Crystal structure and spectral characteristics of {[(C6H5)NH]2C=NH(C6H5)}[B(C6H5)4]·C2H5OH

A novel compound of {[(C₆H₅)NH]₂C=NH(C₆H₅)}[B(C₆H₅)₄]·C₂H₅OH is prepared and examined by single crystal X-ray diffraction. Crystal data: C₄₅H₄₄BN₃O, M = 653.64, monoclinic, space group P2₁/c, unit cell parameters: a = 24.375(2) Å, b = 17.5829(15) Å, c = 18.090(1) Å, β = 105.277(2)°, V = 7479.0(11) ų, Z = 8, d _calc = 1.161 g/cm³, T = 293 K, R ₁ = 0.064. The structure contains two crystallographically independent cations, two anions, and two solvate ethanol molecules. Three types of interactions occur between them: interionic N-H(N)⋯π and N(H)⋯π⋯H(C), π-delocalized system of Ph rings of the anions, and interaction of ions with ethanol molecules N-H⋯O-H(O)⋯π. The compound is characterized by IR and luminescence spectra. At room temperature, the emission intensity grows with time of exposure to UV irradiation. Original Russian Text Copyright ? 2008 by T. M. Polyanskaya, E. A. Il’inchik, V. V. Volkov, M. K. Drozdova, O. P. Yur’eva, and G. V. Romanenko __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 3, pp. 512–521, May–June, 2008.     

C14H3自由基和C14H3+阳离子的结构和热力学稳定性理论研究

采用密度泛函理论B3LYP/6-31G方法对C14H3中性和阳离子所有可能的构型、振动频率及热力学稳定性进行研究。基于目前的计算结果,C14H3和C14H3+最稳定的构型都是具有Cs对称的十四元环构型。如果构型里具有单叁键相互交替的聚炔烃结构,这个异构体就具有≈20cm-1的低频振动。C14通过加氢反应可以减小环内张力,使得十四元环能量降低,结构变得更加稳定。C14H3在温度低于1556K存在的可能性较大。     

Nature of the Ga-Ga bonding in Na2[Arx*GaGaArx*]（Arx*=C6H3 -2,6-（C6H5）2）:Electron localization function analysis

The nature of the Ga-Ga bonding in Na2[Arx*GaGaArx*](Arx* = C6H3-2,6-(C6H5)2) has been investigated and compared with that of in H2[Arx*GaGaArx*] using electron localization function(ELF) and orbital analysis.The calculation results show that in Na2[Arx*GaGaArx*],the Ga-Ga interaction is a non-classical triple bond,the heart of Na2[Arx*GaGaArx*] is the Ga2Na2 cluster rather than a simple Ga-Ga bond,and the contribution of the sodium atoms to the short Ga-Ga bond length is considerable.As the two sodium atoms are substituted by two hydrogen atoms,the Ga-Ga bond is replaced by two 3-center,2-electron(3c-2e) Ga-H-Ga covalent bridged bonding.     

配合物Cu(C14H10N2O2)(C5H5N)的合成和晶体结构

The novel copper(Ⅱ) complex with salicylaldehyde benzoylhydrazone and pyridine ligands， Cu(C₁₄H₁₀N₂O₂)(C₅H₅N)， has been synthesized and characterized by elemental analysis， IR and thermal analysis. The crystal structure of the title complex has been determined by single crystal X-ray diffraction techniques. The crystal belongs to monoclinic with space group P2₁/c. The cell parameters are： a=1.6362(9)nm， b=1.7140(9)nm， c=1.2255(7)nm， β=105.168(9)°， V=3.317(3)nm³， Z=8， D_c=1.525g·cm^-3， μ(MoKα)=1.334mm^-1， F(000)=1560. The structure was refined to final R₁=0.0376， wR₂=0.0909. The copper(Ⅱ) ion lies in a dis-torted square-planar environment composed of two oxygen atoms， one nitrogen atom of tridentate acyhydrazone Schiff base ligand and one nitrogen atom of the pyridine ligand. CCDC： 193111.     

