Crystal Structure of 3′-(4-Methoxyphenyl)-2-Phenyl-4′-(4-Ethoxyphenyl)-1,2-Dihydro-4H,4′H-Spiro [Isoquinoline-3,5′-Isoxazol]-4-One

The title compound, 3′-(4-methoxyphenyl)-2-phenyl-4′-(4-ethoxyphenyl)-1,2-dihydro-4H,4′H-spiro[isoquinoline-3,5′-isoxazol]-4-one was synthesized from the reaction of dipolarophile with p-methoxybenzadoxime in the presence of sodium hypochlorite in chloroform solution. The structure of the synthesized compound was determined by IR, ¹H NMR, mass spectroscopic data, ¹³C NMR spectroscopy, elemental analysis and X-ray crystallography. The structure was solved in monoclinic, space group C2/c with a = 21.941 (4), b = 17.233 (3), c = 15.404 (3) Å, β = 122.193 (2), V = 4928.9 (16) Å³, Z = 8 and with R_int = 0.154. The geometry of the title compound showed that the piperidine ring adopts a half-chair conformation. In the crystal structure, molecules are linked by C–H···O and C–H···N contacts. Weak C–H···π interactions plays an important role in stabilizing the supramolecular structure.     

4′-(4-(4-羧基苯氧基)苯基-4,2′6′,4″-三联吡啶的 合成、晶体结构及性质研究

以4-乙酰基吡啶及对氯苯甲醛为原料合成了一例新的化合物4′-(4-(4-羧基苯氧基)苯基-4,2′6′,4″-三联吡啶,用元素分析、红外光谱、紫外光谱、X射线单晶衍射对此化合物进行了表征,结果表明,该化合物属于P2(1)/c空间群,晶胞参数为:a=1.4405(5)nm,b=0.7708(2)nm,c=2.0567(7)nm,β=107.699(6)°.     

2-甲基4-(4-(吡啶-3-乙炔基)苯基)-3-丁炔-2-醇的合成及晶体结构

由1,4-二碘代苯出发,经过两步Sonogashira偶联反应合成了标题配合物2-甲基4.(4-(吡啶-3-乙炔基)苯基)-3-丁炔-2-醇.通过1H NMR、13C NMR核磁共振、Ⅹ-射线单晶衍射等手段对化合物的结构进行了表征.结果表明,该化合物晶体属于单斜晶系,空间群为P21/c.晶体学参数:a=3.3321 (4) nm,b=1.00539(11) nm,c=0.89158(10) nm,α =90.00°,β=92.442(2)°,y=90.00°,V=2984.2(6) nm3,Z =4.     

Synthesis and mesomorphic properties of 2,4-bis(4′-n-pentyloxybenzoyloxy)- benzylidine-4″- n-alkoxyaniline

The synthesis and mesomorphic properties of a new series of 2,4-bis(4′-npentyloxybenzoyloxy)- benzylidine-4″ -n-alkoxyaniline (DC5An) are reported. The molecular structure of compounds was confirmed by FTIR, ¹H-NMR, ¹³C-NMR, mass spectroscopy and elemental analysis. The mesomorphic properties were studied by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM) measurements. All compounds of the series exhibit nematic (N) and smectic C (SmC) phases. The first four homologues (DC5A1-DC5A4) display a N mesophase, whereas the highest homologues (DC5A5-DC5A10) exhibit an enantiotropic dimorphism N and SmC phases. The mesomorphic properties of the present series are compared and discussed with other structurally related series.     

The Metabolemeter III: Phase Behaviour Under Pressure of bis-(4-4′-n-Heptyloxybenzylidene)- 1, 4-Phenylenediamine and Terephthalylidene-bis-(4-n-Decylaniline)

By using a metabolemeter, the phase transitions of bis-[4, 4′-n-heptyloxybenzylidene]-1, 4 phenylenediamine (HBPD) and terephthalylidene-bis-[4-n-decylaniline] (TBDA) have been studied. The weakly first order phase transitions (S_G-S_F and S_F-S_I) and the narrowly separated phase transitions (S_C-S_A and S_A-I) of TBDA are detectable. For HBPD, both transitions S_G-S_I and S_I-S_C are individually observed and the enthalpy changes are deduced from pressure increments at the tranformations: two triple points are detected, one directly by a change of slope in the drawing of the equilibrium curves. The pressure-temperature phase diagrams are given; for each transiton, the volume increases on increasing the temperture.     

