Synthesis and Crystal Structure of [Ni(II)(L)(py)_3]·(py)

1 INTRODUCTION Schiff bases and their metal complexes are useful reagents in organic synthesis[1], and they have exhi- bited some biological activities as anticancer and antitumor drugs[2]. The crystal structures and physi- cal and chemical properties of many Schiff bases and their transition metals complexes have been re- ported[3~5]. Further interest in the coordination che- mistry of nickel(II) arises from the role of these complexes in several catalytic reactions, such as electrocat…     

DSC study of the phase transitions in [Ni(D2O)6](ClO4)2 and [Ni(H2O)6](ClO4)2

DSC measurements were carried out for [Ni(H₂O)₆](ClO₄)₂ (sampleH) and [Ni(D₂O)₆](ClO₄)₂ (sampleD) in the temperature range 300–380 K. For both compounds two anomalies on the DSC curves were detected. The results for sampleH are compared to those previously obtained using adiabatic calorimetry method. For both compounds studied in this work the high-temperature transition appears at the same temperature while the low-temperature one is shifted towards higher temperatures in sampleD. Disorder connected with H₂O or D₂O groups is suggested in the intermediate phase between the low- and high-temperature transitions.     

Reactions of 3-[N-chloroacetylamino-N-(4-nitrophenyl)]-2-formylindole with alkylamines

The reactions of 3-[N-chloracetylamino-N-(4-nitrophenyl)]-2-formylindole (1a) with 2-(N, N-dialkylamino)ethylamines afford complex condensation products 7b,c consisting of two similar but not identical diazepinoindole fragments. For the reaction of compound 1a with 3-(N,N-diethylamino)propylamine, the process occurs in a different manner, and the predominant product is 4-ethylaminopropyl-1-(4-nitrophenyl)-2-oxo-1,2,3,4,5,6-hexahydro[1,4]diazepino[6,5-b]indole hydrocloride (14). Two routes of these unexpected transformations were proposed. The structures of the synthesized products were proved by the ¹sH and ¹³C NMR, HMBC, and HSQC (direct proton-carbon correlation) spectra. Dedicated to Academician V. A. Tartakovsky on the occasion of his 75th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1536–1542, August, 2007.     

Two Polymorphs of (Anilinium)(18-Crown-6)[Ni(dmit)2]: Structure and Magnetic Properties

Two polymorphs of monovalent [Ni(dmit)₂]⁻ (dmit²⁻=2-thioxo-1,3-dithiole-4,5-dithiolate) crystals A and B, (anilinium)(18-crown-6)[Ni(dmit)₂], were prepared, and the structure and magnetic properties were investigated. In these crystals, the [Ni(dmit)₂]⁻ molecules form dimers, which arranged into chains between the supramolecular cation structure (anilinium)(18-crown-6). In crystal A, supramolecular cation formed a regular stack, inducing ladder structure of [Ni(dmit)₂], whose magnetism had been well fitted by spin ladder equation with the spin gap of Δ=190 K. Crystal B is ca. 3% more densely packed compared to crystal A. Due to the dense packing, supramolecular cation stack is distorted, which prevented the intermolecular interaction between [Ni(dmit)₂]⁻ dimers in direction corresponds to the ladder-leg direction in crystal A. Reflecting the [Ni(dmit)₂]⁻ arrangement, crystal B showed a temperature dependence of magnetic susceptibility well reproduced by the singlet-triplet thermal activation model, whose antiferromagnetic exchange interaction (2J) was 140 K.     

Structural and spectroscopic properties of trans-difluoro(1,4,8,12-tetraazacyclopentadecane)chromium(III) perchlorate hydrate

The structure of [CrF(2)([15]aneN(4))]ClO(4).H(2)O ([15]aneN(4)=1,4,8,12-tetraazacyclopentadecane) has been determined by a single-crystal X-ray diffraction study at 173 K. The complex crystallizes in the space group P1- of the triclinic system with two mononuclear formula units in a cell of dimensions a=9.6117(7) A, b=10.2882(7) A, c=11.0001(7) A and alpha=99.7570(10) degrees, beta=105.6080(10) degrees and gamma=113.7130(10) degrees. The complex cation unit has its central Cr atom in an octahedral coordination with four nitrogen atoms and two fluorine atoms in a trans position. Three six-membered and one five-membered chelate rings of the [15]aneN(4) ligand are in a chair-twist(skew)-chair-gauche conformation sequence. The gauche five-membered ring is disordered with the twist six-membered ring opposite. The four H atoms in the chiral N atoms have the trans-II (CTCg) type configuration. The mean Cr-N and Cr-F bonds are 2.095(2) and 1.8752(13) A, respectively. The IR and visible spectral properties are consistent with the result of X-ray crystallography. The resolved band maxima of the electronic d-d spectrum are fitted with secular determinant for quartet state energy of d(3) configuration in tetragonal field including configurational but neglecting spin-orbit coupling. It is confirmed that the fluoride has strong sigma- and pi-donor properties toward the chromium(III) ion and the nitrogen atoms of the [15]aneN(4) ligand also have a strong sigma-donor character.     

