Synthesis and Crystal Structure of a Novel Organic Adduct Nonlinear Optical Material: 3,5-Dinitrobenzonic Acid·ethanolamine (3,5-DNBEA)

The title compound (C2H7NO·C7H4N2O6) has been obtained by the reaction of etha- nolamine with 3,5-dinitrobenzoic acid in deionized water at room temperature. The crystal crystal- lizes in orthorhombic, space group P212121 with a = 6.048(2), b = 9.146(3), c = 21.955(7)(A), C9H11N3O7, Mr = 273.21, Z = 4, V = 1214.3(7)(A)3, Dc = 1.494 g/cm3, F(000) = 568, μ(MoKα) = 0.131 mm-1, R1 = 0.0338 and wR2 = 0.0497. The new organic adduct is composed of one ethanolamine and one 3,5-dinitrobenzoic acid, which are linked up by O-H…O and N-H…O types of hydrogen bonds to form a nine-membered ring and an eleven-membered ring, extending into a one-dimensional network structure.     

Synthesis,Crystal Structure and Theoretical Calculation of [2-（2,6-Dioxacyclohexyl）-5-methoxylphenols]2

The title compound [2-（2,6-dioxacyclohexyl）-5-methoxylphenols]2 was synthesized by the reaction of 2-hydroxyl-3-methoxylbenzaldehyde and 1,3-propanediol in the presence of DMF-DMS adduct and characterized by IR spectrum, UV-Vis spectrum and X-ray crystallography. The title compound belongs to monoclinic, space group P21 with a = 9.8967（10）, b = 8.2240（9）, c = 13.3654（14） A^°, β= 90.016（2）°, C11H14O4, Mr = 210.22, V = 1087.8（2）A^°3, Z = 4, Dc = 1.284 Mg/m^3, F（000） = 448,μ = 0.098 mm^-1, the final R = 0.0300 and wR = 0.0761 for 2070 observed reflections with I 〉 2σ（I）. The molecules are connected via intermolecular O-H…O hydrogen bonds into a 2D network structure. Moreover, theoretical investigations of the title compound with HF/6-31G（d） method were performed, and its stability, frontier molecular orbital composition and Mulliken charge distribution were also discussed. The compound is a bis-molecule. The two molecules stay together and could not be separated. Two crystallographically independent molecules exist in an asymmetric unit. The bond lengths and bond angles of the two molecules are slightly different with each other.     

1-(4-甲氧基)苯甲酰基-3-(4,6-二甲基嘧啶-2-氨基)硫脲的晶体结构、 理论计算及生物活性

2-氨基-4,6-二甲基嘧啶与硫氰酸钾、4-甲氧基苯甲酰氯在乙酸乙酯中反应, 合成了1-(4-甲氧基)苯甲酰基-3-(4,6-二甲基嘧啶-2-氨基)硫脲, 并用X射线单晶衍射法测定其晶体结构, 晶体属单斜晶系, 空间群为P21/n, 晶胞参数为: a＝1.0134(4) nm, b＝1.3172(5) nm, c＝1.0988(4) nm, β＝91.671(8)°, V＝1.4661(9) nm3, Dc＝1.433 g/cm3, μ＝0.234 mm－1, F(000)＝664, Z＝4, R1＝0.0571, wR2＝0.1328. 运用Gaussian 03程序, 对标题化合物进行了HF/6-31＋g(d)和B3LYP/6-31＋g(d)水平的几何全优化和频率计算, 并对其成键情况及自然键轨道(NBO)进行了分析. 初步实验证明该化合物具有良好的生物活性.     