以2-甲基-丙烯酸,4-(吡啶-4-偶氮)-苯酯为配体的四个配位化合物的合成、晶体结构和紫外吸收

4个单核配位化合物,[Zn(Maape)2(H2O)2(NO3)2] (1, 单核), [Cu(Maape)2(H2O)2(NO3)2] (2, 单核), [Zn(Maape)2Cl2] (3, 单核), [Zn(Maape)(H2O)4SO4] (4, 单核),都是用过渡金属盐和配体2-甲基-丙烯酸,4-(吡啶-4-偶氮)-苯酯合成的.四个化合物由单晶X-射线衍射和结构分析表明都是单核化合物.另外,还通过红外和元素分析对其进行表征.配位化合物的结构不仅受配位金属离子的影响还受不同配位阴离子的影响.化合物1和2的结构都是由一个金属离子中心、2个配位硝酸根离子和2个配体分子组成的单核配合物.化合物3的单核结构中包含一个Zn(II)、2个氯离子和2个配体分子.而化合物4的不对称单元[Zn(Maape)(H2O)4SO4]中Zn(II)中心位于二重对称轴上.在本文中,配体和4个化合物都在323 nm处有最高紫外吸收峰.     

Physical Studies of Homologous 4-Cyanophenyl Esters of 4′- n-Alkylcinnamic Acids

The mean polarizabilities of homologous series of nematic liquid crystals of 4-cyanophenyl esters of 4′- n-alkylcinnamic acids are evaluated by using the MLδP method. From these polarizabilities the mean diamagnetic susceptibilities of the liquid crystals are also calculated. The orientational order parameters of these compounds are also estimated using the Vuks and Neugebauer methods. The variation of the order parameter with temperature is discussed.     

7-Hexyloxy-3-[4’-(3-methylbutyloxy) phenyl]-4H-1-benzopyran-4-one: Study of Smectic behaviour and UV absorption profile

The intermolecular interaction energies between a pair of 7-Hexyloxy-3-[4’-(3-methylbutyloxy) phenyl]-4H-1-benzopyran-4-one (HMBPB) molecules have been estimated with respect to translational and orientational motions. The complete neglect differential overlap (CNDO/S) method has been employed to calculate the net atomic charge and atomic dipole moment components at each atomic center. The modified Rayleigh-Schrodinger perturbation theory along with multicentered-multipole expansion method has been employed to evaluate the long-range intermolecular interactions, while a ‘6-exp’ potential function has been assumed for short-range interactions. The total interaction energy values obtained through these computations have been used to calculate the probability of each configuration at room temperature (300K), and isotropic-smectic transition temperature (412.6K). Molecular arrangements inside a bulk of materials and smectic behavior of the compound in terms of their relative order have been discussed. Translational and rotational rigidity of the molecule has been analyzed to understand the smectic behaviour. The UV absorption profile has been estimated using CNDO/S, and INDO/S methods.     

4-(2,5-二甲基-3,4-二乙酰基)-1-吡咯基苯甲酸的合成及其晶体结构

在强酸性介质中,3,4-二乙酰基-2,5-己二酮与对氨基苯甲酸作用,满意地得到了4-(2,5-二甲基-3,4-二乙酰基)-1-吡咯基苯甲酸,用IR、1H NMR、高分辩质谱等对其进行了表征,用X射线衍射测定了晶体结构.该晶体属三斜晶系,P1空间群,a＝0.80950(10)nm,b＝0.81910(10)nm,c＝1.1900(2)nm,α＝101.600(10)°,β＝98.820(10)°,γ＝104.960(10)°,Z＝2,Dc＝1.364×103kg/m3.拟合了苯环平面和吡咯环平面的平面方程,并求出两平面之间的二面角为68.11°.     

Synthesis of 1 - (4-Alkoxy or Alkyl- Benzoyloxy-Phenyl) - 2- (4′- Pentylphenyl) - Ethanes. Influence of the Central Group on the Mesomorphic Properties

An homologous series of mesomorphic compounds, the I-(4-alkoxy or alkyl-benzoyloxyphényl)-2-(4′-pentylphenyl)-ethanes, has been synthesized. The compounds with R = alkyl have low-melting points and wide mesomorphic ranges, for example from 33.5°C to 106.5C. The compounds with R = alkoxy exhibit a smectic polymorphism; for example a compound of this series is successively smectic B, F and C. The influence of the central linkage when the ethane group is replaced by an ester, single bond, ethylene, azomethine, azo, methylenecetone or cetone groups, is discussed.     