Reactions of [η:σ-Me2C(C5H4)(C2B10H10)]Ru(COD) with Lewis bases: Synthesis, structure, and electrochemistry of ruthenium amine, nitrile, carbene, phosphite and phosphine complexes

Treatment of [η⁵:σ-Me₂C(C₅H₄)(C₂B₁₀H₁₀)]Ru(COD) (1) with phosphites, phosphines, amines or N-heterocyclic carbene in THF afforded the COD displacement complexes [η⁵:σ-Me₂C(C₅H₄)(C₂B₁₀H₁₀)]Ru[P(OEt)₃]₂ (2), [η⁵:σ-Me₂C(C₅H₄)(C₂B₁₀H₁₀)]Ru[PPh₂(OEt)]₂ (3), [η⁵:σ-Me₂C(C₅H₄)(C₂B₁₀H₁₀)]Ru[NH₂CH₂CH₂Prⁱ]₂ (4), [η⁵:σ-Me₂C(C₅H₄)(C₂B₁₀H₁₀)]Ru(NH₂Prⁿ)₂ (5), [η⁵:σ-Me₂C(C₅H₄)(C₂B₁₀H₁₀)]Ru (η²-NH₂CH₂CH₂NH₂) (6), [η⁵:σ-Me₂C(C₅H₄)(C₂B₁₀H₁₀)]Ru[η²-NH(CH₃)CH₂CH₂NH(CH₃)] (7) or [η⁵:σ-Me₂C(C₅H₄)(C₂B₁₀H₁₀)]Ru[NHC]₂ (8, NHC = 1,3,4,5-tetramethylimidazol-2-yilidene), respectively. Ruthenium-amine complexes were much more labile than 1. Upon exposure to moisture, 5 was converted into [{η⁵:σ-Me₂C(C₅H₄)(C₂B₁₀H₁₀)}Ru(μ-H₂O)]₂ (9). Reactions of 5 with PR₃ (R = PPh₃, Cy), TMEDA (TMEDA = N,N,N′,N′-tetramethylethylenediamine) and CH₃CN afforded the corresponding amine replacement products[η⁵:σ-Me₂C(C₅H₄)(C₂B₁₀H₁₀)]Ru(NH₂Prⁿ)(PPh₃) (10), [η⁵:σ-Me₂C(C₅H₄)(C₂B₁₀H₁₀)]Ru(NH₂Prⁿ)(PCy₃) (11), [η⁵:σ-Me₂C(C₅H₄)(C₂B₁₀H₁₀)]Ru(TMEDA) (12) and [η⁵:σ-Me₂C(C₅H₄)(C₂B₁₀H₁₀)]Ru(NCCH₃)₂ (13). These results indicated that the steric factor dominated these substitution reactions. The electrochemical studies showed that the electron richness of the Ru atom decreased in the order L₂Ru(NHC)₂ > L₂Ru(amine)₂ > L₂Ru(NCMe)₂ > L₂Ru(P)₂. All of these complexes were fully characterized by various spectroscopic techniques and elemental analyses. The molecular structures of 2, 3, 5-10, 12 and 13 were further confirmed by single-crystal X-ray analyses.     

Synthesis of (C8H11N)2·Zn(OAc)2, (C8H11N)2·Cu(OAc)2, and (C8H11N)2·CuCl2 complexes and application to the Henry reaction

(C₈H₁₁N)₂·Zn(OAc)₂ (1a), (C₈H₁₁N)₂·Cu(OAc)₂ (1b), and (C₈H₁₁N)₂·CuCl₂ complexes are synthesized by a simple one-pot method. The crystal structures of 1a, 1b, and 1c are determined by X-ray crystallography. The complexes are also characterized by NMR, IR, MS, and elemental analysis and used as the catalysts applied to the Henry reaction; moderate to high yields are obtained at room temperature.     