4,6-二甲氧基-2-[甲氧脲基硫代脲基]嘧啶的合成、晶体结构和理论计算

利用2-氨基-4,6-二甲氧基嘧啶在干燥条件下与硫氰酸钾、氯甲酸甲酯在乙酸乙酯溶液中反应制得4-(4,6-二甲氧基嘧啶-2-基)-3-硫代脲酸甲酯, 在二甲基甲酰胺溶液中培养出单晶, 通过X射线单晶结构分析法测定分子结构和晶体结构, 晶体属单斜晶系, 空间群为C2/m, 晶胞参数为: a＝1.6672(3) nm, b＝0.66383(12) nm, c＝1.1617(2) nm, β＝109.275(2)°, V＝1.2136(4) nm³, D_c＝1.490 g/cm³, μ＝0.281 mm^－1, F(000)＝568, Z＝4, R₁＝0.0341, wR₂＝0.1042. 运用Gaussian 03程序, 在6-311G的基组水平上, 用HF, MP2以及B3LYP三种计算方法对标题化合物进行了几何全优化, 并对其成键情况及自然键轨道(NBO)进行了分析.     

3-(2-对甲苯基乙烯基)-5(4H)-异噁唑酮的合成、晶体结构、1H NMR及其异构化研究

采用甲硫酯与NH2OH·HCl在室温条件下反应,合成了3-(2-对甲苯基乙烯基)-5(4H)-异唑酮,通过单晶X射线衍射确定了产物的结构.由1HNMR确定的构型与晶体结构完全一致,表明标题化合物在弱极性溶剂(如乙醚和氯仿)中是稳定的.半经验AM1和PM3计算的C7和C8净电荷(分别为-0.077,-0.101)可能是H7和H8化学位移(分别为6.83和6.96)很接近的主要原因.B3LYP/6-311G**基组计算的异构体能量数据表明,3-(2-对甲苯基乙烯基)-5(4H)-异唑酮是最稳定的构型     

4-(1,2,4-三唑-5-酮-4-基)-3-硫代脲酸乙酯的合成、晶体结构及理论计算

4-氨基-1,2,4-三唑-5-酮(ATO)与硫氰酸钾、氯甲酸乙酯在乙酸乙酯中反应, 合成了4-(1,2,4-三唑-5-酮-4-基)-3-硫代脲酸乙酯, 在室温下采用缓慢蒸发溶剂二甲基甲酰胺得到合适的可用于X射线衍射的单晶. 晶体属六方系, 空间群为R-3, 晶体结构参数为a＝2.60524(7) nm, b＝2.60524(7) nm, c＝0.82579(6) nm, γ＝120°, V＝4.8540(4) nm³, D_c＝1.442 g/cm³, μ＝0.300 mm^－1, F(000)＝2190, Z＝18, R₁＝0.0569, wR₂＝0.1424. 选取标题化合物的一个结构单元作为初始模型, 运用Gaussian 03程序对化合物进行了HF/6-311G, MP2/6-311G和B3LYP/6-311G水平的几何全优化,并对其原子电荷及自然键轨道(NBO)进行了分析.     

Synthesis and Crystal Structure of Isonicotinic Acid [1-（3,5-Dibromo-2- hydroxyphenyl）methylidene]hydrazide Methanol

A new Schiff base compound, C13H9Br2N3O2·CH3OH, isonicotinic acid [1-(3,5- dibromo-2-hydroxyphenyl)methylidene]hydrazide methanol, has been synthesized and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. The compound comprises a Schiff base moiety isonicotinic acid [1-(3,5-dibromo-2-hydroxyphenyl) methylidene]hydrazide and a methanol molecule. The crystal belongs to the triclinic system, space group P1 with a = 8.464(1), b = 9.511(2), c = 10.901(2) , α = 92.940(2), β = 110.456(2), γ = 96.040(2)o, Z = 2, V = 814.0(2) 3, Dc = 1.759 g/cm3, Mr = 431.09, λ(MoKα) = 0.71073 , μ = 4.994 mm-1, F(000) = 424, R = 0.0440 and wR = 0.1061. A total of 3284 unique reflections were collected, of which 2197 with I > 2σ(I) were observed. The molecule adopts a trans configuration about the C=N double bond. The dihedral angle between the benzene and pyridine rings is 22.0(4)o. The crystal structure is stabilized by intermolecular O-H···N and C-H···O hydrogen bonds, forming layers parallel to the ac plane. The preliminary biological tests show that the compound has potential antibacterial activities.     

