Structural and Spectral Studies of Some Geometric Isomers of N-Pivaloyl-N'-dichlorophenyl Thiourea

N-pivaloyl-Nˊ-(3,4-dichlorophenyl)thiourea (1): monoclinic, P21/a, a=11.57(1), b=9.278(8), c=13.51(1), β=103.85(1)°, V=1408(2)3 , Z=4, μ=0.598 mm-1 ; N-pivaloyl-N'-(3,5- dichlorophenyl)thiourea (2): monoclinic, P21/a, a=7.176(2), b=16.441(4), c=11.923(2), β=92.48(1)°, V=1405.3(6)3 , Z=4, μ=0.600 mm-1 ; N-pivaloyl-Nˊ-(2,6-dichlorophenyl)thiourea (3): orthorhombic, Pnma, a=26.79(1), b=8.780(4), c=5.955(3), V=1400.7(11)3 , Z=4, μ=0.601 mm-1 . All three complexes have an intramolecular hydrogen bond between NˊH and the carbonyl oxygen. Solution 1H NMR studies (CDCl3) show the NH resonance considerable downfield for each thiourea and their positions, as well as that of NH, is affected by substituents on the phenyl ring.     

The effects of anion variation and ligand derivatization on silver coordination networks based upon weaker interactions

This article presents a series of silver(I) coordination networks based upon nonchelating bidentate thioether ligands. Frameworks using AgOTs as the silver(I) starting material form two-dimensional frameworks and are quite stable as shown by differential scanning calorimetry/thermogravimetric analysis (DSC/TGA) data. The networks are sufficiently robust as to maintain the same layered motif when the basic skeleton of the ligand is sequentially derivatized with -OEt, OBu, and OHex groups. Crystal structures of the AgOTs complexes of the underivatized and bis(hexoxy) derivatives, compounds 5 and 8, respectively, are presented as well as powder X-ray diffraction (PXRD) data of the other complexes. For 5, C20H20S3O3Ag, crystal data are as follows: monoclinic, space group P2(1)/n, a = 11.8117(5) A, b = 7.8813(5) A, c = 22.3316(10) A, beta = 102.245(5) degrees, V = 2031.6(2) A(3), Z = 4. For 8, C30H44S3O6Ag, crystal data are as follows: triclinic, space group Ponebar a = 8.445(4) A, b = 10.855(5) A, c = 19.308(9) A, alpha = 84.53(1) degrees, beta = 78.76(1) degrees, gamma = 68.43(1) degrees V = 1613.9(13) A(3), Z = 2. Changing the silver(I) starting material to AgPF6 results in a shift to a one-dimensional structure, 9, as shown by X-ray crystallography and in highly compromised stability. For 9, C14H16S2N2PF6Ag, crystal data are as follows: monoclinic, space group P2/n, a = 11.9658(11) A, b = 3.9056(4) A, c = 19.6400(18) A, beta = 92.87(1) degrees, V = 916.70(15) A(3), Z = 4.     

Pd.H-C Interactions. Preparation and Structure of Orthometalated Tetranuclear Complexes of Palladium(II) and Platinum(II)

The reaction of 2-(1-naphthyl)benzothiazoline with palladium(II) acetate leads to helical mononuclear and orthometalated tetranuclear products. The molecular structures of mononuclear palladium(II) [Pd(H1-nabz)(2)] (1) (H(2)1-nabz = 2-N-(1-naphthylmethylideneamino)benzenethiolate), tetranuclear palladium(II) [Pd(4)(1-nabz)(4)] (2) and tetranuclear platinum(II) [Pt(4)(1-nabz)(4)] (3) have been determined by single-crystal X-ray diffraction method. Crystal data for complex 1 are as follows: a = 14.208(3) ?, b = 18.227(4) ?, c = 14.398(8) ?; beta = 94.55(3) degrees; V = 3717.0(23) ?(3); space group = P2(1)/n, Z = 4. Crystal data for the complex 2 are as follows: a = b = 15.798(3) ?, c = 23.728(4) ?; V = 5921.7(20) ?(3); space group = I4(1)/a, Z = 16 for the Pd(1-nabz) unit. Crystal data for the complex 3 are as follows: a = b = 15.496(2) ?, c = 24.348(3) ?; V = 5846.3(20) ?(3); space group = I4(1)/a, Z = 16 for the Pt(1-nabz) unit. The mononuclear palladium(II) complex reveals short ortho-hydrogen.palladium distances of 2.66(7) and 2.48(7) ?. These short distances and (1)H NMR studies provide a M.H-C interaction which can be regarded as a three-center four-electron interaction. The molecular structures of 2 and 3 confirm the formation of unusual tetranuclear compounds featuring a rare C,N,S-tridentate ligand derived from orthometalation of pendant side arm. The structural and chemical properties of the mononuclear palladium(II) complex 1 clearly suggest that 1 is a potential intermediate in the formation of the tetranuclear complex 2 by orthometalation reactions.     

