Synthesis and THF Accompanied Crystal Structure of 11H-Naphtho[1′,2′,:5,6]-pyrano[2,3-d]pyrimidin-11(10H)-one

8,9,12-Trihydro-9,9-pentamethylene-12-(3-nitrophenyl)-11H-naphtho[1′,25,6] pyrano[2,3-d]pyrimidin-11(10H)-one 1, another conversion product of Friedl(a)ndler reaction, has been synthesized by the reaction of 2-amino-4-(3-nitrophenyl)-4H benzo[f]chromene-3-carbo- nitrile 2 with cyclohexanone in the presence of Lewis acid catalysts. The crystal of the title compound 1 THF solvate, C60H62N6O10, was obtained and determined by X-ray diffraction me- thod. The crystal is of triclinic, space group P with a = 11.4633(11), b = 12.6247(12), c = 19.658(2)(A), α = 72.642(8), β = 89.045(9), γ = 68.340(5)°, V = 2509.6(4), Z = 2, Dc = 1.359 g/cm3, F(000) = 1088, Mr = 1027.16, the final R = 0.0674 and wR = 0.1869 with I > 2σ(I) and the goodness-of-fit S = 1.045 on F2. The pyrimidine ring has an envelope conformation, linked with a six-membered ring through a spiro C atom. The crystal packing of 1 THF solvate is stabilized by N-H…O hydrogen bonds, and π-π stacking interaction occurs between two adjacent nearly planar molecules of 1.     

Synthesis and THF Accompanied Crystal Structure of 11H-Naphtho[1',2':5,6]- pyrano[2,3-d]pyrimidin-11(10H)-one

8,9,12-Trihydro-9,9-pentamethylene-12-(3-nitrophenyl)-11H-naphtho[1',25,6]-pyrano[2,3-d]pyrimidin-11(10H)-one 1,another conversion product of Friedlndler reaction,has been synthesized by the reaction of 2-amino-4-(3-nitrophenyl)-4H-benzo[f]chromene-3-carbo-nitrile 2 with cyclohexanone in the presence of Lewis acid catalysts.The crystal of the title compound 1 THF solvate,C60H62N6O10,was obtained and determined by X-ray diffraction me-thod.The crystal is of triclinic,space group P with a = 11.4633(11),b = 12.6247(12),c = 19.658(2) ,α = 72.642(8),β = 89.045(9),γ = 68.340(5)°,V = 2509.6(4),Z = 2,Dc = 1.359 g/cm3,F(000) = 1088,Mr = 1027.16,the final R = 0.0674 and wR = 0.1869 with Ⅰ > 2σ(Ⅰ) and the goodness-of-fit S = 1.045 on F2.The pyrimidine ring has an envelope conformation,linked with a six-membered ring through a spiro C atom.The crystal packing of 1 THF solvate is stabilized by N-H···O hydrogen bonds,and π-π stacking interaction occurs between two adjacent nearly planar molecules of 1.     

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 and Crystal Structure of [K（2,2,2-crypt）]2HP11

[K（2,2,2-crypt]2HP11 has been prepared from the reaction of K3P11 with the mixed ethylenediamine/2,2,2-crypt solution. The crystal structure was determined by singlecrystal X-ray diffraction. The crystal is of tdgonal system, space group P^-3c1 with a = 12.068（2）, b = 12.068（2）, c = 22.319（6）A, V = 2815.0（10）A^3, Dc = 1.384 g/cm^3, C36h73K2N4O12P11, Mr = 1172.85, F（000） = 1232,μ = 0.536 mm^-1, Z= 2, R = 0.0678 and wR = 0.2211 for 1763 observed reflections （I 〉 2σ（I））. In this compound, the P11 cluster has ideal 32-D3 symmetry, and the three-fold axis, corresponds to the crystallographic c axis. The （HP11）^2- anions are stable due to the completely sequestered alkali metal cations through only ion-ion interactions.     

