Isolation,Crystal Structure and Na~+/K~+-ATPase Inhibitory Activity of 1β-Hydroxydigitoxigenin

The title compound 1β-hydroxydigitoxigenin(1) was isolated from the ethanol extract of the roots of Streptocaulon juventas. The crystal structure of 1, C_(23)H_(34)O_5·H_2O, was determined by Synchrotron X-ray diffraction analysis due to small crystal size(0.14 mm × 0.04 mm × 0.01 mm). The crystal belongs to monoclinic, space group P21, with a = 7.6624(15), b= 13.460(3), c = 10.370(2) ?, b = 92.40(3)°, V = 1068.6(4) ?3, Z = 2, Mr = 406.50, Dx = 1.263 g/cm3, λ(synchrotron) = 1.2399 ?, μ(synchrotron 1.23990) = 0.333 cm~(-1), F(000) = 550, S = 1.059, R = 0.0625 and w R = 0.1687 for 4247 unique reflections, of which 3687 were observed(I 2σ(I)). The asymmetric unit contains one independent molecule of 1 and one water molecule which are connected through hydrogen bonds. The conformation of 1 in crystalline state is in good agreement with the solution structure in methanol as indicated by ~1H-NMR analysis. The absolute configuration of 1 could be assigned by referring to the known configuration of the lactone ring at C(17b). In the solid state, intermolecular hydrogen bonds involving carbonyl group in the lactone moiety and the hydroxyl groups in the steroid moiety ester linked adjacent molecules into a three-dimensional network. Compound 1 showed significant inhibition on Na+/K+-ATPase with an IC50 of 2.46 mM, which is stronger thiocarbonylbufalin but weaker than a close analog digitoxigenin, suggesting that a lactone ring is important and the substitution of a hydroxyl group at C(1) is not favored for the inhibition of Na~+/K~+-ATPase.     

Synthesis,Crystal Structure and Biological Activity of 25,27-Di(α,γ-diketo-p-methylphenylbutoxy)-26,28-dihydroxy p-tert-butylcalix[4]arene

The title complex(C66H76O8·CH3CN) was synthesized and structurally determined by single-crystal X-ray diffraction method. It crystallizes in monoclinic, space group P21/c with a = 22.384(13), b = 13.413(7), c = 21.867(12), β = 112.257(7)°, C68H78NO8, Mr = 1037.31, Dc = 1.133 g/cm3, V = 6076(6) 3, Z = 4, F(000) = 2224, μ(MoKa) = 0.073 mm-1, T = 296(2) K, 10276 independent reflections with 5469 observed ones(I 2σ(I)), R = 0.0797 and wR = 0.2316 with GOF = 1.027(R = 0.1442 and wR = 0.2689 for all data). The calixarene moiety maintains the symmetric cone conformation through intramolecular O–H···O hydrogen bonds. The inhibition of the strand transfer process of HIV-1 integrase of the title compound was also evaluated. Preliminary bioassays indicated that it has a low inhibition ratio(24.85%) at the concentration of 50 μM.     

Synthesis,Crystal Structure and Antiproliferative Activity of 2-（（（5-（（（5,7-Dimethyl-[1,2,4]triazolo-[1,5-a]pyrimidin-2-yl）thio）methyl）-4-phenyl-4H-1,2,4-triazol-3-yl）thio）methyl）-4Hchromen-4-one Methanol Solvate

The novel crystal of the title compound 2-(((5-(((5,7-dimethyl-[1,2,4]triazolo-[1, 5-a]-pyrimidin-2-yl)thio)methyl)-4-phenyl-4H-1,2,4-triazol-3-yl)thio)methyl)-4H-chromen-4-one methanol solvate(C27H25N7O3S2, Mr = 559.66) has been prepared and its structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monocline system, space group P21/c with a = 11.9879(9), b = 14.0743(10), c = 15.9706(11), β = 98.509(2)°, V = 2664.9(3)3, Z = 4, Dc = 1.395 g/cm3, F(000) = 1168, μ = 0.116 mm-1, MoKa radiation(λ = 0.71073), R = 0.0652, and wR = 0.1425 for 5220 observed reflections with I 2σ(I). X-ray diffraction analyses reveal that the molecule adopts a C-shape. The planes of the benzopyrone and triazolopyrimidine were nearly parallel to each other, with a dihedral angle of 1.21(3)°. Intramolecular and intermolecular hydrogen bonds together with π-π interations are found to exist in the structure. The results of MTT assay indicate that the title compound displays excellent antiproliferative activity against two human cancer cell lines.     