Synthesis and Crystal Structure of Copper(II) Complex with N-Acetoxyl-picolinamide

1 INTRODUCTION The picoloylhydrazide compounds are close to thebiologic environment and can react with microele-ments in organism so as to have antitubercular andantineoplastic activities. However, owing to the exis-tence of amino group, this kind of compounds aretoxic to some extent[1]. In order to decrease theirtoxicity, hydrazone or hydrazide compounds synthe-sized by the condensation reaction of amino and car-bonyl groups have been well studied in recentyears[1～7]. Herein we report t…     

由6-氨基取代富烯合成二茂锆配合物及其结构研究

富烯已被广泛应用于合成各种取代环戊二烯基、茚基和芴基金属配合物[1] .富烯的取代基对于它本身的反应性质以及由富烯所派生出的金属配合物的性质都起着重要的作用 .另外 ,富烯在手性配体及手性金属配合物的合成方面起着非常重要的作用 [2 ,3] ,仅就 6,6-二烷基富烯的加成反应而言 ,不但可以合成出多种烷基取代的手性金属配合物 [4 ] ,还可以引入杂原子而合成出手性配体 [5] .在研究 6-氨基富烯的加成反应时人们发现 ,由它不仅可以生成手性配体 ,而且其取代基上的氨基还可以与中心金属原子发生配位 [6 ] .最近 ,我们研究了 6-二甲氨基 - 6-…     

Synthesis and Crystal Structure of Diisopropyl Genistein-7-yl Phosphate

Diisopropyl genistein-7-yl phosphate (C21H23O8P, Mr = 434.11) has been synthesized by a facile phosphorylated reaction with genistein and diisopropyl phosphite, and its structure was determined by IR, NMR, HR MS and X-ray single-crystal diffraction. The crystal belongs to monoclinic, space group P21/n, with a = 9.0690(18), b = 9.0412(18), c = 26.544(5), β = 99.44(3)°, V = 2147.0(7) 3, Z = 4, Dc = 1.344 Mg/m3, μ = 0.172 mm-1, F(000) = 912, the final R = 0.0545 and wR = 0.1352. In the crystal structure, the title compound is constructed by both intramolecular (O–H···O=C) and intermolecular (O–H···O=P) hydrogen bonding as well as π-π stacking interaction.     

Structure of Molybdenum Complex of Benzothiazole－2－thiolate（η~5－C_5H_5）Mo（CO）_2（C_7H_4NS_2）

ＳｔｒｕｃｔｕｒｅｏｆＭｏｌｙｂｄｅｎｕｍＣｏｍｐｌｅｘｏｆＢｅｎｚｏｔｈｉａｚｏｌｅ－２－ｔｈｉｏｌａｔｅ（η~５－Ｃ_５Ｈ_５）Ｍｏ（ＣＯ）_２（Ｃ_７Ｈ_４ＮＳ_２）ＣｈｅｎｇＧｕｏ－Ｂａｏ~ａ；ＷｕＱｉａｎｇ－Ｊｉｎ~ｂ；ＨｕａｎｇＸｉａｏ－Ｙｉｎｇ~...     

Rotational spectra of 1-chloro-2-fluoroethylene. I. Main isotopologues and deuterated species of the trans isomer

Guided by theoretical predictions, the rotational spectra of the mono- and bideuterated species of trans-1-chloro-2-fluoroethylene, CH35Cl=CDF, CH37Cl=CDF, CD35Cl=CHF, CD37Cl=CHF, CD35Cl=CDF, and CD37Cl=CDF, have been recorded for the first time. Assignment of the Delta J = 0 and Delta K(-1) = +1 bands with K(-1) = 3,4,5,... (all isotopic species) as well as of several Delta J = +/-1 and Delta K(-1) = +1 transitions (all isotopic species except CH37Cl=CDF, CD37Cl=CHF, and CD37Cl=CDF) led to the accurate determination of the ground-state rotational constants, the quartic, and some sextic centrifugal distortion constants, as well as the nuclear quadrupole coupling constants for both 35Cl and 37Cl in good agreement with corresponding theoretical predictions based on high-level coupled-cluster calculations. Inconsistencies of the present spectroscopic parameters with respect to those reported earlier for the two main isotopologues, i.e., CH35Cl=CHF and CH37Cl=CHF, necessitated a reinvestigation of the rotational spectra for these two isotopic species. Supported by quantum chemical calculations, the previously recorded spectra are reassigned to a vibrationally excited state, while analysis of the Delta J = 0 and Delta K(-1) = +1 as well as some Delta J = +/-1 and Delta K(-1) = +1 transitions provided a revised set of spectroscopic parameters for the vibrational ground state of these two isotopic species.     