Synthesis, Crystal Structure and Theoretical Calculation of 1,1',5,5'-Tetramethyl-2,2'-diphenyl-4,4'-[i-phenylene-bis(methylidynenitrilo)] di-1H-pyrazol-3(2H)-one

1,1',5,5'-Tetramethy1-2,2'-diphenyl-4,4'-[i-phenylenebis(methylidynenitrilo)]di1H-pyrazol-3(2H)-one was synthesized and characterized by X-ray single-crystal diffraction analysis. The crystal crystallizes in monoclinic, space group P21/c with a = 6.1375(1), b =24.6571(4), c = 17.7487(3)(A), β = 94.781(1)°, V= 2676.62(8)(A)3, C30H28N6O2, Mr= 504.58, Z = 4,Dc = 1.252 g/cm3, F(000) = 1064, μ = 0.081 mm-1, R = 0.0463 and wR = 0.1153 (I ＞ 2σ(Ⅰ)).Theoretical studies of the title compound were carried out by density functional theory (DFT) BLYP method, using ADF program package. It indicates that N(26) and N(41) are active sites of the title compound.     

Synthesis and Crystal Structure of a Novel Layered Lead(Ⅱ) Carboxylate-sulfonate Compound Templated by 4,4''-Bipyridine

A new lead(Ⅱ) carboxylate-sulfonate has been hydrothermally synthesized and characterized by X-ray single-crystal and elemental analyses. It crystallizes in triclinic, space group P,(1) with a=8.1573(6), b=9.4663(7), c=12.7488(9) (A), α=89.2320(10), β=80.7380(10), γ=77.9760(10)°, Z=2, V=950.10(12) (A)3, Mr=599.57, Dc=2.096 g/cm3, μ=9.032 mm-1, F(000)=572, the final R=0.0412 and wR=0.1035. It has a 1D chain structure, and the Pb(Ⅱ) is six-coordinated. Two PbO6 polyhedra are interconnected via edge-sharing into a two-core unit. Such units are further interconnected by 3-sulfonato-benzoic acids into 1D chains which are linked by hydrogen bonds into a layer structure. The 4,4'-bipyridines are located at the interlayer space and link the layers into a supramolecular structure by π-π stacking interactions.     

Crystal Structure, Thermal Analysis and Theoretical Calculation of a One-dimensional Chain Complex [Zn（dafo）2（H2O）2]（NO3）2

Introduction Molecular recognition and molecular self-assemblycarried out by cooperation of the weak interactions(electrostatic reaction, hydrogen bonds, van der Waalsforce, short-range repulsive force, etc) are the commonphenomena in nature. In recent years, the research onsupramolecular complex has been a crossing focus ofseveral subjects such as chemistry, physics, biology,material and information.1 Supramolecular complex hasa wide application foreground in material, catalysis,conductor,…     

4- (4,6-二甲基嘧啶-2-基)-3-硫代脲酸甲酯的合成晶体结构及量子化学研究

4-（4,6-Dimethylpyrimidin-2-yl）-3-thio-allophanic acid methyl ester was synthesized with mixing 2-amino-4,6- dimethylpyrimidine, potassium thiocyanate and methyl chloroformate in ethyl acetate. Single crystals suitable for X-ray diffraction measurement were obtained by recrystallization from dimethylformamide at room temperature. The crystal belongs to monoclinic symmetry with space group C2/m, and crystal parameters of a= 1.7537（5） nm, b= 0.6759（2） nm, c=1.1148（3） nm, β=118.557（4）°, V=1.1605（6） nm^3, Z=4, De= 1.375 g/cm^3,μ=0.271 mm^-1, F（000）=504, and 1519 [1〉2σ（I）] observable independent reflections were used for the determination and refmement of the crystal structures with final R1 of 0.0372 and wR2 of 0.0992. The theoretical investigation of the title compound was carried out with DRT-B3LYP/6-311G, HF/6-311G and MP2/6-311G methods, and the atomic net charges and the population were discussed.     