Cu2O(SO4), dolerophanite: Refinement of the crystal structure,with a comparison of [O Cu(II)4] tetrahedra in inorganic compounds

The refinement of the crystal structure of Cu₂O(SO₄), dolerophanite, [a=9.370 (1) Å,b=6.319 (1) Å,c=7.639 (1) Å, =122.34 (1)°; space group C 2/m;Z=4;R=0.035] confirmed the trigonal dipyramidal coordination of one Cu(II) atom (mean distance Cu-O=2.025 Å). One O atom is tetrahedrally surrounded by four Cu(II) atoms; the mean Cu(II)-O distance of 1.918 Å compares well to [O Cu(II)₄] tetrahedra found in inorganic crystal structures.de|Die Verfeinerung der Kristallstruktur von Cu₂O(SO₄), Dolerophanit, [a=9.370 (1) Å,b=6.319 (1) Å,c=7.639 (1) Å, =122.34 (1)°; Raumgruppe C 2/m;Z=4;R=0.035] bestätigte die trigonal dipyramidale Koordination des einen Cu(II)-Atoms (mittlerer Cu-O-Abstand=2.025 Å). Ein O-Atom ist tetraedrisch von vier Cu(II)-Atomen umgeben; der mittlere Cu(II)-O-Abstand von 1.918 Å entspricht den in ähnlichen [O Cu(II)₄]-Tetraedern von anorganischen Kristallstrukturen gefundenen Werten.

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Cu₂O(SO₄), Dolerophanit: Verfeinerung der Kristallstruktur mit einem Vergleich von [O Cu(II)₄]-Tetraedern in anorganischen Verbindungen

     

Reactions ofo-tosylaminobenzaldehyde withp-aminobenzenesulfonamides. Synthesis and structures of 13-(4-aminosulfonylphenyl)-6,12-epimino-5,11-ditosyl-5,6,11,12-tetrahydrodibenzo[b,f]-1,5-diazocine and itsN-substituted derivatives

The reactions ofo-tosylaminobenzaldehyde (1) withp-aminobenzenesulfonamides (2a-c) yielded 13-(p-RNHSO₂C₆H₄)-6,12-epimino-5,11-ditosyl-5,6,11,12-tetrahydrodibenzo[b f]-1,5-diazocines (3a-c) (R=H (a); 2-thiazolyl (b); or 2,6-dimethoxy-4-pyrimidinyl 2,6-dimethoxy-4-pyrimidinyl (c). The structure of compound3c was confirmed by X-ray diffurction study. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2035–2039, November, 1997.     

Molecular Structure of 1-Substituted Bicyclo[2.2.0]hexanes: A Combined X-Ray Structural and Ab Initio Study

The synthesis and X-ray crystal structure of the p-bromoanilide derivative of bicyclo[2.2.0]hexane-l-carboxylic acid (1), N-(4-bromophenyl)-bicyclo[2.2.0]hexane-l-carboxamide (2), is reported. N-(4-Bromophenyl)-bicyclo[2.2.0]hexane-l-carboxamide is synthesized in good yield via the DCC coupling of bicyclo[2.2.0]hexane-l-carboxylic acid (1) with p-bromoaniline. Low-temperature X-ray analysis of 2 reveals that the bonds of the bicyclo[2.2.0]hexane skeleton vicinal to the amide group show a slight lengthening due to conjugative interaction with the -accepting amide group. Ab initio calculations at the 6-31G* level of theory on bicyclo[2.2.0]hexane-l-carboxamide, a model for 2, and for other 1-substituted bicyclo[2.2.0]hexanes are also reported.     