Polymorphism and design of noncentrosymmetric crystals of 4-hydroxybenzaldehyde-4-nitrophenylhydrazone and N′-(2-phenyl-1H-indole-3-aldehyde)-4-nitrophenylhydrazone

The products of crystallization of 4-hydroxybenzaldehyde-4-nitrophenylhydrazone (I) and N′-(2-phenyl-1H-indole-3-aldehyde)-4-nitrophenylhydrazone (II) from different solvents are studied by X-ray diffraction with the aim of examining the polymorphism of hydrazone derivatives. The structural features of the crystals prepared are analyzed. It is shown that, in the case when molecules of organic compounds with a high molecular hyperpolarizability are capable of forming stable acentric supramolecular associates in the crystal, knowledge of their polymorphism offers strong possibilities for designing the noncentrosymmetric crystal structure necessary for a manifestation of the nonlinear optical activity.     

Crystal structure of (4α,4aα,8aα)-(±)-octahydro-2-(phenylmethyl)-2H-1,2-benzoxazin-4-ol, 4-methylbenzenesulfonate(ester)

The title compound, a bicyclic tetrahydro-1,2-oxazine, crystallizes in a monoclinic lattice, space group P2₁/c, with a = 12.9809(18)Å, b = 12.920(2)Å, c = 13.631(2)Å, = 110.713(12)°, and Z = 4. The structure found in the solid state for this conformationally mobile molecule shows the tosyl group in an axial position and a benzyl group in an equatorial position of the bicyclic system.     

5-溴-2-(4-甲基哌啶-1-基)嘧啶的晶体结构及密度泛函理论研究

嘧啶类衍生物在医药、化工和功能材料等领域有着重要应用。在药物研发,特别是抗癌药物研发领域中,5-溴-2-(4-甲基哌啶-1-基)嘧啶是一种含嘧啶环的重要中间体。本文通过一步芳香亲核取代反应合成了5-溴-2-(4-甲基哌啶-1-基)嘧啶,经溶液结晶法获得其单晶体,并进行了晶体学分析(晶系:正交晶系,空间群:P2₁2₁2₁,晶胞:a=10.181 42(6) nm, b=17.620 0(8) nm, c=10.179 02(5) nm,Z=4,ρ_c＝1.478 g·cm^-3,R=0.056 6,wR=0.168 8)。标题化合物的最优结构和前线轨道能量在B3LYP/6-311G(d, p)模式下使用密度泛函理论(DFT)计算得到,经DFT优化的结果与实验确定的数据相近。此外,为进一步揭示标题化合物的物理化学性质,通过DFT进一步研究了分子的静电式和前线分子轨道。     

7-Hydroxy-2-(2,3,4-trimethoxyphenyl)-4H-1-benzopyran-4-one: (7-hydroxy-2′,3′,4′-trimethoxyflavone)

7-Hydroxy-2,3,4-trimethoxyflavone, (C₁₈H₁₆O₆),M _r =328.32 crystallizes in the orthorhombic system, space groupPbna, with the following crystal data:a=8.853(2),b=12.870(2),c=26.293(3)Å,V=2996(1)ų,Z=8, MoK, =0.67 cm^–1,D _c =1.454 g·cm^–3,F(000)=1376,T=294K. The structure was solved by direct-methods and has been refined by full-matrix least-squares methods to a finalR value (F>(F)) of 0.0496. The molecule is not planar, the dihedral angle between the phenyl ring and the fused ring system is 27.3°. There are no intramolecular hydrogen bonds, but intermolecular short hydrogen contacts exist between hydroxyl hydrogen and carbonyl oxygen atoms.     

Crystal Structure?4-(2,4-Dihydroxybenzylideneamino)-5-methyl-2H-1,2,4-triazol-3(4H)-one

Abstract  

The title compound (I), 4-(2,4-dihydroxybenzlideneamino)-5-methyl-2H-1,2,4-triazol-3(4H)-one was characterized by single crystal X-ray diffraction. This crystal is monoclinic, space group P2₁/c with a = 10.1447(7) ?, b = 7.0972(3) ?, c = 14.6726(10) ?, β = 98107(5)°, V = 1045.85(11) ?³, Z = 4, D _c = 1.487 g/cm³, F ₀₀ = 488, R = 0.039 and wR = 0.1025, S = 1.003, T = 293 (2) K. The title molecule is planar: the angle between the triazole ring and benzene ring is 179.1(1)°. The crystal structure contains two intramolecular (O–H···N and C–H···O) and three intermolecular interaction (O–H···N, N–H···O, and C–H···O). In addition, there is also π–π interactions.     