Isolation, Crystal Structure and Inhibitory Activity against Magnaporthe Grisea of （2R,3R）-3,5,7-trihydroxyflavanone 3-Acetate from Myoporum Bontioides A. Gray

The title compound, (2R,3R)-3,5,7-trihydroxyflavanone 3-acetate, is a flavanonol derivative which was first isolated from Myoporum bontioides A. Gray and characterized by MS, NMR and CD spectra. In addition, the structure was determined by X-ray single-crystal diffraction analysis. It crystallizes in the triclinic lattice, space group P21 with a = 10.686(3), b = 6.862(2), c = 11.267(3) , β = 107.46(1), V = 788.3(4) 3, Z = 2, C17H16O7, Mr = 332.30, Dc = 1.400 g/cm3, μ(MoKα) = 0.110 mm-1, F(000) = 348, the final R = 0.0283 and wR = 0.0826 for 3428 independent reflections (Rint = 0.017) and 1500 observed ones (I > 2σ(I)). The structure consists of one flavone and one water molecule. The flavone molecules form a 1D column by the p…π stacking interactions and C–H…O hydrogen bonds. The weak intermolecular/intermolecular O–H…O hydrogen bonds observed in the crystal give further rise to a complicated network structure. Primary bioassay showed that the title compound has high inhibitory activity against Magnaporthe grisea with the EC50 values of 199.41 μg/mL.     

Synthesis,Crystal Structure and Biological Activity of 8-（（4-（（2,3-diaminopyridin-4-yl）oxy）-3-fluorophenyl）-amino）-2-（4-fluorophenyl）-3-methyl-2,7-naphthyridin-1（2H）-one

The new title compound 8-((4-((2,3-diaminopyridin-4-yl)-oxy)-3-fluorophenyl)-amino)-2-(4-fluorophenyl)-3-methyl-2,7-naphthyridin-1(2H)-one(C26H20F2N6O2, Mr = 486.48) has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/c with a = 15.365(3), b = 13.144(2), c = 11.863(2), β= 108.882(3)°, Z = 4, V = 2267.0(7)3, Dc = 1.425 g/cm3, F(000) = 1008, μ = 0.105 mm-1, MoKa radiation(λ = 0.71073), R = 0.0480 and wR = 0.1294 for 3197 observed reflections with I 2σ(I). X-ray diffraction analysis reveals that the region C(substituents of 8-amino group and 3-methyl group on the 2,7-naphthyridin-1(2H)-one ring) of compound 6 are effectively planar. Intramolecular and intermolecular hydrogen bonds together with π···π interations are found in the structure. In addition, compound 6 shows potent c-Met and c-Kit kinase inhibition activities.     

Synthesis,Crystal Structure and Antibacterial Activity of （E）-N1,N4-Bis（2,3,4-trimethoxy-6- methylbenzylidene）butane- 1,4-diamine

The title compound （E）-N1,N4-bis（2,3,4-trimethoxy-6-methylbenzylidene） butane- 1,4- diamine （C26H36N2O6, Mr = 472.57） was synthesized and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The crystal belongs to triclinic, space group C2/c with a = 36.102（4）, b = 5.6620（11）, c = 13.015（2）A,β = 105.491 （2）°, V = 2563.7（7）A3, Z = 4, Dc = 1.224 g/cm3, 2 = 0.71073 A,μ（MoKα） = 0.087 mm^-1, F（000） = 1016, the final R = 0.0456 and wR = 0.1257 for 2255 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that the molecule adopts an E configuration about the central C=N functional bond. The phenyl rings of two 2,3,4-trimethoxy-6-methylbenzaldehyde groups are parallel by symmetry. The molecules are linked through π-π and C-H…π stacking interactions and C-H…O hydrogen bonding interactions. The title compound possesses moderate antibacterial activity.     