Hydrothermal Synthesis,Crystal Structure and Fluorescence Spectrum Studies of a Supramolecular Compound {[2-（2-Pyridyl）benzimidazoleH2]2＋ ·[SbCls]2-}2

A new supramolecular compound, { [2-（2-pyridyl）benzimidazoleH2]2＋.[SBC15]2-}2, was synthesized by the hydrothermal reaction of o-diaminobenzene, 2-pyridinecarboxylie acid and SbCl3 in 1：1 HC1 solution, and characterized by chemical analysis, elemental analysis, IR spectra, thermogravimetfic analysis and fluorescence spectra. The crystal structure was deter- mined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P211c, with a = 16.0397（13）, b = 14.3189（12）, c = 15.6370（13） A, β = 105.8980（10）°, V = 3454.0（5） A3, Z = 4, C24H22Cl10N6Sb2, Mr = 992.48, Dc = 1.909 g/cm3,/z = 2.366 mm-1, S = 1.010, F（000） = 1920, R = 0.0254 and wR = 0.0555. The coordination anion, [SbCl5]2- which is a distorted tetragonal pyramid, is composed by coordinating action with Sb3＋ ion and five adjacent chloride ions. Every four coordination anions of [SbCl5]2- form a biquaternion ring structure through the secondary bonding of Sb...Cl. Moreover, the compound adopts a three-dimensional network supramolecular structure because of the hydrogen bonds and π-π stacking between the rings and the 2-（2-pyridyl）benzimidazole divalent cations. The title compound also shows good fluorescent behaviors.     

Synthesis and Crystal Structure of 5-（p-Toly1）-4- [2-（2,4-dichlorophenoxy）acetamido]-l,2,4- triazole-3-thione Ethyl Acetate Solvate

A novel compound 5-（p-tolyl）-4-[2-（2,4-dichlorophenoxy）acetamido]-1,2,4-tria zole- 3-thione 2a has been synthesized by the reaction of 5-（p-tolyl）-4-amino-1,2,4-triazole-3-thione 1 with 2-（2,4-dich/orophenoxy）acetyl ch/oride. Interestingly, the title compound 2 was obtained when 2a crystallizes from a mixed solution of petroleum ether and ethyl acetate, and it has been characterized by elemental analysis, IR, ^1H NMR spectra and single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 9.780（5）, b = 10.876（6）, c = 11.615（6） /A, a = 104.822（7）, β= 94.105（6）, ）, = 94.305（6）°, V= 1185.7（11）/A3, Z = 2,μ = 0.397 mm^-1, Mr= 497.39, Dx= 1.393 g/cm^3, F（000） = 516, S = 1.097, the final R = 0.0730 and wR = 0.2133 for 4111 unique reflections （Rint = 0.0525） with 3212 observed ones. The dihedral angles made by the triazole ring with the methyl- and chloro-substituted benzene rings are 43.5（7） and 50.2（9）°, respectively. Some intra- and intermolecular hydrogen bonds together with C-H…π interactions existing in the lattice stabilize the crystal structure.     

Synthesis and Crystal Structure of 7-Amino-2,3,4,5-tetrahydro- 1,3-dimethyl- 5-（2-nitrophenyl）-2,4-dioxo-lH-pyrano[2,3- d]pyrimidine-6-carbonitrile DMF Solvate

The title compound 7-amino-2,3,4,5-tetrahydro-1,3-dimethyl-5-（2-nitrophenyl）- 2,4- dioxo-1H-pyrano[2,3-d] pyrirnidine-6-carbonitrile DMF solvate 1 （C19H20N6O6, Mr = 428.41） was synthesized and crystallized. The crystal belongs to the monoclinic system, space group P2 1/c with a = 11.383（2）, b = 13.372（2）, c = 13.673（2）A, β = 97.380（4）°, Z = 4, V = 2063.8（6）A^3, Dc = 1.379 g/cm^3,μ（MoKα） = 0.105 mm^-1, F（000） = 896, the final R = 0.0738 and wR = 0.1647 for 2964 observed reflections （I〉 2σ（I））. X-ray analysis reveals that the new pyran ring is coplanar, which is obviously different from those of other similar compounds. In addition, the unclassical hydrogen bonds of C-H…O and C-H…N are presented in the crystals except for the normal hydrogen bonds of N-H…O.     

Synthesis,Structure and Property of a 1D Coordination Polymer [Mn{5-（NO2）sal}2（phen）]n with 5-Nitrosalicylate Ligand

A new coordination polymer [Mn{5-（NO2）sal}2（phen）]n （5-（NO2）sal = 5-nitrosalicylate, phen = 1,10-phenanthroline） was synthesized by a hydrothermal reaction and characterized by elemental analysis, IR and X-ray single-crystal diffraction. The title complex crystallizes in orthorhombic, space group Pbcn with α = 25.747（8）, b = 13.220（4）, c = 7.009（3） A, V= 2386（1）A^3, Z = 4, R = 0.0427 and wR = 0.0890. The 5-nitrosalicylate anions doubly bridge the Mn（Ⅱ） atoms to form a one-dimensional polymeric chain with repeated eight-membered ring units （Mn-O-C-O）2. The crystal structure is stabilized by intra- and interchain hydrogen bonding interactions. The cyclic voltammetric behavior of the title complex is also reported.     