Chain Ordering and Sm-N Transition in Different Members of the Homologous Series 4-(4′- n-AIkoxy Benzylideneamino) Biphenyls

Our extension of Marcelja's theory of nematic-isotropic transition to the smectic A phase is used to calculate the smectic A-nematic (Sm-N) transition temperatures for the homologous series 4–(4′- n-alkoxy benzylideneamino) biphenyls. In a mean field calculation, explicit inclusion of the conformational energies of the alkyl chain of a molecule in the partition function shows an even-odd effect generally observed in experiments on Sm-N transitions. It is found that the members of this series showing the smectic phase will have first order Sm-N transitions and the transition entropies for individual members are calculated.     

Some Cholesteric Derivatives of S-(+)-4-(2′-Methylbutyl) Phenol

A facile synthesis of S-(+)-4-(2′-methylbutyl)phenol and its interaction with a number of different acids are used to provide a wide variety of new chiral nematic liquid crystals. These new cholesterogens display a range of liquid crystal and other physical properties, and are potentially useful for application in display device and other technologies. Of particular interest in this respect are the materials containing two chiral centres and which therefore have very small helical pitch lengths-as low as 0.1 μm.     

Synthesis and crystal structure of 1-(1′,3′-dimethyl-5′-chloropyrazol-4′-carbonyl′-3-(2′-chlorophenyl)-5-amino-4-cyanopyrazole

The title compound 1-(1,3-dimethyl-5-chloropyrazol-4-carbonyl)-3-(2-chlorophenyl)-5-amino-4-cyanopyrazole (C₁₆H₁₂Cl₂N₆O) has been synthesized and characterized by X-ray diffraction: Triclinic, space group P1, with a = 8.6712(8) Å, b = 9.5091(10) Å, c = 11.2170(11) Å = 71.531(2)°, = 84.683(2)°, = 74.099(2)° Z = 2; V = 843.7(14) ų. C(10), O(1), C(11), and N(2) atoms are coplanar with the average deviation of 0.0071 Å, which form 11.03° and 43.93° dihedral angles with pyrazole planes (I) and (II), respectively.     

Novel manganese(III) oxidation chemistry: X-ray crystal structures of (1α,2α,4β)-1,2-diacetoxy-4-(4-methoxyphenyl)-6-methoxy-1,2,3,4-tetrahydronaphthalene (compound A) and (1α,2α,4β)-1,2-diacetoxy-4-(2-methoxyphenyl)-8-methoxy-1,2,3,4-tetrahydronaphthalene (compound B)

CompoundA is (1,2,4)-1,2-diacetoxy-4-(4-methoxyphenyl)-6-methoxy-l,2,3,4-tetrahydronaphthalene, C₂₂H₂₄O₆,M _r=384.43, monoclinic, P2₁/n, witha=11.074(3),b=10.353(4),c=17.616(4)Å,=94.96(2)°,V=2012.1ų,D _calc=1.27 g cm^–3 and=0.55 cm^–1 forZ=4. Least-squares refinement of 1371 observed [F ₀5 (F ⁰)] reflections led to the final agreement index ofR=0.052. A twofold disorder was observed for the 1-acetoxy group whereas the 2-acetoxy group was ordered. CompoundB, (1,2,4)-1,2-diacetoxy-4-(2-methoxyphenyl)-8-methoxy-l,2,3,4-tetrahydronaphthalene, C₂₂H₂₄O₆,M _r=384.43, crystallizes in the monoclinic space group, P2₁/c, witha=16.209(2),b=10.076(1),c=13.357(4)Å,=111.41(2)°,V=2030.9ų,D _calc=1.26 g cm^–3 and=0.54 cm^–1 forZ=4. A final agreement index ofR=0.045 was realized by least-squares refinement of 1486 observed [F _o5 (F _o)] reflections. Intermolecular interactions in the cell lattices of compoundsA andB are noted. The title compoundsA andB were prepared by manganese(III) acetate oxidative dimerization of two molecules of 4-methoxystyrene and 2-methoxystyrene, respectively.     

A Homologous Series containing Ester and Amide Groups as Central Linkages: 4(4'-n-Alkoxybenzoyloxy)-4”-n-Heptyloxy Benzanilides

The first extensive homologous series, comprising thirteen members, with both ester and amide groups as central linkages has been synthesised and the mesomorphic properties have been determined. The homologues are comparatively high melting and exhibit liquid crystal phases. The molecular structure seems to favour smectic properties since smectic phases commence with the ethoxy derivative as a monotropic phase. The ethoxy to hexadecyloxy derivatives are poly-mesomorphic in nature, while the octadecyloxy derivative is purely smectic. The mesomorphic behaviour and mesophase thermal stabilities are compared with those of other structurally related series, and the effect of the amide group on mesomorphism is evaluated.