Synthesis,Crystal Structure and Biological Activity of N-tert-butyl-N-(4-methyl-1,2,3-thiadiazole)-5-yl-N’-(4-methyl-1,2,3-thiadiazole)-5-formyl-N’-3,5-dichloropyridin-2-yl-diacylhydrazine

The title compound N-tert-butyl-N-(4-methyl-1,2,3-thiadiazole)-5-yl-N'-(4-me-thyl-1,2,3-thiadiazole)-5-formyl-N'-3,5-dichloropyrid-2-yl-diacylhydrazines (C18H17Cl2N7O3S2, Mr = 514.41) has been synthesized by the reaction of N-tert-butyl-N'-3,6-dichloropyridine-2-formyl hydrazine with 4-methyl-1,2,3-thiadiazole-5-carbonyl chloride and triethylamine, and its structure was characterized by 1H NMR, HR MS, and single-crystal X-ray diffraction. The crystal of the title compound belongs to monoclinic, space group C2/c with a = 27.726(8), b = 11.045(3), c = 14.507(4), β = 96.758(4)°, Z = 8, V = 4412(2) 3, Dc = 1.549 g/cm3, μ = 0.521 mm-1, F(000) = 2112, R = 0.0405 and wR = 0.1153. X-ray analysis indicates that all rings are non-planar in this molecule. The bioassay results indicate that both the title compound and the positive control RH-5992 have weak fungicide activities, while the title compound has good insecticidal activity against Plutella xylostella L. and no insecticidal activity against Culex pipiens pallens.     

Synthesis,Crystal Structure and Antiproliferative Activity of Ethyl 1-（Phenylcarbamoyl）-2-3,4,5-trimethoxyphenyl）cyclopropanecarboxylae

Many small-molecule compounds have been evaluated with potential antiproliferative activities. Ethyl 1-(phenylcarbamoyl)-2-(3,4,5-trimethoxyphenyl)cyclopropanecarboxylate, one novel cyclopropylamide analogue of combretastatin-A4(CA-4), has been synthesized and its crystal structure was characterized by X-ray single-crystal diffraction. The crystal belongs to monoclinic, space group P21/n, with a = 15.0263(3), b = 7.6574(2), c = 19.4117(4), β = 111.9010(10)o, V = 2072.36(8)3, Z = 4, C22H24NO6, Mr = 398.42, Dc = 1.277 Mg/cm3, F(000) = 844, λ(MoKα) = 1.54178 , μ = 0.770 mm–1, R = 0.0546 and wR = 0.1889 for 3319 observed reflections(I 2σ(I)). Meanwhile, the compound revealed potential antiproliferative activities in several cancer cells in vitro.     

Synthesis and Crystal Structure of 3-（2,4-Dichlorophenyl）- 4-dydroxy-5-cyclohexanyl-△3-dihydrofuran-2-one

The title compound 3-（2,4-dichlorophenyl）-4-dydroxy-3-（2,4-dichlorophenyl）-4- dydroxy-5-cyclohexanyl-A3-dihydrofuran-2-one 5 has been synthesized by the cyclization of methyl O-（2,4-dichlorophenyl-acetyl）-1-hydroxycyclo-hexane-carboxylate 4, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group Pi with a = 6.8192（3）, b = 10.5053（5）, c = 10.5811（5）A,α = 71.681（10）, β = 78.905（12）, γ = 81.036（12）°, C15H14C1203, Mr = 313.18, V= 702.44（6）A3, Z = 2, De= 1.481 g/cm^3, F（000） = 324,μ = 0.465 mm^-1, S = 1.006, the final R = 0.0331 and wR = 0.1363 for 2505 observed reflections with I 〉 2σ（I） and 183 variable parameters. The crystal analysis shows that the cyclohexene unit of the title compound has a quasi-chair conformation, and a one-dimensional chain structure is formed via the intermolecular hydrogen bond O（1）-H（101）…O（2）.     