Structure of (C17H22FN3O3)[MCl4]·H2O (M = Cd, Hg)

Two isostructural compounds (C₁₇H₂₂FN₃O₃)[MCl₄]·H₂O (M = Cd, Hg), C₁₇H₂₀FN₃O₃ is 1-ethyl-N-methyl-6-fluoride-1,4-dihydro-4-oxo-7-(4-methyl-1-piperazinyl)-3-quinoline carboxylic acid (PefH, pefloxacin), are synthesized and their crystal structure is determined. The crystals contain PefH₃²⁺ and MCl₄²⁻ ions. The neighboring [MCl₄]²⁻ ions are bonded together by two bridging water molecules through four Cl...(H-O-H)₂...Cl hydrogen bonds with the formation of the supramolecular motif R ₂⁴(8). The supramolecular architecture of crystals is analyzed.     

Theoretical Study of Adsorption and Dehydrogenation of C2H4 on Cu(410)?

Adsorption and dehydrogenation of ethylene on Cu(410) surface are investigated with firstprinciples calculations and micro-kinetics analysis. Ethylene dehydrogenation is found to start from the most stable π-bonded state instead of the previously proposed di-σ-bonded state. Our vibrational frequencies calculations verify the π-bonded adsorption at step sites at low coverage and low surface temperature and di-σ-bonded ethylene on C-C dimer (C₂H₄-CC) is proposed to be the species contributing to the vibrational peaks experimentally observed at high coverage at 193 K. The presence of C₂H₄-CC indicates that the dehydrogenation of ethylene on Cu(410) can proceed at temperature as low as 193 K.     

新型一维链状配位聚合物[Cd2(C23H14O6)2(C10H9N3)2(H2O)]n的研究

配位超分子聚合物的设计合成与应用研究一直是配位化学、超分子化学、生物无机化学及材料科学等领域的热点研究课题之一,具有微孔结构的配位聚合物吸引了许多科学家的目光,这不仅因为该类配合物具有新颖的结构,展现出多种诱人的拓扑结构,更主要的 是因为它们在离子交换、催化、磁性材料、光学材料及气体贮存领域的应用潜力[1～3].     

Synthesis and crystal structures of [UO2(C6H4NO2)2(C6H5NO2)] and [UO2SO4(C6H5NO2)(H2O)] · H2O

The complexes [UO₂(C₆H₄NO₂)₂(C₆H₅NO₂) (I) and [UO₂SO₄(C₆H₅NO₂)(H₂O)] · H₂O (II) were synthesized and studied by X-ray diffraction analysis. Crystals I are monoclinic: a = 7.0081(3), b = 14.9624(7), c = 9.1837(5) ?, β = 96.594(2)°, Z = 2, space group P2₁/m. Crystals II are triclinic: a = 6.8097(6), b = 9.3837(8), c = 10.4556(10) ?, α = 85.279(3), β = 75.434(3), γ = 69.180(3)°, Z = 2, space group . The main structural unit of crystal I is a mononuclear fragment, which belongs to the crystal chemical group AB ₂ ⁰¹ M¹ (A = UO ₂ ²⁺ , B⁰¹ are ions of pyridine-2-carboxylic (picolinic) acid, M¹ are molecules of picolinic acid) of the uranyl complexes. The main structural unit of crystal II is a chain, which belongs to the crystal chemical group AT³M ₂ ¹ (where T³-SO ₄ ²⁻ , M¹ are water and picolinic acid molecules) of the uranyl complexes. Picolinic acid in complexes I, II was found to have a zwitterion structure. Original Russian Text ? E.V. Grechishnikova, E.V. Peresypkina, A.V. Virovets, Yu.N. Mikhailov, L.B. Serezhkina, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 6, pp. 468–475.     

