Mechanochemical Modification of Deoxypeganine Hydrochloride by Polyampholite

The solubility and dialysis of deoxypeganine hydrochloride and natural polyampholite were studied by IR spectra and x-ray diffraction analysis. Inclusion complexes form during mechanical treatment of a 1:1 mixture of deoxypeganine hydrochloride and natural polyampholite     

Binuclear Orthometalated N,N-Dimethylbenzylamine Complexes of Palladium(II): Synthesis,Structures and Thermal Behavior

Abstract

Organochalcogenolate-bridged cyclometalated palladium(II) complexes of the formulae, [Pd₂(μ-Epy)₂(Me₂NCH₂C₆H₄-C,N)₂] (2) (E = S (2a), Se (2b)), [Pd₂(μ-SAr)(μ-Cl)(Me₂NCH₂C₆H₄-C,N)₂] (3) (Ar = Ph (3a), Mes (Mes = 2,4,6-Me₃C₆H₂) (3b)) and [Pd₂(μ-SeAr)₂(Me₂NCH₂C₆H₄-C,N)₂] (4) (Ar = Ph (4a), Mes (4b)), have been synthesized by the reactions of [Pd₂(μ-Cl)₂(Me₂NCH₂C₆H₄-C,N)₂] with lead or sodium salts of the chalcogenolate ligand. These complexes have been characterized by elemental analysis, mass spectral data, and NMR (¹H and ⁷⁷Se{¹H}) spectroscopy. The molecular structure of 2, determined by single crystal X-ray diffraction analysis, revealed a Epy-bridged head-to-tail arrangement in which the eight-membered “(PdECN)₂” ring adopts a distorted twist boat conformation. The Pd····Pd separation in 2a is within the van-der-Waals interaction but in 2b it is too large to support the presence of any metal–metal interaction. The thermal behavior of these complexes has been studied by thermogravimetric analysis.     

Inclusion complexes of the natural product gossypol. Crystal structure of the 1 : 1 complex of gossypol with isovaleric acid

The crystal structure of the 1 : 1 lattice inclusion complex of gossypol with isovaleric acid has been determined by X-ray structure analysis. The crystals of C₃₀H₃₀O₈C₅H₁₀O₂ are monoclinic, space groupC2/c,a=28.835(7),b=9.063(2),c=26.880(4)Å, =109.66(1)°,V=6615(2) ų,Z=8,D _x = 1.25 g cm^–3, (CuK) = 7.14 cm^–1,T = 295 K. The structure was solved by direct methods and refined with isotropic thermal parameters to the finalR value of 0.132 for 1114 observed reflections. Hydrogen bonded gossypol molecules form columns along the [1 0 1] direction. These columns pack into layers parallel to the (101) plane. The layers of gossypol molecules are separated by the layers of isovaleric acid. The acid molecules are connectedvia a pair of O-H...O hydrogen bonds forming centrosymmetric dimers. There is no hydrogen bond interaction between the carboxylic acid dimers and gossypol molecules.     

Axial and Equatorial Dimethylamine Substitution on Phosphorus in the 1,3,2-Oxazaphosphorinane Ring System: Structures of 2-Dimethylamino-4-Phenyl-2H-1,3,2-Oxazaphosphorinane-2-Oxides