Synthesis,Crystal Structure and Antibacterial Activity of （2E,3E）-N1,N2-Bis（2,3,4-trimethoxy-6-methylbenzylidene）ethane-1,2-diamine

The title compound （2E,3E）-N1,N2-bis（2,3,4-trimethoxy-6-methylbenzylidene）- ethane-l,2-diamine （C24H32N2O6, Mr = 444.52） was synthesized and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The crystal belongs to triclinic, space group P2/c, with a = 8.5480（10）, b = 9.3710（12）, c = 15.280（2）A, β = 90.780（2）°, V= 1223.9（3）A3, Z = 2, Dc= 1.206 g/cm3, 2 = 0.71073A,μ（MoKa） = 0.087 mm^-1, F（000） = 476, the final R = 0.0680 and wR = 0.1450 for 2144 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that the molecule adopts an E configuration about the central C=N functional bond. The phenyl rings of two 2,3,4-trimethoxy-6-methylbenzaldehyde groups are symmetrically parallel. The molecules are linked through C-H…O hydrogen bonding interactions. The title compound possesses moderate antibacterial activity.     

Synthesis, Crystal Structure and Antitumor Activity of 4-tert-Butyl-N-（2-fluorophenyl）-5- （1H-1,2,4-triazol-1-yl）-thiazol-2-amine

The title compound has been synthesized by the reaction of 1-bromo-3,3-dime- thyl-1- (1H-1,2,4-triazol-1-yl)butan-2-one with 1-(2-fluorophenyl)thiourea, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the orthorhombic system, space group Pbca with a=15.2568(6), b=12.1533(5), c=16.7307(7) , Z=8, V=3102.2(2)3, Mr=317.39, Dc=1.359 g/cm3, S=1.05, μ=0.223 mm-1, F(000)=1328, the final R=0.034 and wR=0.097 for 2590 observed reflections (I>2σ(I)). X-ray crystal structure presents the intramolecular N-H…N hydrogen bond, which plays an important role in stabilizing the crystal structure. In addition, the preliminary biological test on the title compound shows good antitumor activity, with IC50 of 0.122 μmol/mL against the Hela cell line.     

Synthesis,Crystal Structure and Fluorescent Properties of a 4-Fold Interpenetrating Zn(Ⅱ) Polymer

A new coordination polymer [Zn(isop)(bps)]n 1(H2isop=benzene-1,3-dicer-boxylic acid,bps=4,4'-dipyridyl sulfide) has been prepared and structurally characterized by X-ray diffraction method.It crystallizes in monoclinic,space group P21/n with a=12.1936(11),b=10.7720(9),c=13.0685(11),V=1709.0(3)3,C18H12N2O4SZn,Mr=417.76,Z=4,Dc=1.624g/cm3,S=1.046,F(000)=848,the final R=0.0305 and wR=0.0858 for 3085 independent reflections with Rint=0.0147.Single-crystal X-ray diffraction analyses reveal that 1 is a 4-fold interpenetrating diamondoid network.The zinc(Ⅱ) atom is coordinated by two nitrogen atoms of two bps and two carboxylate oxygen atoms of isop ligands,resulting in a tetrahedral geometry.     

Preparation and Crystal Structure of 15α-Hydroxyl-oleanolic Acid

The compound 15α-hydroxyl-oleanolic acid was biotransformed from oleanolic acid with Colletotrichum lini AS3.4486,and its structure was characterized by 1H NMR,13C NMR,HR-ESI-MS and single-crystal X-ray diffraction.The crystal of the title compound belongs to monoclinic,space group R3 with a=34.255(5),b=34.255(5),c=6.8671(14),β=90°,Z=9,V=6978(2)3,Mr=490.70,Dc=1.051 mg/m3,μ=0.069 mm-1,F(000)=2430,R=0.0375 and wR=0.0808.The title compound is stacked into a three-dimensional network through hydrogen bonds.     