Large bite bisphosphite, 2,6-C5H3N{CH2OP(-OC10H6)(μ-S)(C10H6O-)}2: Synthesis, derivatization, transition metal chemistry and application towards hydrogenation of olefins

Large bite bisphosphite ligand, 2,6-C₅H₃N{CH₂OP(-OC₁₀H₆)(μ-S)(C₁₀H₆O-)}₂ (2), is obtained by reacting chlorophosphite, {-OC₁₀H₆(μ-S)C₁₀H₆O-}PCl (1) with 2,6-pyridinedimethanol in presence of triethylamine.Treatment of 2 with aqueous solution of H₂O₂ or elemental sulfur resulted in the formation of bis(oxide) or bis(sulfide) derivatives, 2,6-C₅H₃N{CH₂OP(E)(-OC₁₀H₆)(μ-S)(C₁₀H₆O-)}₂ (3, E = O; 4, E = S) in quantitative yield.The 10-membered cationic chelate complex, [RuCl(η⁶-C₁₀H₁₄)η²-2,6-C₅H₃N{CH₂OP(-OC₁₀H₆)(μ-S)(C₁₀H₆O-)}₂-κP,κP]Cl (5) is produced in the reaction between [Ru(p-cymene)(μ-Cl)(Cl)]₂ and bisphosphite 2, whereas the neutral chelate complex, cis-[Rh(CO)Cl{2,6-C₅H₃N{CH₂OP(-OC₁₀H₆(μ-S)C₁₀H₆O-)}₂}-κP,κP] (6) is isolated in the reaction of 2 with 0.5 equiv.of [Rh(CO)₂Cl]₂.Compound 2 on treatment with M(COD)Cl₂ (M = Pd, Pt) produce the chelate complexes, [MCl₂{η²-2,6-C₅H₃N{CH₂OP(-OC₁₀H₆)(μ-S)(C₁₀H₆O-)}₂}-κP,κP] (7, M = Pd;10, M = Pt).Similarly the reaction of bisphosphite 2 with Pd(COD)MeCl affords cis-[PdMe(Cl)η²-2,6-C₅H₃N{CH₂OP(-OC₁₀H₆)(μ-S)(C₁₀H₆O-)}₂-κP,κP] (8).Treatment of 2 with [Pd(η³- C₃H₅)Cl]₂ in the presence of AgClO₄ furnish the cationic complex, [Pd(η³-C₃H₅)η²-2,6-C₅H₃N{CH₂OP(-OC₁₀H₆)(μ-S)(C₁₀H₆O-)}₂-κP,κP]ClO₄ (9). The binuclear complex, [Au₂Cl₂{2,6-C₅H₃N{CH₂OP(-OC₁₀H₆)(μ-S)(C₁₀H₆O-)}₂}-κP,κP] (11) is obtained in the reaction of compound 2 with two equiv. of AuCl(SMe₂), where the ligand exhibits bridged bidentate mode of coordination. All the complexes are characterized by the ¹H NMR, ³¹P NMR, elemental analysis and mass spectroscopy data. The cationic ruthenium complex 5 is proved to be an active catalyst for the hydrogenation of styrene and α-methyl styrene.     

Synthesis and crystal structure of π-complex of copper(I) with 1-allylbenzimidazolium cation [C7H5N2H(C3H5)]+ [Cu3Cl4]?

Single crystals of [C₇H₅N₂H(C₃H₅)]⁺[Cu₃Cl₄]^– were obtained for the first time by ac electrochemical synthesis from 1-allylbenzimidazolium and copper(II) chlorides in ethanol and structurally characterized. The unit cell parameters are a=8.6755(9) , b=8.846(1) , c=10.4540(7) , =85.36(1)°, =70.529(7)°, =83.29(1)° , V=750.5(3) ³, space group P , R(F)=0.0551. In the -complex, the copper and chlorine atoms form complicated infinite chains along the x axis. The 1-allylbenzimidazolium cation functions as an original bridge: it is coordinated by the Cu atom of one cuprous-chloride chain through the C=C bond of the allyl group and forms a N-HCl hydrogen bond with another inorganic chain through the N atom of the imidazole ring. The trigonal pyramidal environment of the Cu(1) atom includes three Cl atoms and the C=C bond; the environments of the Cu(2), Cu(3), and Cu(3a) are composed only of chlorine atoms. The positions of the Cu(2) and Cu(3a) atoms are partially disordered, which is manifested by the high thermal parameters for the Cu(2) atom and by the splitting of another copper atom into two equally occupied positions Cu(3) and Cu(3a).Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 3, 2005, pp. 199–203.Original Russian Text Copyright © 2005 by Goreshnik, Schollmeyer, Myskiv.This revised version was published online in April 2005 with a corrected cover date.This revised version was published online in April 2005 with a corrected cover date.     