Thermal, oxidative and radiation stability of polyimides. Part IV: Polyimides based on N-[4-benzoyl-2-(2,5-dioxo-2,5-dihydro-pyrrol-1-yl)-phenyl]-acetamide and different diamines

Polyimide resins were obtained from the reaction between N-[4-benzoyl-2-(2,5-dioxo-2,5-dihydro-pyrrol-1-yl)-phenyl]-acetamide and the following compounds with terminal amino groups: urea, 4-[(4-aminophenyl)sulfonyl]aniline, thiourea, 2-aminoethylamine, and 4,4′-diaminodiphenylmethane. The thermal and thermooxidative behaviour of the polyimide resins was studied by thermogravimetric measurements (TG) in oxygen and nitrogen. Polyimide resins have been irradiated (500 kGy) and their radiation stability evaluated on the basis of thermal and thermooxidative behaviour of irradiated samples.The thermal and oxidative degradation of the examined polyimides is complex and occurs in two phases. The first step occurs in both nitrogen and oxygen but it is somewhat less pronounced in oxygen due to oxidation and formation of more stable products. All samples showed very good radiation stability and there is almost no change in the first degradation step while the span of the peaks in the second step is narrowed and temperatures are slightly lower.     

Synthesis of novel 3-(1,3-thiazol-2-yl)-7,8-dihydroquinoline-2,5(1H,6H)-diones

An efficient method for the synthesis of novel 3-(1,3-thiazol-2-yl)-7,8-dihydroquinoline-2,5(1H,6H)-diones from various 2-dimethylaminomethylidenecyclohexane-1,3-diones, (1,3-thiazol-2-yl)acetonitriles, and dimethylformamide dimethyl acetal was developed. These transformations proceeded through intermediate 2-[2-(4-aryl-1,3-thiazol-2-yl)-2-cyanoethenyl]-3-oxocyclohex-1-en-1-olates. They were isolated as piperidinium salts and used in further heterocyclization reactions with aromatic amines, giving novel 1-aryl-3-(1,3-thiazol-2-yl)-7,8-dihydroquinoline-2,5(1H,6H)-diones. These compounds were also obtained by preparative three-step “one pot” synthesis under controlled microwave irradiation. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 412–417, February, 2008.     

Synthesis,Structure, and Biological Activity of [2.2]Paracyclophane Derivatives. 8. α-Pyridyl([2.2]paracyclophan-4-yl)-phenylmethanol: Structure of the Complex with Cu(II) Chloride and Intramolecular Cyclization

The reaction of 2-benzoylpyridine with 4-([2.2]paracyclophanyl)lithium or of 4-benzoyl[2.2]paracyclophane with 2-pyridyllithium gave α-pyridyl([2.2]paracyclophan-4- yl)phenylmethanol. X-ray analysis has been used to study the molecular and crystalline structure of its complex with Cu(II) chloride. It was found that this triaryl-substituted methanol undergoes an intramolecular cyclocondensation in refluxing formic acid and involves the pyridine ring and the cyclophane substituent. Heterocyclization at the ortho-position of the latter gives 10-phenyl[2.2]paracyclophano[4,5-b]indolizine and cyclization at the pseudo-gem-position the 1-phenyl-1,1a-dehydro-6-aza[3.2.2](1,2,5)-6H-cyclophano[1,2-a]pyridine. The compounds prepared have luminescent properties. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 864–873, June 2005.     

Low-temperature X-ray study of benzoid-quinoid tautomerism in crystals of 2-(N,N-diphenylhydrazinoethylidene)-3(2H)-benzo[b]thiophenone

An X-ray investigation of 2-(N,N-diphenylhydrazinoethylidene)-3(2H)-benzo[b]thiophenone was performed at room and low (–80 °C) temperatures. It was established that the structure of this compound in the crystalline state at R-20 °C is intermediate between the ketoenehydrazine and hydroxyhydrazone forms, while at –80 °C the molecular structure is completely transformed to the hydroxyhydrazone form. This confirms the dynamic nature of hydrogen atom disordering in the molecule at 20 °C.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 104–106, January, 1995.This work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-04355).     

基于3-(羧甲基)-7-甲基-2-丙基-3H-苯并[d]咪唑-5-羧酸的新型锌(Ⅱ)配位聚合物的合成及其晶体结构

以7-甲基-2-丙基-3H-苯并[d]咪唑-5-羧酸甲酯为原料,经还原反应和水解反应两步制得配体3-(羧甲基)-7-甲基-2-丙基-3H-苯并咪唑-5-羧酸(MZ);以Zn(NO_3)_2·6H_2O为锌源,MZ经配位反应合成一个新型的锌(Ⅱ)配合物{[Zn(MZ)_2]·2H_2O}_n(3),其结构经~1H NMR,FT-IR,X-射线单晶衍射和元素分析表征。3属单斜晶系,P2/c空间群,晶胞参数a=0.786 42(16)nm,b=1.072 1(2)nm,c=1.725 9(3)nm,α=γ=90°,β=93.63(3)°,V=1.452 2(5)nm3,D_c=1.482 g·cm~(-3),Z=2,R1=0.059 3,wR_2=0.141 5。     