Synthesis and Crystal Structure of [2-Hydroxy- 5-（4-hydroxy-3-phenyliminomethylbenzyl）-benzylidene]-phenyl-amine

The title compound [2-hydroxy-5-（4-hydroxy-3-phenyliminomethyl-benzyl）-benzylidene]-phenyl-amine （C27H22N2O2, Mr = 406.47） was synthesized by 5,5′-methylene-bissalicylal- dehyde with aminobenezene, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group C2/c with a = 4.4026（6）, b = 1.501（13）, c = 0.95818（12） nm, β = 90.868（2）°, V= 4.2813（9） nm^3, Z= 8, Dc= 1.292 g/cm^3,μ = 0.010, F（000） = 1744, R = 0.0576 and wR = 0.1450 for 3766 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the molecule has a pair of intramolecular OH…N hydrogen bonds.     

Synthesis and Crystal Structure of 3,6-Bis（4-methyl-1,2,3-thiadiazol-5-yl）-1,2,4-triazolo[3,4-b][1,3,4]thiadiazole

The compound 3,6-bis(4-methyl-1,2,3-thiadiazol-5-yl)-1,2,4-triazolo[3,4-b][1,3,4] thiadiazole(C9H6N8S3,Mr = 322.40) has been synthesized by the reaction of 4-amino-3-(4-methyl-1,2,3-thiadiazolyl)-5-mercapto-1,2,4-triazole with 4-methyl-1,2,3-thiadiazol-5-carboxylic acid and phosphorus oxychloride,and its structure was characterized by IR,1H NMR,EI-MS,elemental analysis and single-crystal X-ray diffraction.The crystal of the title compound belongs to monoclinic,space group C2/c with a = 2.0053(4),b = 1.3081(3),c = 1.0556(2) nm,β = 112.69(3)°,Z = 4,V = 2.5548(9) nm3,Dc = 1.676 g/cm3,μ = 0.582 mm-1,F(000) = 1312,R = 0.0546 and wR = 0.1523.X-ray analysis indicates that all rings are essentially planar in this molecule,and an intermolecular hydrogen bond C(9)-H(9)…N(2) and weak intramolecular interactions between S(1)…N(7),S(3)…N(1) and S(2)…N(4) are observed.     

Synthesis,Bioactivity and Crystal Structure Analysis of Diisopropyl[（4-cyanopyrazol-3-ylamino）（2-hydroxyl-phenyl） methyl]phosphonate

The title compound,diisopropyl[(4-cyanopyrazol-3-ylamino)(2-hydroxylphenyl) -methyl] phosphonate was synthesized by the addition reaction of diisopropyl phosphite and N-(4-cyanopyrazole-3-yl) -2-hydroxylphenyl-imine. Its structure was characterized by IR,1H NMR,elemental analysis and single-crystal X-ray diffraction. The crystal belongs to the triclinic system,space group P1 with a = 9.1840(13) ,b = 9.2278(13),c = 12.1952(17) ,α = 93.846(2) ,β = 90.947(2) ,γ = 111.289(2) °,V = 959.9(3) 3,Dc = 1.309 g/cm3,Z = 2,μ(MoKa) = 0.173,F(000) = 400,the final R = 0.0414 and wR = 0.1196 for 2985 observed reflections(I > 2σ(I)) . The pyrazole and benzene moieties are approximately coplanar in each case. The dihedral angle between planes 1 and 2 is 82.99°. The crystal structure is stabilized by three intermolecular hydrogen bonds of O(1) -H(1) …O(2) ,N(2) -H(2) …N(3) and N(2) -H(2) …O(1) . Preliminary bioassay indicated that the title compound possessed antiviral activity to some extent.     

Synthesis and Crystal Structure of N-phenyl-N-[（o-nitrophenylacetyl）oxy]benzamide

The compound N-phenyl-N-[（o-nitrophenylacetyl）oxy]benzamide （C21HI6N2Os, Mr = 376） has been synthesized by the reaction of N-hydroxy-N-phenylbenzamide with 2-（2-nitro- phenyl）acetyl chloride in dichlorom-ethane and its structure Was characterized by 1H NMR, 13C NMR, IR, H RMS（ESI） and single-crystal X-ray diffraction. The crystal of the title compound belongs to monoclinic, space group C2/c with a = 32.30（2）, b = 8.400（5）, c = 15.099（9） A, fl = 114.256（10）°, V = 3735（4） A3, Z = 8, D, = 1.339 g/cm3, F（000） = 1568, p = 0.097 mm-1, the final R = 0.0506 and wR = 0.1176 for 2318 observed reflections （1 〉 2a（/））. The title molecule contains three branched chains with its center placed at the midpoint of N. The phenyl ring （C（1）＇-C（6）） makes a dihedral angle of 70.3（1）° with the phenyl ring （C（10）-C（15）） of benzoyl group, and 14.3（1）° with the phenyl ring （C（16） - C（21））, Hydrogen bonds C（5）-H（5）...O（1） and C（12）-H（12）...O（3） together with it-Jr stacking interactions contribute to the stability of the structure.     