Synthesis and Crystal Structure of 3,3''-Bis(2-benzimidazolyl)-2,2''-dipyridine with Hydrated Zinc(Ⅱ) Perchlorate

The reaction of Zn(ClO4)2·6H2O with 3,3'-bis(2-benzimidazolyl)-2,2'-dipyridine (L) gave a mononuclear zinc(Ⅱ) complex: [ZnL2](ClO4)2·2DMF·4H2O, which was structurally characterized by EA, IR, UV, 1H NMR, fluorescence spectrum and single-crystal X-ray diffraction. The crystal (C54H54Cl2N14O14Zn, Mr=1259.38) belongs to the monoclinic system, space group C2/c with a=20.874(2), b=14.9953(16), c=20.462(3) (A), β=101.553(2)°, V=6274.8(13) (A)3, Z=4, Dc=1.333 g/cm3, F (000)=2608, μ(MoKα)=0.548 mm-1, R=0.0682 and Wr=0.1931 for 4984 observed reflections with Ⅰ ＞ 2σ(Ⅰ). The Zn(Ⅱ) is four-coordinated in a slightly distorted tetrahedral geometry through four N atoms from four benzimidazole units of two ligands. In the crystal lattice, the [ZnL2]2 cations are linked to each other by extensive intermolecular hydrogen bonds between nitrogen atoms of benzimidazole rings, water and DMF molecules.     

Synthesis, Crystal Structure and Bioactivities of 1-（4-Chlorophenyl）-3- [ 5-（pyrid-4-yl）- 1,3,4-thiadiazol-2-yl] urea

The title compound 1-(4-chlorophenyl)-3-[5-(pyrid-4-yl)-1,3,4-thiadiazol-2-yl]urea (C14H10ClN5OS, Mr = 331.79) has been synthesized by the reaction of 2-amino-5-(pyrid-4-yl)- 1,3,4-thiadiazole with 4-chlorobenzoyl azide, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to triclinic system, space group P with a = 5.8550(8), b = 7.5668(10), c = 16.416(2) , α = 78.364(2), β = 81.204(2), γ = 84.749(2)°, V = 702.58(16) 3, Z = 2, Dc = 1.568 g/cm3, μ = 0.429 mm-1, F(000) = 340, the final R = 0.0442 and wR = 0.1092 for 2001 observed reflections (I > 2σ(I)). X-ray diffraction analysis reveals that the title molecule is nearly planar. In the crystal structure, the molecules are linked by strong intermolecular N-H…N hydrogen bonds together with weak nonclassical intermolecular (C-H…Y, Y = N, O and Cl) hydrogen bonds and stacked through π-π interactions. The preliminary bioassay shows that the title compound exhibits good fungicidal activities against Rhizoctonia solani, Botrytis cinerea and Dothiorella gregaria.     

Synthesis and Crystal Structure of a 1-D Coordination Polymer [Pb（ANS）2（phen）]n

A new one-dimensional coordination polymer, [Pb(phen)(ANS)2]n (ANS = 2-ami- nonaphthalene-1-sulfonate, phen = 1,10-phenanthroline), has been prepared by hydrothermal synthesis and structurally characterized by elemental analysis, IR and single-crystal X-ray diffrac- tion. The results determined by XRD reveal that the complex crystallizes in monoclinic, space group P21/c with a = 16.8374(14), b = 16.9825(14), c = 9.9392 (8) , β = 95.9830(10)o, V = 2826.5(4) 3, Mr = 831.86, Dc = 1.955 g/cm3, μ(MoKα) = 6.173 mm-1, F(000) = 1624, Z = 4, the final R = 0.0272 and wR = 0.0694 for 4305 observed reflections (I > 2σ(I)). In the complex, the adjacent lead(II) ions are bridged through the oxygen atoms of sulfonate groups in a syn-syn conformation, yielding an infinite zigzag chain. And the intermolecular N–H···O hydrogen bonds link the chains into two-dimensional layered networks, which are further assembled into a separate two-layer-film-like packing structure.     