Synthesis and Crystal Structure of 2-（ 4-Decarboxydehydroabietyl）- 5-p-tolyl-[ 1,3,4 ]-oxadiazole

2-（4-Decarboxydehydroabietyl）-5-p-toyl-[1,3,4]-oxadiazole, C28H34N2O, has been synthesized and characterized by IR, NMR, elemental analysis and single-crystal X-ray diffraction method. The crystal belongs to the orthorhombic system, space group P212121 with a = 6.1351（5）, b = 14.8495（19）, c = 25.9050（2） A, V = 2360.0（4） A3, Z = 4, Mr = 414.57, Dc = 1.167 Mg/m^3, 2 = 0.71073 A,μ（MoKa） = 0.070 mm^-1, F（000） = 896, the final R = 0.0452 and wR = 0.1076 for 1647 observed reflections with I 〉 2σ（I）. There are five rings in the crystal structure of the title compound, but the oxadiazole ring is non-coplanar with the benzene ring D.     

2-Thioxo-1,2-dihydrobenzo[d][1,3]thiazin-4-one： Synthesis, Crystal Structure and Its Photoinduced Proton Transfer Reaction

2-Thioxo-1,2-dihydrobenzo[d][1,3]thiazin-4-one （TDBTO）, a new thiazin-one derivative, was synthesized and investigated. The crystal structure of TDBTO （CsHsNOS2, Mr = 193.8） was determined by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 6.946（3）, b = 7.402（3）, c = 8.954（4）A, α = 66.931（7）°,β = 89.866（7）°, γ = 72.289（7）°, V = 399.8（3） A^3, Z = 2, Mr = 195.25, Dc = 1.622 g/cm^3,μ = 0.606 mm^-1, F（000） = 200, R = 0.0361 and wR = 0.1032. There exist intermolecular hydrogen bond of N（1）-H（1A）-..O（1） and weak C（6）-H（6A）...O（1） contact in the structure as well as face-to-face π-π stacking interactions between the benzene ring and the thiazin ring of an adjacent benzothiazin unit. The photoinduced proton transfer reaction, transforming the initial thione into thiol form, was found, and the latter form was characterized by UV absorption spectra, fluo-rescence spectra and infrared spectra.     

Synthesis and Crystal Structure of 4-tert-Butyl-6-（4-chlorophenyl）-3,6- dihydro-2H-1,3-thiazin-2-iminium Chloride

The title compound, 4-tert-butyl-6-（4-chlorophenyl）-3,6-dihydro-2H-1,3-thiazin- 2-iminium chloride （C14H18C12N2S）, has been synthesized by the reaction of 1-（4-chlorophenyl）- 4,4-dimethylpent-1-en-3-one with thiourea, and its crystal structure was determined by single- crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P211c with a = 16.3064（11）, b = 9.4471（6）, c = 11.2626 （8）A, β = 108.400（1）°, Z = 4, V = 1646.28（19） A^3, Mr = 317.26, Dc = 1.280 g/cm^3, S = 1.078,μ = 0.510 mm^-1, F（000） = 664, the final R = 0.0514 and wR = 0.1412 for 3210 observed reflections （I 〉 2σ（I））. The thiazine ring system displays a twisted boat conformation, and three N-H,..Cl hydrogen bonds exist in the crystal. The combination of two N-H...Cl hydrogen bonds generate an R2^1 （6） ring.     

CRYSTAL STRUCTURE OF [Ce~(Ⅲ)Cl_2(THF)_5][Ce~ⅣC15(THF)]

<正> INTRODUCTION. The attempt to prepare C_9H_7CeCl_2. nTHF(C_9H_7=indenyl) by the reaction of CeCl_4 3THF with C_9H_7Na in THF(tetrahydrofuran) has failed, but an unexpected orange crystal was obtained and determined by single cryntal X-ray diffraction to be a new complex [Ce~ⅢCl_2 (THF)_5]~+[Ce~ⅣCl_5 THF]~-. The valence state of the cerium atom in the cation is different from that in the anion, the former being trivalent while the latter quadrivalent. In this paper the crystal structure of the new complex is reported.     