Synthesis,Spectroscopic Properties and Crystal Structure of 3,3＇-（Anthracene-9,10-diyl）bis（1-phenylpropan-1-one）

The compound 3,3'-(anthracene-9,10-diyl)bis(1-phenylpropan-1-one)(C32H26O2,Mr=442.55) has been synthesized by the reaction of 2,2'-(anthracene-9,10-diylbis(methy-lene))bis(1,3-diphenylpropane-1,3-dione) with CsCO3,and its structure was characterized by 1H NMR and single-crystal X-ray diffraction.The crystal of the title compound belongs to monoclinic,space group P21/c with a=9.154(3),b=5.2777(16),c=24.897(7) nm,β=107.337(10)°,Z=2 and V=1.1482 nm3.X-ray analysis indicates that an intermolecular hydrogen bond C(8)-H(8A)…O(1),weak C-H···π between H(9A) and the centre of anthracene rings and weak π-π interactions between two anthracene ring planes are observed.     

Synthesis and Crystal Structure of the Optical Activity of （Z）-Nitromethylene Neonicotinoid Analogue

A novel (Z)-nitromethylene neonicotinoid analogue (C23H27Cl2N5O4·2H2O) (II) with optical activity has been synthesized, the structure was characterized by elemental analysis, IR and 1H NMR spectra, and the (Z)-configuration was confirmed by single-crystal X-ray diffraction. The crystal belongs to triclinic, space group P1 with a = 7.4638(3), b = 12.6232(5), c = 15.2990(6), α = 71.907(1), β = 89.397(2), γ = 80.314(1)°, V = 1349.28(9)3, Z = 2, Dc = 1.340 g/cm3, μ = 0.286 mm-1, Mr = 544.43, F(000) = 572, S = 1.056, R = 0.0801 and wR = 0.2366 for 4998 unique reflections with 3012 observed ones (I > 2σ(I)). In the crystal, the dihedral angle between the pyridine and 4-Cl-phenyl rings is 58.13°. Intermolecular O–H···O, C–H···O and C–H···Cl hydrogen bonds involving water molecules stabilize the crystal structure.     

Synthesis, Crystal Structure and Pyrolysis of a Heterobimetallic Peroxo-titanium（IV） Nitrilotriacetate Complex

A new heterobimetallic nitrilotriacetatoperoxotitanate complex with the formula of [Mn(H2O)5]2[Ti(O2)2O(nta)2]·7H2O (1, C6H6O6N = H3nta) has been isolated in pure crystals. It was characterized by elemental analyses, IR, thermal analysis (TGA) and single-crystal X-ray diffraction. Complex 1 crystallizes in monoclinic, space group C2/c with a = 15.088(3), b = 13.311(3), c = 17.741(4) , β = 100.92(3)°, Z = 4, V = 3498.6(12) 3, Mr = 968.19, Dc = 1.838 g/cm3, μ = 1.266 mm-1, F(000) = 1992, R = 0.0337 and wR = 0.0819. Single-crystal X-ray analysis reveals that the titanium atom is N,O,O',O'-chelated by the nitrilotriacetate and O,O'-chelated by the peroxo group, and is coordinated to the bridging O atom in an overall pentagonal-bipyramidal geometry. The manganese ions in the compound are both 6-coordinated by five water molecules and one bridged carboxylato oxygen atom. A decameric water cluster consisting of a cyclic water hexamer in a boat fashion is also found in complex 1. The TGA and XRD results prove that 1 undergoes facile thermal decomposition to form the mixture of Mn2O3 and TiO2 at 600～800 ℃, and pure MnTiO3 at 900 ℃.