Synthesis, Crystal Structure, and Cytotoxic Property of Di(μ1",1"-azide)bis(4-nitro-2-(3 ''-dimethylamino-n-propylimino)methylenephenolate)dizinc(Ⅱ)

The title azide-bridged dinuclear Schiff base zinc(Ⅱ) complex [Zn2(C12H16N3O3)2-(μ1,1-N3)2] was prepared and characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group F21/n with a = 8.736(2), b = 14.850(3), c = 11.775(2) (A), β = 102.42(3)°, V= 1491.8(5) (A)3, Z= 2, Dc = 1.593 g/cm3, Mr = 715.36, λ(MoKα) = 0.71073 (A), μ = 1.669 mm-1, F(000) = 736, the final R = 0.0338 and wR = 0.0789. A total of 3411 unique reflections were collected, of which 2777 with Ⅰ＞2σ(Ⅰ) were observed. The molecule of the complex is located on a crystallographic inversion centre. Each Zn atom in the complex is five-coordinated by one Schiff base ligand and two bridging azide groups, forming a trigonal bipyramidal configuration. The Zn…Zn distance is 3.328(2) (A). In the crystal structure, molecules are linked through intermolecular C-H…N hydrogen bonds, forming layers parallel to the bc plane. The complex shows low cytotoxic property to both normal and carcinoma cells.     

Synthesis, Crystal Structure, Fluorescence Properties and Geometrical Calculation of 4,8,10-Trimethyl-2-(3,5-dimethylpyrazol)pyrido-[2',3':3,4]-pyrazol[1,5-a]-pyrimidin

A novel compound 4,8,10-trimethyl-2-(3,5-dimethylpyrazol)-pyrido-[2',3':3,4]-pyrazol-[1,5-5-a]-pyrimidine (C17H18N6) has been synthesized from 2,6-dichloro-4-methylnico-tinonitrile, hydrazine and acetylacetone by substitution and cyelolization. The structure was characterized by elemental analysis, 1H NMR and IR, and single-crystal structure was determined by X-ray diffraction analysis. The compound crystallizes in the monoclinic system, space group P21/c with a = 8.0338(9), b = 28.618(3), c = 7.2688(8) (A),β = 111.051(2)°, V= 1559.6(3) (A)3, Z = 4, Dc=1.305 g/cm3,μ = 0.083 mm-1, Mr = 306.37, F(000) = 648, S = 0.971, the final R = 0.0795 and wR =0.1746 for 1457 observed reflections (Ⅰ > 2σ(Ⅰ)). The results demonstrate that the pyridine, pyrazole and pyrimidine rings are nearly eoplanar, which is evident from the dihedral angles among the four rings in the range of 0.13～4.15°. The face-to-face π-π stacking interactions among pyridine,pyrazol and pyrimidine rings result in a supramolecular crystal, in which they seem to be effective in stabilizing the structure. Meanwhile, the fluorescence properties of the title compound were discussed, which showed very strong fluorescence. The calculated results (selected bond lengths,bond angles and torsion angles) are all typical and agree well with the experimental results, which demonstrates that B3LYP/6-31+G* is suitable for the title compound.     

Synthesis, Crystal Structure and Quantum Chemistry Study of Tri（o-bromobenzyl）tin Ferrocenecarboxylate

A novel complex tri(o-bromobenzyl)tin ferrocenecarboxylate has been synthesized and its crystal structure was determined by X-ray diffraction. It belongs to orthorhombic, space group Pbca with a = 1.1340(3), b = 1.7823 (4), c = 3.0119(8) nm, V = 6.088(3) nm3, Mr = 857.81, Z = 8, Dc = 1.872 g/cm3, μ(MoKα) = 52.63 cm-1, F(000) = 3328, R = 0.0683 and wR = 0.1057. The tin atom adopts a distorted tetrahedral coordination geometry. Further studies on the title com- plex have been performed with quantum chemistry calculation at the Lanl2dz basis set level using G98W package. The stability of the complex, some frontier molecular orbital energies and com- position characteristics of some frontier molecular orbitals have been investigated.     