Single crystal x-ray structures of the diastereomeric 2-dimethylamino-4-phenyl-2H-1,3,2-oxazaphosphorinane-2-oxides, 5c and 6c, have been determined. The pair has been prepared in a straightforward manner by reaction of 3-amino-3-phenylpropanol with Mo₂P(O)Cl₂, and separated into pure forms by column chromatography. Crystal data of 5c: space group P2₁/n, a = 11.087(3), b = 6.087(6), c = 18.465(6)Å, β = 98.40(3)°, R = 0.035 for 1845 reflections. Crystal data of 6c: space group P2₁/n, a = 11.176(2), b = 6.893(2), c = 16.673(3)Å, β = 95.29(1)°, R = 0.037 for 1253 reflections. The fast-migrating 5c is cis (Ph and P = O group cis) with the configuration of 2RS, 4SR. The slow migrating 6c is trans with the configuration of 2RS, 4RS. In both structures the 1,3,2-oxazaphosphorinane rings are chair like with the P-end essentially flattened, The skeleton made up with 4-phenyl-1,3,2-oxazaphosphorinane is essentially the same. With a conformationally demanding 4-phenyl substituent, 5c has an axial Mc₂N whereas 6c has an equatorial Me₂N. For 6c, the exocyclic P-N bond has a partial double bond character the geometry about exocyclic N is planar. On the other hand, for 5c, the geometry about exocyclic N deviates considerably from planarity, the sum of the angles around N being 348.1°. In the crystalline state, the screw-related 5c molecules are hydrogen bonded whereas in the crystalline state, the centro-symmetrically related 6c molecules are paired-up by hydrogen bonds, both through the N-H and P = O system.     

柱芳烃机械互锁结构的制备及功能化

柱芳烃是一类具有柱状空腔结构的大环主体,近年来逐渐成为主客体作用构筑超分子体系的重要模块之一。柱芳烃家族包含柱[5]芳烃到柱[15]芳烃等成员,其中柱[5]芳烃为热力学稳定产物,合成产率最高;其次为柱[6]芳烃。柱[5]芳烃或柱[6]芳烃可做为主体,参与构筑[1](准)轮烷、[1](准)索烃等机械自锁结构,以及[n]轮烷(n≥2)、[2]索烃、雏菊链等机械互锁结构;体系中独立分子之间存在相对运动,如轮烷中柱芳烃在轴线上可以进行穿梭运动;丰富的衍生基团赋予柱芳烃互锁结构相应的功能,如手性翻转、荧光共振能量转移、超分子凝胶、Langmuir膜、催化反应等,甚至基于柱芳烃轮烷还可构筑更复杂的树枝状分子。本文综述了柱芳烃超分子互锁体系的研究进展,详细阐述了基于柱芳烃的互锁结构的合成方法及其功能化并讨论了其在构筑分子器件及其他超分子复杂体系方面的应用前景。     

Zur Reaktion von WOCl4 mit Mesitylgrignardreagenz – Kristallstrukturanalysen von [ClMg(THF)4{OWCl4(THF)}], [Mg(THF)4{OWCl4(THF)}2] und WOMes3(THF)2

Mesityl Oxo Molybdenum and Tungsten Compounds. III. Reactions of WOCl₄ with Mesityl Grignard Reagent – X-Ray Crystal Structures of [ClMg(THF)₄{OWCl₄(THF)}], [Mg(THF)₄{OWCl₄(THF)}₂], and WOMes₃(THF)₂ The reaction of WOCl₄ with MesMgBr (1 : 1) in tetrahydrofuran (THF) proceeds via reduction to tungsten(V), which can be isolated as [MgX(THF)₄][WOCl₄(THF)] ( 2 ) and by elimination of MgX₂ in form of [Mg(THF)₄{OWCl₄(THF)}₂] ( 3 ). The reaction of WOCl₄ with MesMgBr in the molar ratio 1 : 4 yields after reduction [WOMes₃(THF)] · THF ( 4 ). All complexes are characterized by X-ray structure analyses. In 2 and 3 [WOCl₄(THF)]^– anions are linked via their oxo ligands to the magnesium ions. 4 has a distorted trigonal bipyramidal coordination sphere.     