Stabilization of new forms of the intermetallic phases beta-RENiGe2 (RE = Dy, Ho, Er, Tm, Yb, Lu) in liquid indium

Flux conditions using liquid indium bypass the thermodynamically stable structure and yield new forms of the phases RENiGe2 (RE = Dy, Er, Yb, Lu). The compounds crystallize in the orthorhombic Immm space group and possess the YIrGe2 structure type. Lattice parameters for ErNiGe2, DyNiGe2, YbNiGe2, and LuNiGe2 are a = 4.114(1) A, b = 8.430(2) A, c = 15.741(5) A; a = 4.1784(9) A, b = 8.865(2) A, c = 15.745(3) A; a = 4.0935(6) A, b = 8.4277(13) A, c = 15.751(2) A, and a = 4.092(1) A, b = 8.418(3) A, c = 15.742(5) A, respectively. These phases represent a new structural arrangement (beta) of the compound type RENiGe2 as another set of compounds with identical stoichiometry are known to adopt the orthorhombic Cmcm CeNiSi2 type structure (alpha). In this paper we report the crystal and electronic band structure of four new members of the YIrGe2 structure type, as well as an investigation of the relative thermodynamic stabilities of the two forms.     

Synthesis and characterization of novel homoleptic N,N-dialkylcarbamato complexes of antimony: precursors for the deposition of antimony oxides

A series of tris(N,N-dialkylcarbamato)antimony(III) complexes, Sb(O(2)CNR(2))(3) (R = Me, Et, Pr(i)()), have been synthesized and are the first members of this class of compound to have been crystallographically characterized. Sb(O(2)CNMe(2))(3) (1) exists as a weakly bound dimer, whereas its diethyl and diisopropyl analogues (2, 3) are monomeric. In addition, tetrakis(N,N-diethylcarbamato)tin(IV) (4) has been prepared for comparison and shown by single-crystal X-ray analysis to exhibit the relatively rare SnO(8) coordination. Crystallographic data: for 1, a = 8.7520(5) A, b = 14.2970(8) A, c = 11.8150(7) A, beta = 108.029(2) degrees, monoclinic, P2(1)/c, Z = 4; for 2, a = b = 14.4690(2) A, c = 16.6740(2) A, trigonal, Rthremacr;, Z = 6; for 3, a = 11.9881(2) A, b = 11.6521(3) A, c = 19.8780(6) A, beta = 90.401(1) degrees, monoclinic, P2(1)/n, Z = 4; for 4, a = 13.9654(2) A, b = 12.0817(2) A, c = 16.6752(2) A, beta = 108.1960(7) degrees, monoclinic, C2/c, Z = 4. Sb(O(2)CNMe(2))(3) has been used as a single-source precursor in the low-pressure chemical vapor deposition of the senarmonite form of Sb(2)O(3).     

Alkali metal complexes of a phosphine-borane-stabilised carbanion: influence of co-ligands on structure

The adducts [[(Me(3)Si)(2){Me(2)P(BH(3))}C]K(L)(n)](m) [L = THF, n = 0.5, m = infinity (2a); L = tmeda (2b), pmdeta (2c), n = 1, m = 2] may be synthesised by treatment of solvent-free [[(Me(3)Si)(2){Me(2)P(BH(3))}C]K](infinity) (2) with the corresponding Lewis base (tmeda = N,N,N',N'-tetramethylethylenediamine; pmdeta = N,N,N',N',N'-pentamethyldiethylenetriamine). X-Ray crystallography reveals that, whereas 2 crystallises with a complex 2-dimensional sheet structure, 2a crystallises as a ribbon-type one-dimensional polymer and both 2b and 2c crystallise as dimers. The corresponding complex with 12-crown-4, [K(12-crown-4)(2)][(Me(3)Si)(2){Me(2)P(BH(3))}C] (2d) crystallises as a separated ion pair. The complexes [[(Me(3)Si)(2){Me(2)P(BH(3))}C]M(pmdeta)](n) [M = Na, n = 1 (6); M = Rb, n = 2 (7)] may be synthesised by treatment of [(Me(3)Si)(2){Me(2)P(BH(3))}C]M with pmdeta. Whereas crystallises as a discrete monomer, compound 7 crystallises as a dimer. Compounds 2, 2a-2d, 6, 7 and the corresponding caesium derivative [[(Me(3)Si)(2){Me(2)P(BH(3))}C]Cs(pmdeta)](2) () provide an opportunity to consider the influence of the ionic radius of the metal and the nature of the co-ligands on the structures of alkali metal complexes of a phosphine-borane-stabilised carbanion.     