Synthesis and crystal structure of (C3N5H6S)2[UO2(C2O4)2(H2O)] · C2N4H4

The formation of the thioammelinium cation in an aqueous solution in the presence of uranyl ions is demonstrated. Single crystal X-ray diffraction study of (C₃N₅H₆S)₂[UO₂(C₂O₄)₂(H₂O)] · C₂N₄H₄ was carried out and the geometric characteristics of thioammelinium were determined for the first time. The crystals are triclinc, space group , Z = 2, a = 8.5201(11) ?, b = 11.4027(14) ?, c = 14.329(2) ?, α = 103.182(5)°, β = 99.607(6)°, γ = 109.698(4)°, R = 0.0526. The main structural units in the crystal are mononuclear complex groups [UO₂(C₂O₄)₂(H₂O)]²⁻ corresponding to the crystal chemical group AB ₂ ⁰¹ M¹ (A = UO ₂ ²⁺ , B⁰¹ = C₂O ₄ ²⁻ , M¹ = H₂O) of uranyl complexes. Uranium-containing mononuclear complexes are connected into a three-dimensional framework through electrostatic interactions and hydrogen bonds involving thioammelinium ions, water molecules, and cyanoguanidine. Original Russian Text ? L.B. Serezhkina, A.V. Virovets, E.V. Peresypkina, I.V. Medrish, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 5, pp. 380–385.     

Complexation between N-allylmorpholinium derivatives and copper(I) halides. Synthesis and crystal structure of π-complex {[C4H8ONH(C3H5)]+}2[Cu2Cl4]2?

Copper(I) -complex {[C₄H₈ONH(C₃H₅)]⁺}₂[Cu₂Cl₄]^2– (I) was obtained by ac electrochemical synthesis from N-allylmorpholine hydrochloride and copper(II) chloride in ethanol and structurally characterized. In structure I, copper and chlorine atoms form unique noncentrosymmetric Cu₂Cl ₄ ^2– fragments. Both crystallographically independent N-allylmorpholinium cations are involved in the -interaction and are coordinated by the copper atom through the C=C bond of the allyl group. The trigonal pyramidal environment of the Cu(1) atom is composed of three chlorine atoms and the C=C bond, while the Cu(2) atom coordinates two chlorine atoms and the C=C bond forming a planar triangle. The extremely strong N-CCl hydrogen bond (HCl 2.2 ) prevents the Cl(1) atom from acting as a bridge and favors the formation of fragments Cu₂Cl ₄ ^2– .__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 4, 2005, pp. 306–310.Original Russian Text Copyright © 2005 by Goreshnik, Davydov, Myskiv.     

Synthesis and crystal structure of [Fe4O2(H2O)10(C5H5NCOO)4](NO3)8 · 2H2O

Crystals of the tetranuclear complex [Fe₄O₂(H₂O)₁₀(C₅H₅NCOO)₄](NO₃)₈ · 2H₂O are obtained by the slow evaporation of an aqueous solution of iron(III) nitrate and isonicotinic acid. According to the X-ray diffraction data, four metal atoms lie in the same plane and together with two μ₃-O oxygen atoms form the fragment [Fe₄(μ₃-O)₂]¹⁰⁺. The [Fe₄O₂(H₂O)₁₀(C₅H₅NCOO)₄]⁸⁺ cation has been obtained and structurally characterized for the first time.     