Crystal structure of supramolecular complexes formed by 18-crown-6 andcis-anti-cis-dicyclohexano-18-crown-6 (host) with 3,4-diaminofurazane (guest)

An X-ray—diffraction study is reported for two molecular complexes containing 3,4-diamino-1,2,5-oxadiazole as guest (G) with 18-crown-6 (18-C-6) andcis-anti-cis-dicyclohexano-18-crown-6 (DCH-6B) as host. Both complexes are of the polymeric-chain structure with the guest molecule bridging two crown neighbours. ComplexI: [18-C-6*G*H₂O], 111, monoclinic,P2₁/n,a=8.171(1),b=15.042(2),c=16.209(6) Å, =101.15(2)°, finalR-factor 0.068. ComplexII: [DCH-6B*G], 11, monoclinicC2/c,a=21.212(4),b=9.380(2),c=13.049(3) Å, =108.61(3)°, finalR 0.047.     

Hydrothermal Synthesis and Structure of a Novel Binuclear Molybdenum Complex with Oxalate Ligand, （enH2） {NH4[Co（en）3] [Mo2O7（C2O4）] }2.2H2O~

1INTRODUCTIONThecurrentinterestinoxalatesreflectstheirstructuralrichnessandwideuseinanalyticalche-mistryandindustry[1].BecausemolybdenumintheVandVIoxidationstatesformsaconsiderablenumberofoxocomplexes,andtheequilibriainsolutionbetweenpolyoxomolybdenumspec…     

Hydrothermal Synthesis and Structure of a Novel Binuclear Molybdenum Complex with Oxalate Ligand,(enH2){NH4[Co(en)3][Mo2O7(C2O4)]}2·2H2O

The title complex (enH2){NH4[Co(en)3][Mo2O7(C2O4)]}2·2H2O (C18H70Co2Mo4- N16O24, Mr = 1396.52) was obtained under hydrothermal conditions and its crystal structure has been determined by single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group P21/c with a = 17.8023(8), b = 7.7527(4), c = 16.9781(4)A,β= 103.878(7)°, V = 2274.8(2) A3, Dc = 2.039 g/cm3, Z = 2,μ(MoKα) = 1.878 mm-1 and F(000) = 1408. The final R = 0.0410 and Wr = 0.1070 for 4065 observed reflections with I≥2σ(I). The crystal structure is composed of bi- nuclear [Mo2O7(C2O4)]4- anions, complex [Co(en)3]2+ cations, protonated ethylenediamine cations, ammonium cations and crystal water molecules, which are held together into a three-dimensional network via hydrogen-bonding interactions. The binuclear structure of [Mo2O7(C2O4)]4- consist of one MoO4 and one MoO6 octahedra through sharing a bridging oxygen atom, where the oxalate ligand acts as a bidentate ligand coordinating to the octahedral molybdenum atom though two deprotonated corboxylate groups.     

Crystal and Molecular Structure of 2,3-Tetramethylen-3,4-dihydroquinazoline

The crystal and molecular structure of the alkaolid 2,3-tetramethylen-3,4-dihydroquinazoline hydrochloride was solved by X-ray structure analysis. It was demonstrated that the crystal contains an aqua system similar to those in the isostructural 2,3-trimethylen-3,4-dihydroquinazoline (deoxypeganine), and 2,3-pentamethylen-3,4-dihydroquinazoline hydrochlorides.     

Structures of crystalline mixed peganole-brompeganole systems

The structures of mixed crystals — solid solutions in the peganole-brompeganole system with molar ratios 0.72:0.28, 0.32:0.68, 0.10:0.90 and of pure peganole are determined by single crystal X-ray diffraction. It is shown that the solid solutions (mixed crystals) exist as three different phases. These crystal structures tend to form closed centrosymmetric dimers involving two molecules (probably different) joined by “anti-parallel” centrosymmetric hydrogen O-H...N(1) bonds. The development of this dimer is the cause of forming mixed crystals in the peganole–brompeganole system.     