Synthesis and transformations of 3-(1H-pyrrol-1-yl)thieno[2,3-b]pyridines

Reactions of 2,5-dimethoxytetrahydrofuran with 3-aminothieno[2,3-b]pyridines afford a number of substituted 3-(1H-pyrrol-1-yl)thieno[2,3-b]pyridines. The possibility of the reaction and the yield of the product are determined by the character of a substituent in position 2 of thieno[2,3-b]pyridine. The Curtius rearrangement of 2-acylazido-3(1H-pyrrol-1-yl)thieno[2,3-b]pyridines yields 4,5-dihydropyrido[3",2":4,5]thieno[2,3-e]pyrrolo[1,2-a]pyrazin-4-ones. The molecular and crystal structures of ethyl 4-methoxymethyl-6-methyl-3-(1H-pyrrol-1-yl)thieno[2,3-b]pyridine-2-carboxylate were determined by X-ray diffraction analysis.     

Electrochemical properties of <Emphasis Type="Italic">n</Emphasis>-sulfonatothiacalyx[4]arene complexes with Fe<Superscript>3+</Superscript> and [Co(dipy)<Subscript>3</Subscript>]<Superscript>3+</Superscript> ions

The electrochemical properties of n-sulfonatothiacalyx[4]arene (H₄XNa₄) complexes with [Co(dipy)₃]³⁺ and Fe³⁺ ions were studied by means of cyclic voltammetry in aqueous solution at pH 2.5. The observed single-electron reduction of [Co(dipy)₃]³⁺ bound extraspherically to the upper rim and Fe³⁺ ion bound intraspherically to the lower rim of n-sulfonatothiacalyx[4]arene in binary [Co(dipy)₃]³⁺ · H₃X^5?, H₃X^5? · Fe³⁺, and ternary [Co(dipy)₃]³⁺ · H₃X^5? · Fe³⁺ heterometal complexes was more difficult than in the free state. The reversible single-electron transfer to the metal ion results in lower binding energy ([Co(dipy)₃]³⁺, ΔΔG ₀ = 3.9 kJ/mol) or in full fast dissociation of the complex (Fe³⁺). The ternary complex in the solution forms the aggregates, in which inner encapsulated Fe(III) and Co(III) ions are not reduced on the electrode. Their quantitative reduction takes place by the relay mechanism of intra- and intermolecular electron transfer through electrochemically generated [Co(dipy)₃]²⁺ outer ions.     

Interaction of 3-p-toluoyl-1,2-dihydro-4H-pyrrolo-[2,1-c][1,4]benzoxazine-1,2,4-trione with benzylamine. Synthesis and crystal and molecular structure ofZ-3-(1-benzyl-2-hydroxy-4,5-dioxo-2-p-tolyltetrahydropyrrol-3-idene)-3,4-dihydro-2H-1,4-benzoxazin-2-one

3-p-Toluoyl-1,2-dihydro-4H-pyrrolo-[2,1-c][1,4]benzoxazine-1,2,4-trione reacts with benzylamine to yieldZ-3-(1-benzyl-2-hydroxy-4,5-dioxo-2-p-tolyltetrahydropyrrol-3-idene)-3,4-dihydro-2H-1,4-benzoxazin-2-one. The crystal and molecular structure of the latter compound was studied by X-ray structural analysis. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 566–569, March, 1997.     

Reactions of cyclic 1,3-dicarbonyl compounds with 1,2(1,4)-dihydro-1-methyl-2(4)-methylene-N-heterocycles. A new access to 6,12-methano-dibenz[d,g]-[1,3]oxazocinones

Summary The enamine-type methylene-N-heterocycles1–5 react with cyclic 2-ethoxymethylene-1,3-dicarbonyl compounds6 to give 2-[2-(hetarylidene)ethylidene]-1,3-dicarbonyl compounds7–14. The result of the reactions between 1,2-dihydro-1-methyl-2-methylene-quinoline (1a) and cyclic 1,3-dicarbonyl compounds depends on the nature of the dihydro intermediatesA/B. Dehydrogenation of keton intermediatesA results in 2-(1,2-dimethyl-4(1H)-quinolylidene)-1,3-dicarbonyl compounds17–21. Enol intermediatesB with 6-membered dicarbonyl ring form 6,12-methano-dibenz-[d,g][1,3]oxazocinones22–25.¹H NMR spectra and X-ray structure analysis prove the structure of23.