Dielectric Barrier Discharge Initiated Gas-Phase Decomposition of CO2 to CO and C6–C9 Alkanes to C1–C3 Hydrocarbons on Glass, Molecular Sieve 10X and TiO2/ZnO Surfaces

Atmospheric Pressure Dielectric Barrier Discharge (APDBD) initiated decomposition of CO₂ and C₆–C₉ alkanes (in Ar carrier) with uncoated and TiO₂/ZnO coated glass surfaces, and under molecular sieve 10 X packing are presented in this study. Alkanes employed include 2-methylpentane, cyclohexane, n-hexane, n-heptane, n-octane, n-nonane and their decomposition products studied include C₁–C₃ hydrocarbons viz. CH₄, C₂H₄, C₂H₆ and C₃H₈. Generally the yields of all these C₁–C₃ products increased with discharge energy, however to a major extent the parent alkane structure controlled the relative concentration profiles of the individual products. Typically the slopes of the increase in various products yield varied from 0.025 to 0.25 ppm (v/v) mm V⁻¹. However, in the case of cyclohexane the total yield of methane, ethane and propane were only ∼20% of ethylene yield. Use of TiO₂ as well as TiO₂/ZnO coated central glass electrode in the APDBD apparatus showed ∼11% enhancement in degradation efficiency. However, while overall 2-methylpentane decomposition reduced significantly to ∼30%, in case of n-octane its decomposition to the C₁–C₃ products remained unaffected. On the other hand under molecular sieve 10X packing, yield of CH₄ and C₂H₄ increased significantly in both cases.     

Synthesis, crystal structure, and biological activity of the binuclear complex [Pr2(C10H9N2O4)2(C7H5O3)4(H2O)2] · 2H2O

A novel binuclear praseodymium(III) complex with N-(2-propionyl)salicyloylhydrazone (C₁₀H₁₀N₂O₄, H₃L) and p-hydroxybenzoic acid (C₇H₆O₃, Phba) was prepared in a H₂O-C₂H₅OH mixed solution, and the crystal structure of [Pr₂(H₂L)₂(Phba)₄(H₂O)₂] · 2H₂O (I) was determined by X-ray single crystal diffractometry. Complex I crystallizes in the monoclinic system, space group P2₁/c, a = 1.1050(4), b = 1.9534(7), c = 1.2376(4) ?, β = 94.955(7)°, and Z = 4. In the structure each Pr³⁺ ion lies in a single capped square antiprism geometry coordinated by carboxyl O and acyl O atoms and azomethine N atom of one ligand (H₂L⁻ form), which coordinates via the keto form, four carboxyl O atoms from two Phba, and O atoms of two water molecules. In each molecule, two tridentate ligands were coordinated by the H₂L⁻ form, and each Pr³⁺ ion was chelated by the carboxyl group from Phba. The carboxyl groups of H₂L⁻ and other two Phba were coordinated via μ₂-bridging form and bidentate bridging form, respectively. Complex I and ligands Phba and H₃L were also searched for biological activity against Valsa mali by the growth rate method. The result showed that the inhibitory rate of ligands Phba and H₃L is better than complex I, especially Phba.     

含硫有机膦多酸衍生物α–[RP(S)]2PW9O345-(R = –C6H5, –C6H11)的合成及结构表征

In the presence of Bu4NBr acting as phasetransfer reagent, organothiophosphoryl polyoxotungstate derivatives α-[RP(S)]2PW9O54^5- (R=C6Hs, C6H11) have been obtained by reaction of the trivacant β-[PW9O34]^9- anions with electrophilic C6H5P(S)Cl2 or C6H11P(S)Cl2 in acetonitrile. These new organic-inorganic hybrid anions have been characterized by elemental analysis, IR, ^31P and ^183W NMR spectroscopy. The collective application of the spectroscopy data of these new species indicates that the hybrid anion consists of an α-[PW9O34] framework on which are grafted two RP(S) groups through P-O-W bridges. The five-line ^183W spectra indicate that the hybrid anions possess Cs symmetry in acetonitrile.