Cyclic porphyrin dimers as hosts for coordinating ligands

Bicovalently linked tetraphenylporphyrins bearing dioxypentane groups at the opposite (transoid, H₄A) and adjacent (cisoid, H₄B) aryl groups have been synthesised. Protonation of the free-base porphyrins leads to fully protonated species H₈A⁴⁺/H₈A⁴⁺ accompanied by expansion of cavity size of the bisporphyrins. The electrochemical redox studies of these porphyrins and their Zinc(II) derivatives revealed that the first ring oxidation proceeds through a two-electron process while the second ring oxidation occurs at two distinct one-electron steps indicating unsymmetrical charge distribution in the oxidized intermediate. The axial ligation properties of the Zinc(Il) derivatives of H₄A/H₄B with DABCO and PMDA investigated by spectroscopic and single crystal X-ray diffraction studies showed predominant existence of 1: I complex. The Zn₂A.DABCO complex assumes an interesting eclipsed structure wherein DABCO is located inside the cavity between the two porphyrin planes with Zn-N distances at 2.08 and 2.22 ?. The Zn atoms are pulled into the cavity due to coordination towards nitrogen atoms of DABCO and deviate from the mean porphyrin plane by 0.35 ?. The electrochemical redox potentials of the axially ligated metal derivatives are found to be sensitive function of the relative coordinating ability of the ligands and the conformation of the hosts.     

Syntheses, Structures and Luminescent Properties of Two Zinc Complexes Containing N-P-Acetamidobenzenesulfonyl-glycine Acid Ligand

Using N-P-acetamidobenzenesulfonyl-glycine acid （abbreviated as abglyH2） as a ligand, two zinc（II） complexes [Zn（abglyH）2（bipy）2（H2O）2], （1） and {[Znz（abgly）2（bipy）2（H2O）2]. 2（H2O）}n （2） （bipy = 4,4＇-bipyridine） have been synthesized under mild conditions and characterized by IR, elemental analysis and X-ray diffraction analysis. Complex 1 is a monomeric compound, which is further assembled by intermolecular hydrogen bonds and π-π interactions into a 3-D supramolecular network. Complex 2 adopts a one-dimensional double chain structure and is further linked by hydrogen bonds to form a 2-D structure. Fluorescent analysis shows that complex 1 has an emissive maximum at 337 nm and complex 2 exhibits an emissive maximum at 339 nm in the solution state at room temperature.     

Structure of Dibenzocrown Ethers and their H-Bonded Adducts.1. [1.5]Dibenzo-18-Crown-6 and Biphenyl-20-Crown-6: Complexes with Amidosulfuric Acid

The interaction of the amidosulfuric acid NH ₃ SO ₃ with 15 distal and proximal dibenzocrown ethers, including diphenyloxide, diphenylsulfide and biphenyl ones leads to the stable (1:1) complexes only in the case of [2.4]- and [1.5]dibenzo-18-crown-6 and biphenyl-20-crown-6. According to the data of the X-ray analysis, in the two last adducts the amidosulfuric acid coordinates to hexadentate crown ethers in a zwitterion form through a near-ideal ‘tripod’ arrangement to alternate crown oxygen atoms. The conformations of crown molecules are different in complexes and in initial macrocyclic ligands.This revised version was published online in July 2005 with a corrected issue number.     

Pericyclic reactions with participation of the (PC)-double bond

Abstract

Equilibrium between the tetraphospha-bicyclo[2.2.0]hexane and tetraphosphahexadiene-structure, opening of CC-bonds in organic ringsystems by [3.3]-sigmatrope rearrangements, Diels-Alder-reactions with phosphaalkenes.     

Direction of bromination and nitration of deoxypeganine and its hydrochloride using HPTLC. Synthesis of 6-bromo(nitro)-, 6,8-dinitrodeoxyvasicinones, 6-nitro(bromo)-, 6,8-dinitrodeoxypeganines,and 6H(bromo)peganols

The reaction of deoxypeganine (DOP) (1) and its hydrochloride (DOP·HCl) (2) with N-bromosuccinimide and a nitrating mixture was studied. It was found that bromination of DOP occurred at C-4 and the aromatic ring. Nitration of DOP·HCl produced either 6-nitro- or 6,8-dinitro-deoxypeganines and 6-nitrodeoxyvasicinone or their mixture in various ratios depending on the substrate:nitrating mixture ratio. 6Hand 6-Br-deoxypeganines were transformed into the 4-hydroxy derivatives, 6H(Br) peganols or deoxyvasicinones. A method for qualitative and quantitative analysis of the pure compounds and the mixture of reaction products using HPTLC was developed. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 505–509, September-October, 2008. Original article submitted March 26, 2008.     