Synthesis and Crystal Structure of 2-Ethoxy-3-n-butyl-benzofuro[2,3-d]pyrimidin-4（3H）-one

The crystal structure of the new title compound 2-ethoxy-3-n-butyl- benzofuro[2,3d]pyrimidin-4（3H）-one （C16H18N2O3, Mr = 286.32） has been prepared and determined by singlecrystal X-ray diffraction. The crystal is of monoclinic, space group P21/c with a = 13.7167（14）, b = 13.113（1）, c = 8.378（1） A, β = 98.992（2）^o, V = 1488.4（3） A^3, Z = 4, Dc = 1.278, F（000） = 608, μ = 0.089 mm^-1, MoKa radiation （2 = 0.71073）, R = 0.0498, wR = 0.1238 for 2336 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that all ring atoms in the benzo[4, 5]furo [2,3-d] pyrimi- dinone moieties are almost coplanar.     

Hydrothermal Synthesis,Crystal Structure and Electrochemical Properties of a New Dinuclear Copper Complex [C2H6ON]2[Cu2Cl2（μ-CH3COO）4]

The hydrothermal reaction of copper chloride dihydrate and 5,5-dimethyl-imidazolidine,-2,4-dione with a mole ratio of 1：1 in acetonitrile resulted in the formation of a new acetate-bridged dinuclear copper complex, [C2H6ON]2[Cu2Cl2（μ-CH3COO）4]. Protonated acetamide in eaolie form and acetic acid were yielded by the hydrolysis of acetonitrile under hydrothennal condition. The rifle complex （C12H24Cl2Cu2N2O10） was characterized by X-ray single-crystal diffraction, IR spectrum, elemental and electrochemical analysis. It crystallizes in the monoclinic system, space group P21/c with a = 8.298004）, b = 14.358（2）, c = 12.0010（2） A^°, β= 130.620（3）°, V = 1085.3（2） A^°^3, Dc = 1.696 g/cm^3, 34, = 554.31, Z = 2, F（000） = 564 and μ = 2.254 mm^-1. The crystal structure consists of a tetraacetate-bridging dinulcear copper complex anion [Cu2Cl2（μ-CH3COO）4]^2-, with the chlorine anions in the axial positions, and two protonated acetamide cations [C2H6ON]^＋, which were connected through hydrogen bonds to form a three-dimensional infinite network.     

Synthesis, Crystal Structure and Quantum Chemistry of Tris[（2-methyl- 2-phenyl）propyl] （2,4-dinitro-phenolato）tin

The tris[(2-methyl-2-phenyl)propyl](2,4-dinitro-phenolato)tin was synthesized by the reaction of bis[tri(2-methyl-2-phenyl)propyltin] oxide with 2,4-dinitrophenol. The compound was characterized by IR, 1H NMR spectra and elemental analysis. The crystal structure has been determined by X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/n with a = 0.9649(0), b = 1.0087(8), c = 3.4867(4) nm, β = 90.965(7) , Z = 4, V = 3.3933(7) nm3, Dc = 1.369 Mg·m-3, (MoKa) = 0.796 mm-1, F(000) = 1440, R = 0.0345 and wR = 0.0821. The tin atom has a distorted tetrahedral geometry. The 2D network structure of the complex is formed by hydrogen bonds and π-π effects. The stabilities, orbital energies and composition characteristics of some frontier molecular orbitals of the complexes have been investigated with the aid of G98W software.     

蒂巴茵衍生物的合成研究

The reaction of 7α-acetyl-6,14-endoethano-6,7,8,14-tetrahydrothebaine with 2-（thien-2-yl）ethylmagnesium bromide was investigated. The tertiary alcohol derivative 7α-[R-l-hydroxyl-l-methyl-3-（thien-2-yl）propyl]）-6,14- endoethano-6,7,8,14-tetrahydrothebaine （3） and a by-product 4 were isolated. The structure of 4 was elucidated by X-ray analysis. The Grignard reaction shows high degree of stereoselectivity according with Cram rule. The crystal structure of 4 indicates that dihydrofuran ring was opened to form a phenolic hydroxyl group and a three-membered ring structure. It maintains the main rigid structure of morphine and contains a C（6）-C（14） enthano bridge. The 1-hydroxyl-1-methyl-3-（thien-2-yl）propyl group at C（7） position adopted S-configuration.     