Synthesis, Crystal Structure and Electrochemistry Properties of a (N,N''-Ethylene-bis(salicylaldiminato)) Nickel(Ⅱ) Complex, [Ni2(salen)2]·NCS-NH4

A new Ni(Ⅱ) complex [Ni2(salen)2]·(NCS)·NH4 (salen = N,N'-bis(salicylidenea-mino)ethanato) has been prepared and structurally characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. It crystallizes in the orthorhombic system, space group Pbca with a = 16.8725(13), b = 19.0046(15), c = 20.0583(16) (A), Z = 8, V = 6431.8(9) (A)3, C33H32N6Ni2O4S1, Mr= 726.13, Dc = 1.500 g/cm3, F(000) = 3008, μ = 1.284 mm-1, the final R = 0.0394 and wR = 0.0767 for 4449 observed reflections with Ⅰ＞2σ(Ⅰ). The complex involves a N,N'-ethylene-bis(salicylaldiminato) Schiff base, an isothiocyanato anion and an ammonium cation. The nickle(Ⅱ) ion adopts a distorted square coordination geometry with N2O2 set of Schiff base ligand. The complexes are linked into a dimmer via intermolecular hydrogen bonds and the [Ni(salen)] moieties are connected together to form a 2-D layer structure by intermolecular N-H…O hydrogen bonds and π-π stacking. Cyclic-voltammetry method was used to characterize electrochemically the complex.     

Synthesis, Crystal Structure and Electrochemical Properties of a One-dimensional Chain Coordination Polymer [Mn（phen）（2,4,6-TMBA）2（H2O）]n

A one-dimensional chain-like coordination polymer [Mn(phen)(2,4,6-TMBA)2(H2O)]n has been synthesized from 2,4,6-trimethylbenzoic acid, 1,10-phenanthroline and anhydrous manga- nese(Ⅱ ) sulfate and then characterized. Crystal data for this complex: tetragonal, space group I41, a = 2.05643(16), b = 2.05643(16), c = 1.3939(2) nm, V = 5.8946(11) nm3, Mr = 579.54, Z = 8, Dc = 1.306 g/cm3, μ(MoKα) = 0.490 mm-1, F(000) = 2424, S = 0.985, the final R = 0.0411 and wR = 0.0950. The Flack factor is -0.01(2). The crystal structure shows that two neighboring man- ganese(Ⅱ ) ions are linked together by one bridge-chelating 2,4,6-trimethylbenzoic group, forming a one-dimensional chain structure. The manganese(Ⅱ ) ion is coordinated with two nitrogen atoms of one 1,10-phenanthroline, three oxygen atoms from three 2,4,6-trimethylbenzoic acids and one water oxygen atom, giving a distorted octahedral coordination geometry. The cyclic voltametric behavior of the complex was also investigated.     

Synthesis, Crystal Structure and Electrochemical Properties of One-dimensional Chain Coordination Polymer [Co(Ⅱ)(C6H5CH=CHCOOH)2(4,4''-bipy)(H2O)5]n

A one-dimensional chain coordination polymer [Co(Ⅱ)(C6H5CH=CHCOOH)2(4,4'-bipy)(H2O)5]n has been synthesized with cinnamylic acid, 4,4'-bipy and cobaltous chloride as raw materials. Crystal data for this complex: monoclinic, space group P21/c, a - 1.1481(3), b =1.1230(2), c = 1.1759(3) nm, β = 97.054(4)°, V = 1.5046(6) nm3, Mr= 617.50, Dc = 1.363 g/cm3, Z= 2, μ(MoKα) = 0.627 mm-1, F(000) = 646, S = 1.062, R 0.0443 and wR = 0.1178. The crystal structure shows that two neighboring cobalt(Ⅱ) ions are linked together by one 4,4'-bipy, and the whole complex molecule adopts a one-dimensional chain structure. Each cobalt(Ⅱ) ion is coordinated with two nitrogen atoms from two 4,4'-bipy molecules and four oxygen atoms from four water molecules, giving a distorted octahedral coordination geometry. The electrochemical properties were analyzed by combining with the crystal structure.