Structures of poly(p-hydroxybenzoic acid) (PHBA) at ambient temperature

The molecular structure of poly (p-hydroxybenzoic acid) (C₆H₄COO)_x at ambient temperature was determined by x-ray powder diffraction analysis. The diffraction pattern is explained as a mixture of two orthorhombic phases having the same space group Pbc2₁ with four C₆H₄COO chemical repeats in the unit cell and the following cell parameters: a = 7.42 Å, b = 5.70 Å, and c = 12.45 Å for phase I (ρ_calc = 1.51 g cm^?3); and a = 3.83 Å, b = 11.16 Å, and c = 12.56 Å for phase II (ρ_calc = 1.48 g cm^?3). The chain conformation is the same in both phases, involving two benzoyl rings staggered by ca. 120° along the chain. Disorder has been considered in the packing of phase I by giving equal occupancy to the two molecules oriented up or down along the c chain axis. ©1995 John Wiley & Sons, Inc.     

Synthesis and reactivity of μ-η2-carbamato complexes of triosmium decacarbonyl

The synthesis of (-H)(-²-RRNCO₂)Os₃(CO)₁₀ (R=R=CH₃ 2a; R=R=CH₂CH₃,2b; R=CH₃, R=CH₂CH₃,2c) and their cyclic analogs (-H)(-²--CO₂)Os₃(CO)₁₀(n=42d,n=5,2e) from carbon dioxide, secondary amine, and Os₃(CO)₁₀(CH₃CN)₂ (1) are reported. A solid-state structure of2c reveals a bonding mode for the carbamato ligand very similar to that observed for related carboxylato complexes. Compound2c crystallizes in the orthorombic space group Pbca witha=9.136 (3),b=15.310 (4) andc=30.361 (5) Å;V=4247 ų,Z=8. Least-squares refinement of 2405 observed reflections gave a final agreement factor ofR=0.043 (R _w =0.043). The reactivity of the complexes2a–2e was examined. Compound2c or2b give good yields of the cluster derivatives (-H)(-X)Os₃(CO)₁₀ (X=Cl,3; X=OCH₃,4; X=N(CH₃)₂,7) when reacted with HX. Reaction of2a with P(CH₃)₃ at 68°C gives good yields of the otherwise difficult to obtain 1,1,2-(P(CH₃)₃)₃Os₃(CO)₉ (5). Evidence is presented that suggests that2a–2e form by oxidative addition of preformed carbamic acids to1.     

联咪唑镍、镉配合物的合成、晶体结构及其与DNA相互作用

分别通过水热法和室温挥发法合成了2,2'-联咪唑(H₂biim)镍、镉配合物([Ni(H₂biim)₃](phth)(phth,邻苯二甲酸根)(1)、[Cd(H₃biim)₂Cl₄](2)),并通过X射线单晶衍射、元素分析和红外等技术手段对它们进行了表征。 单晶X衍射结果表明,配合物1的配离子中心镍离子周围的配体以3个中性联咪唑分子形式分别进行二齿螯合配位,构成六配位的畸变八面体构型,邻苯二甲酸根离子在外界与配体形成丰富的氢键;而在配合物2中,两个联咪唑配体却以含有氢质子的阳离子H₃biim⁺形式与中心镉离子单齿配位,镉离子同时结合4个氯原子形成六配位配位环境。 通过紫外光谱、荧光光谱和黏度法测试结果表明配合物1和2分别与小牛胸腺DNA(ct-DNA)以经典插入和部分插入模式进行相互作用。