Hydrothermal Synthesis, Crystal Structure and Fluorescence Spectrum Studies of a Supramolecular Compound {[2-(2-Pyridyl)benzimidazoleH2]2+·[SbCl5]2-}2

A new supramolecular compound, {[2-(2-pyridyl)benzimidazoleH2]2 ·[SbCl5]2-}2, was synthesized by the hydrothermal reaction of o-diaminobenzene, 2-pyridinecarboxylic acid and SbCl3 in 1:1 HCl solution, and characterized by chemical analysis, elemental analysis, IR spectra, thermogravimetric analysis and fluorescence spectra. The crystal structure was deter- mined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P21/c, with a = 16.0397(13), b = 14.3189(12), c = 15.6370(13) (A), β = 105.8980(10)°, V = 3454.0(5) (A)3, Z = 4, C24H22Cl10N6Sb2, Mr = 992.48, Dc = 1.909 g/cm3, μ = 2.366 mm-1, S = 1.010, F(000) = 1920, R = 0.0254 and wR = 0.0555. The coordination anion, [SbCl5]2- which is a distorted tetragonal pyramid, is composed by coordinating action with Sb3 ion and five adjacent chloride ions. Every four coordination anions of [SbCl5]2- form a biquaternion ring structure through the secondary bonding of Sb…C1.Moreover,the compund adopts a three-dimensional network supramolecular structure because of the hydrogen bonds and π-π stacking between the rings and the 2-(2-pyridy1)benzimidazole divalent cations.The title compound also shows godd fluorescent behaviors.     

Studies on Properties of p—Nitrophenylazo Calix[4]arene Derivatives

The p-nitrophenylazo calix[4] arene derivatives la-ld with nonlinear optical(NLO)properties were prepared by the diazo-coupling reaction of calix[4]arene with p-nitrophenyl diazonium.The diazotization reaction of p-nltroaniline was caried out with isoamyl nitrite as a source of nitrous acid in EtONa/EtOH under refluxing conditon.X-Ray crystallographic analysis and ^1H NMR sptectra reveal that they exist as cone conformation in crystal state or in soution.HRS measurements at 1064 nm in THF indicate that p-nitrophenylazo calix[4]arenes have higher hyperpolarizability βz values than the corresponding reference compound 4-(4-nitrophenylazo)-2,6-dimethyl-phenol,without red shift of the charge transfer band.The tetrakis p-nitropheylazo calix[4]arene(2)with longer alkyl chains can form monolayer aht the air/water interface.     

Synthesis and Structural Characterization of 1,4-Di（2-methoxyphenyl）-2,5-piperazinedione

A new derivative of 2,5-piperazinedione, 1,4-di（2-methoxyphenyl）-2,5-piperazinedione （I）, was synthesized by the cyclocondensation reaction of N-2-methoxyphenyl chloroacetamide, and its structure was characterized by elemental analysis, IR, ^1H NMR and single crystal X-ray diffraction method. The crystal belongs to monoclinic system, space group P21/c with unit cell dimensions a=0.56934（10） nm, b=1.3880（2） nm, c=1.00329（17） nm, β= 90.376（3）°, V= 0.7928（2） nm^3, Z=2, Dc = 1.367 g·cm^-3,μ = 0.98 cm^-1, R and wR being 0.0606 and 0.1564 respectively for 1549 unique reflections with 1247 observed reflections [I〉2σ（I）]. The molecule has a crystallographically imposed symmetry center. The three rings in the molecule are each coplanar with their attached groups, excluding methyl H atoms and the H atoms attached to the piperazinedione ring, while the whole molecule is not planar, with dihedral angles of 74.7（1）° between the piperazinedione and each of the two aromatic rings. The crystal structure is stabilized by van der Waals and dipole-dipole forces.     

Synthesis,Structure Analysis,and Antitumor Activity of （R）-2,4-Dioxo-5-fluoro-l-[1-（methoxycarbonyl） Ethylaminocarbonylmethyl]-1,2,3,4-tetrahydropyrimidine

A new dipeptide compound, （R）-2,4-dioxo-5-fluoro-1-[1-（methoxycarbonyl） ethylaminocarbonylmethyl]-1,2,3, 4-tetrahydropyrimidine （5-FUAPM）, has been synthesized and identified by means of elemental analysis, IR, ^1H NMR and ^13C NMR spectra. The single crystal of compound 5-FUAPMoDMF was also obtained and characterized by DSC-TGA techniques. The crystal belongs to orthorhombic space group P212121 with the cell parameters： a= 0.4740（7） nm, b= 1.923（3） nm, c= 1.9229 nm, a=β=y=90°, V= 1.753 nm^3, Z=4, Dc= 1.312 g/cm^3, Mr=346.32, F（000）=728 and u=0.111 mm^-1. The final R and wR are 0.1378 and 0.2862, respectively. The result of the biological test showed that the compound 5-FUAPM has certain antitumor activities.