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Reaktionen cyclischer 1,3-Dicarbonylverbindungen mit 1,2(1,4)-Dihydro-1-methyl-2(4)-methylen-N-heterocyclen. Ein neuer Zugang zu 6,12-Methano- dibenz[d,g][1,3]oxazocinonen

Zusammenfassung Aufgrund ihres Enamincharakters reagieren die Methylen-N-heterocyclen1–5 mit cyclischen 2-Ethoxymethylen-1,3-dicarbonylverbindungen6 zu den 2-[2-(Hetaryliden)ethyliden]-1,3-dicarbonylverbindungen7–14. Das Ergebnis der Reaktionen zwischen 1,2-Dihydro-1-methyl-2-methylen-chinolin (1a) und cyclischen 1,3-Dicarbonylverbindungen hängt von der Natur der zwischenzeitlich entstehenden DihydroverbindungenA/B ab. Die Intermediat-KetoneA gehen durch Dehydrierung während der Reaktion in die 2-(1,2-Dimethyl-4(1H)chinolyliden)-1,3-dicarbonylverbindungen17–21 über. Die Intermediat-EnoleB mit sechsgliedrigem Dicarbonylring bilden in intramolekularer Reaktion die 6,12-Methano-dibenz[d,g][1,3]oxazocinone22–25, deren Struktur am Beispiel der Verbindung23 durch¹H-NMR sowie durch Röntgenkristallstrukturanalyse bewiesen wird.

     

Improved synthesis and crystal structure of tetrakis(acetonitrile)(η-1,5-cyclooctadiene)ruthenium(II) bis[tetrafluoroborate(1−)]

An improved, one-step synthesis of [Ru^II(1,5-COD)(CH₃CN)₄]²⁺ as the BF₄⁻ salt has been accomplished in 51% yield, an approximately 75% higher yield than the three-step literature synthesis of the corresponding PF₆⁻ salt. The improved synthesis consists of (i) grinding the insoluble [RuCl₂(1,5-COD)]_x precursor to increase the reaction rate and yield, (ii) treating the resultant [RuCl₂(1,5-COD)]_x with 2Ag⁺BF₄⁻ in refluxing acetonitrile with excess 1,5-COD present to inhibit 1,5-COD loss in the product and, most importantly, (iii) following the reaction directly by ¹H-NMR spectrometry which revealed that the substitution reaction of the Ru(II), d⁶ precursor is, as expected, quite slow and requires ca. 120 h. The [Ru(1,5-COD)(CH₃CN)₄][BF₄]₂ product was characterized by ¹H, ¹³C, and ¹⁹F-NMR, elemental analysis, and single-crystal X-ray crystallography. Problems in commercial Ru and F analyses are also addressed since this issue has been inadequately treated in the existing literature.     

Facile synthesis of 2-(substituted amino)-4<Emphasis Type="Italic">H</Emphasis>-thieno[3,2-<Emphasis Type="Italic">e</Emphasis>]-1,3-thiazin-4-ones

Interaction between 2,5-dichlorothiophene-3-carbonyl isothiocyanate, accessible via 2,5-dichlorothiophene-3-carbonyl chloride, and model heterocyclic amines produced the respective 2,5-dichloro-N-(substituted aminocarbonothioyl)thiophene-3-carboxamides. Upon heating, the deprotonated form of the latter underwent intramolecular cyclization to deliver the corresponding 2-(substituted amino)-4H-thieno[3,2-e]-1,3-thiazin-4-ones. The structures of these new bicyclic derivatives and their acyclic precursors are based on microanalytical and spectral (IR, MS, and NMR) data. Correspondence: Rajab Abu-El-Halawa, Chemistry Department, Faculty of Science, Al al-Bayt University, Mafraq, Jordan.     

9,9-二甲基-2-(4-甲氧基苯基)-4-苯基-9H-吡啶并[1,2-a]吲哚高氯酸盐的微波合成及晶体结构

利用2,3,3-三甲基-3H-吲哚高氯酸盐、1-苯基-3-(4-甲氧基苯基)-2-丙烯-1-酮与哌啶在微波辐射条件下合成了9,9-二甲基-2-(4-甲氧基苯基)-4-苯基-9H-吡啶并[1,2-a]吲哚高氯酸盐, 在甲醇中培养出单晶, 通过X射线单晶结构分析法测定分子结构和晶体结构, 晶体属于正交晶系, Pca2₁空间群, 晶胞参数为: a＝2.7923(6) nm, b＝0.92126(17) nm, c＝1.8345(4) nm, V＝4.7190(16) nm³, D_c＝1.345 g/cm³, μ＝0.201 mm^－1, F(000)＝2000, Z＝8, R₁＝0.0566, wR₂＝0.1320.