1-苯基-5-(3,4-二甲氧基苯基)-3-羟基吡唑的合成和晶体结构

标题化合物(I)是由 1-苯基-5-(3, 4-二甲氧基苯基)-3-吡唑烷酮在 FeCl3催化下被氧气氧化得到的。它的结构经过了元素分析、IR、1H NMR 的表征,用 X-射线衍射法测定了化合物的晶体结构。C17H16N2O3(I)的晶体学参数分别为:三斜晶系,P1空间群,a = 6.6600(13),b = 8.4200(17),c = 14.060(3) ?,α= 85.61(3), β= 76.89(3), γ= 81.18(3)?, Z = 2, Dc= 1.298g/cm3, V = 758.1(3) ?3, Mr = 296.32,μ= 0.090 mm–1, F(000) = 312, R = 0.048,wR = 0.1231。结构测定表明化合物的吡唑环存在着一个大的共轭体系,含有一个稳定的烯醇结构,分子通过分子间的氢键形成了网状的结构。     

Synthesis, Structure and Photo- luminescence of Cu[（PPh3）2]（acac） （PPh3 = Triphenylphosphine, acac = Acetylacetone）

A novel complex Cu(PPh3)2(acac) 1 (PPh3 = triphenylphosphine, acac = acetylacetone) was obtained by a solution reaction and structurally characterized by X-ray diffraction. The crystal belongs to monoclinic, space group P21/n with a = 13.7361(8), b = 12.8204(7), c = 19.7638(13) , β = 95.946(2)°, C41H37CuO2P2, Mr = 687.19, V = 3461.7(4) 3, Z = 4, Dc = 1.319 g/cm3, S = 1.067, μ(MoKα) = 0.758 mm–1, F(000) = 1432, R = 0.0403 and wR = 0.0990. Complex 1 is characterized by an isolated structure. X-ray structure analysis of 1 shows that acac behaves as a chelating ligand and PPh3 coordinates as a monodentate ligand to the Cu(I) atoms. Photoluminescent investigation reveals that the title complex displays a strong green-light emission.     

弱桥联二聚体氯代二苄基锡二甲基氨荒酸酯的合成、 表征及晶体结构

利用二苄基二氯化锡和二甲基氨荒酸盐反应,合成了氯代二苄基锡二甲基氨荒酸酯。通过元素分析、红外光谱和核磁共振氢谱对其结构进行了表征。用X-射线单晶衍射测定了该化合物的晶体结构。它属于三斜晶系,空间群为P1,a=0.75750(15),b=1.0615(2),c=1.2059(2)nm,α=95.053(3)°,β=95.539(4)°,Υ=99.113(4)°,Z=2,V=0.9476(3)nm^3,Dx=1.600g/cm^3,μ=1.705mm^-^1,F(000)=456,R1=0.0409,wR2=0.1194[I≥2σ(I)]。分子中锡原子的配位数为5,形成一个严重扭曲的三角双锥构型,并且化合物以弱桥联二聚体存在。     

Direct high-performance liquid chromatographic method for enantioselective and diastereoselective determination of selected pyrethroic acids

