_ax angles and Sb-C_ax distances are, respectively, 176.31(6)° and 2.177(2) Å for I and 179.40(4)° and 2.162(1) Å for II. The Sb-C_eq distances lie in the intervals of 2.108(2)-2.127(2) Å for I and 2.117(1)-2.128(1) Å for II. In compounds I and II, the Sb-O bond lengths are equal to 2.235(1) Å and 2.250(1) Å, respectively, and the intramolecular contacts Sb··· are equal to 3.402(2) Å and 3.282(1) Å, respectively.     

3β-Methoxyolean-18-ene (miliacin) from the marine fungus Chaetomium olivaceum

A pentacyclic tritepenoid, 3-methoxyolean-18-ene (miliacin), was isolated for the first time from the marine fungus Chaetomium olivaceum. Its structure was determined on the basis of 2D NMR spectroscopy and X-ray diffraction data.     

Phenylation of Antimony(V) Organic Compounds with Pentaphenylantimony. The Structure of Tetraphenylantimony Chloride

Tetraphenylantimony chloride and bromide were synthesized through the reaction of pentaphenylantimony with diphenylantimony trichloride or tribromide taken at a molar ratio of 2 : 1 in toluene. When the initial compounds were taken at a molar ratio of 1 : 1, triphenylantimony dichloride or dibromide was formed. The phenylation of triphenylantimony sulfate with pentaphenylantimony yielded tetraphenylantimony sulfate. According to the X-ray diffraction data, the antimony atom in the tetraphenylantimony chloride molecule has a distorted trigonal bipyramidal configuration with the chlorine atom in the axial position. The Sb–Cl distance is equal to 2.686(1) and Sb–C distances are equal to 2.113(4) and 2.165(4) Å (av. 2.130 Å).     

Ionic Mobility, Phase Transitions, and Superionic Conduction in Solid Solutions (100 ? x)PbF2-xZrF4 and Crystals K2ZrF6, (NH4)2ZrF6, KSnZrF7, and M(NH4)6Zr4F23 (M = Li, Na)

Methods of (¹⁹F, ¹H) NMR and impedance spectroscopy are used to investigate the internal mobility and ionic conduction in solid solutions arising in the system PbF₂-ZrF₄ and polycrystals KSnZrF₇, Li(Na)(NH₄)₆Zr₄F₂₃, and M₂ZrF₆ (M = K, NH₄). Factors responsible for the form of ionic motions and their energetics at 170–550 K are considered. It is established that the phase transitions in these compounds are connected with the crystal transition to a superionic state and that the high ionic (superionic) conductivity of beta phases is due to the diffusion of fluoride ions, ammonium cations, and possibly alkali metal cations. The obtained data testify to a substantial role of chainlike aggregation of anionic groupings and a variableness of structural mechanisms of formation of such chains in fluorozirconates for the development of translational diffusion in these compounds.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 573–582.Original Russian Text Copyright © 2005 by Kavun, Uvarov, Slobodyuk, Goncharuk, Kotenkov, Tkachenko, Gerasimenko, Sergienko.     

μ-Oxo-Bis(Tetraphenylantimony): Synthesis,Structure, and Reactions

Heating of a solution of pentaphenylantimony in toluene in atmospheric oxygen affords -oxo-bis(tetraphenylantimony) (I) in a 63% yield. The latter compound can be converted to bis(tetraphenylantimony) carbonate or phthalate by the action of carbon dioxide or phthalic anhydride, respectively. According to X-ray diffraction data, the antimony atoms in compound Ihave a distorted trigonal-bipyramidal coordination (Sb–O 2.0050(4) Å, the SbOSb angle 151.71(9)°). The molecule of bis(tetraphenylantimony) phthalate is composed of two equal fragments, and its Sb atoms also have trigonal-bipyramidal coordination (Sb–O 2.2421(8) Å; Sb–C 2.176(1), 2.115(1), 2.130(1), and 2.137(1) Å).     

Synthesis and Structure of N,N-Dimethyldithiocarbamates of Tetraphenylantimony and Tetra-p-tolylantimony

Tetraphenylantimony N,N-dimethyldithiocarbamate (I) and tetra-p-tolylantimony N,N-dimethyldithiocarbamate (II) were synthesized via the reaction of tetraarylantimony chloride Ar₄SbCl (Ar = C₆H₅ or C₆H₄Me-4) with sodium N,N-dimethyldithiocarbamate in water. According to the X-ray diffraction data, the tetraarylantimony N,N-dimethyldithiocarbamate molecules have a distorted octahedral configuration. The Sb–S bond lengths are equal to 2.7158(5) Å, 2.7440(5) Å and 2.761(2) Å, 2.8002(2) Å for I and II, respectively.