This study reports on the direct HPLC stereoisomer separation of selected pyrethroic acids employing commercial cinchona alkaloid derived chiral stationary phases (CSPs). cis/trans-Chrysanthemic acid (cis/trans-CA), cis/trans-chrysanthemum dicarboxylic acid (cis/trans-CDCA), cis/trans-permethrinic acid (cis/trans-PA), and fenvaleric acid (FA) were resolved into the individual stereoisomers, i.e. enantiomers and diastereomers as well. To achieve satisfactory baseline separation an optimisation of the variables of the chromatographic method including chemical structure of the cinchona carbamate CSP, mobile phase composition, and flow rate was required. All four stereoisomers of PA were successfully separated in a single run (alphacis = 1.20, alphatrans = 1.26, critical Rs = 1.65) with an acetonitrile (ACN)-based polar-organic eluent. The complete baseline resolution of all CA stereoisomers succeeded in polar-organic (alphacis = 1.20, alphatrans = 1.35, critical Rs = 3.03) as well as in acetonitrile-based reversed-phase media (alphacis = 1.24, alphatrans = 1.22, critical Rs = 2.73). The latter elution mode was also found to be suitable for the enantio- as well as diastereoselective resolution of CDCA (alphacis = 1.09, alphatrans = 1.50, critical Rs = 1.43), which is to the best of our knowledge the first reported enantiomer separation of this analyte. The enantiomers of FA could be baseline separated employing also reversed-phase mode (alpha = 1.16, Rs = 2.91). These separation methods may be applied for quality control processes in the production of stereoisomerically pure insecticides as well as stereoselective toxicokinetic studies, as CDCA, PA, and FA are suitable biomarkers for monitoring human pyrethroid burden.     

Isolation and Crystal Structure of 1',4'-Trans-diol of Abscisic Acid

1 INTRODUCTION It has been reported that botrytis cinerea, a plant pathogenic fungus, can produce abscisic acid ((2- cis,4-trans)-5-(1-hydroxy-2,6,6-trimethyl-4-oxo-2- cyclohexen-1-yl)-3-methyl-2,4-pentadienoic acid 1)[1] and 1?,4?-trans-diol of abscisic acid 2 that is a pre- cursor of 1[2]. Abscisic acid is an important plant hormone that can inhibit the germination of seeds[3]. Meanwhile, the derivatives of 2, 1?,4?-trans-diol of abscisic acid ester 3 and 4?-methoxy derivative 4, are oil…     

Synthesis under Micromave Irradition and Crystal Structure of 4''-Acetylbenzo-15 -crown-5thiosemicarbazone

The title compound is a bifunctional receptors including a thiourea group and a crown ether ring. Due to many possible potentials as a new class of reagents for membrane transports,ion-selective electrodes as well as reaction catalysts, the design and synthesis of bifunctional receptors for simultaneous binding of cations and anions is of ongoning interest in srprarnolecular chemistry1-5. In bifunctional receptors, the binding sites for anions and cations are covalently linked so as to exhibit allosteric or cooperative complexation where the binding affinity for anions(cations)is modified as a result of the cation(anion) complexation.Literature[6] reported that the ability of the thiourea group to bind anions is significantly enhanced when Na+ is bound to the crown moiety. To date, however only a few receptors of this class have been reported.6-8In this paper, we report an improved procedure under microwave irradiation that gives higher yields of title compound and needs fewer reaction times than traditional method.The structure of this compound was determined by IR ,element analysis and X-ray analysis.Scheme 1 The reaction equationThe crystal belongs to triclinic crystal system, P-1 space group, a=0.9547(0)nm, b=1.3637(3)nm,c=1.6029(3)nm, α =75.33(3) , β =83.62(3) , γ =70.99(3) ,Z=4,Dc=1.335g/cm3,F(000)=816,R1= 0.0557 ,wR2=0.1281. It is assembled into a three-dimensionalsupramolecule by intermolecular hydrogen bonds.     

Ring-opening polymerisation of rac-lactide mediated by cationic zinc complexes featuring P-stereogenic bisphosphinimine ligands

The diastereomerically pure P-stereogenic bis(phosphinimine) ligands 4,6-(ArN[double bond, length as m-dash]PMePh)(2)dbf [Ar = 4-isopropylphenyl (Pipp): rac-4, meso-4; Ar = 2,6-diisopropylphenyl (Dipp): rac-4a; dbf = dibenzofuran] were synthesised and complexed to zinc using a protonation-alkane elimination strategy. The cationic alkylzinc complexes thus obtained, RZn[4,6-(ArN[double bond, length as m-dash]PMePh)(2)dbf][B(Ar')(4)] [Ar = Pipp, Ar' = C(6)H(3)(CF(3))(2): rac-6 (R = Et), meso-6 (R = Et), rac-7 (R = Me) meso-7 (R = Me); Ar = Dipp: rac-6a (R = Et, Ar' = C(6)H(3)(CF(3))(2)), rac-6b (R = Et, Ar' = C(6)F(5))] were investigated for their competency as initiators for the ring-opening polymerisation of rac-lactide. The formation of polylactide was achieved under relatively mild conditions (40 °C, 2-4 h) and the microstructures of the resulting polymers exhibited a slight heterotactic bias [polymer tacticity (P(r)) = 0.51-0.63].