3-芳基-6-甲基-1,6-二氢-1,2,4,5-四嗪及其衍生物的合成和晶体结构

以乙腈和芳基腈为原料, 经过醚化、环化和还原三步方便且有效地合成了3-芳基-6-甲基-1,6-二氢-1,2,4,5-四嗪, 并在此基础上合成了一系列新的3-芳基-6-甲基-1,6-二氢-1,2,4,5-四嗪衍生物, 通过元素分析, ¹H NMR, IR和HRMS对这些化合物进行了表征. 对化合物N-邻甲基苯-3-苯基-6-甲基-1,6-二氢-1,2,4,5-四嗪-1-甲酰胺(5a)的X射线晶体衍射研究表明: 其属于单斜晶系, P2_{1 /c空间群, 晶胞参数a＝1.3941(6) nm, b＝0.5675(2) nm, c＝2.0614(8) nm; α＝γ＝90°, β＝102.055(6)°; V＝1.5949(11) nm³, 此类化合物的四嗪环采用不对称船式结构, 且具有同芳香性.}     

A Three-dimensional Supramolecular Complex {[Co(H2btec)(2,2'-bipy)(H2O)3]·H2O}n Assembled via Hydrogen Bonding and π-π Stacking Interactions

A new cobalt compound, {[Co(H2btec)(2,2'-bipy)(H2O)3]·H2O}n (1, H4btec =1,2,4,5-benzenetetracarboxylic acid, 2,2'-bipy = 2,2'-bipyridine), has been synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR and X-ray powder diffraction. The crystal belongs to the triclinic system, space group P-1, with a = 7.230(3), b = 11.626(5), c =14.001(6) (A), α = 108.12(0)°, β= 95.85(0)°, V= 1095.33(157)(A)3, C20H20CoN2O12, Mr= 539.31,Z=2, Dc = 1.635 g/cm3,μ = 0.855 mm-1, F(000) = 554, R = 0.0427 and wR = 0.1042 for 3883 observed reflections (Ⅰ ＞ 2σ(Ⅰ)). The title compound features a discrete molecular structure, which is connected with each other through extensive O-H…O hydrogen bonds into an intricate 3D supramolecular network. Additionally, two different patterns of π-π stacking interactions further consolidate the framework.     

Synthesis and Crystal Structure of N,N''''-Diphenyl-3, 6-diethyl-1,4-dihydro-s-tetrazine-1,4-dicarbonamide

1INTRODUCTIONIthasbeenarousedmoreandmoreinterestsinces-tetrazinewasfirstsynthesizedbyHautgschin1900[1].Thesynthesisofdihydroderivativeof3,6-dimethyl-s-tetrazinewasreportedindetailbySkorianetz[2].UsingX-ray,Jennison[3]foundthat1,6-dihydro-s-tetrazinehashom…     

Crystal Structure of Norfloxacin Methanol Solvate: C16H18FN3O3·CH3OH·H2O

Norfloxacin methanol solvate (1-ethyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-3-quinoline carboxylic acid methanol solvate) has been prepared. The crystal and molecular struc- tures of the title compound, C16H18FN3O3·CH3OH·H2O, were determined by X-ray diffraction me- thod. The compound crystallizes in monoclinic, space group P21/c with a = 7.8660(16), b = 22.525 (5), c = 10.253(2)(A), β = 108.31°, Mr = 369.39, V = 1724.7(6) (A)3, Z = 4, Dc = 1.423 g/cm3, F(000) = 784, R = 0.0557 and wR = 0.1224. The TGA analysis indicates that it decomposes completely at 723.75 ℃.     

Synthesis and Crystal Structure of Cis-syn Cyclobutane 1-（Carboxyethyl）thymine Dimer Monopentyl Amide Monotryptophan Methyl Ester Amide

The crystal structure of the title compound (C34H47N7O9, Mr = 697.79) has been determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21 with a = 9.000(8), b = 11.360(10), c = 17.841(15) , β = 97.083(14)°, V = 1810(3) 3, Z = 2, F(000) = 744, Dc = 1.280 g/cm3, μ = 0.094 mm-1, the final R = 0.0721 and wR = 0.1942 for 2479 observed reflections with I > 2σ(I). The two methyl groups attached to the cyclobutane ring are cis oriented. An intramolecular hydrogen bond (N(6)-H(6)…O(8)) introduces rigidity into the title molecule and the crystal structure is stabilized by intermolecular N-H…O hydrogen bonds.     

A Chiral Helical Compound Based on Achiral Components

The title compound, [Cu(dpa)(2,2'-bipy)(H2O)2]n 1 (H2dpa = diphenic acid and 2,2'- bipy = 2,2'-bipyridine), has been synthesized and its structure was determined by single-crystal X-ray diffraction. The crystal is of orthorhombic, space group P212121 with a = 10.597(4), b = 11.317(4), c = 17.630(7) , V = 2114.3(14) 3, C24H20CuN2O6, Mr = 495.97, Z = 4, Dc = 1.558 g/cm3, μ = 1.079 mm-1, F(000) = 1020, Flack value = 0.052(18), R = 0.0430 and wR = 0.1016 for 3381 observed reflections (I > 2σ(I)). In compound 1, the dpa ligands link metal ions into helical structures in the same direction.     

A New Supramolecular Compound Based on Cd（II）-Schiff-base and Keggin-type [PMo_（12）O_（40）]~3

A new supramolecular compound, {[Cd(L)2]2[PMo12O40NO3]·CH3CN·2H2O}n 1 (L is 1,4-bis(4-imidazolyl)-2,3-diaza-1,3-butadiene), based on Cd(II)-Schiff-base and Keggin- type [PMo12O40]3- was synthesized via self-assembly and structurally characterized by elemental analysis, infrared spectroscopy, and single-crystal X-ray diffraction analysis. The crystal is of triclinic, space group P1 with a = 12.0128(11), b = 13.6196(13), c = 13.9995(13) , α = 103.868(2), β = 95.225(2), γ = 101.024(2)°, V = 2160.0(3) 3, Z = 1, C34H39N26O45Cd2Mo12P, Mr = 2938.96, Dc = 2.259 g/cm3, μ = 2.276 mm-1, F(000) = 1400, the final R = 0.0565 and wR = 0.1613 for 4973 observed reflections with I 2σ(I). The crystal structure can be described by the packing of Keggin anionic and Metal-Schiff-base cationic layers.     

Synthesis and Crystal Structure of 1,4-Dimethyl-2,5-di{[2′-（3-pyridylmethylamino- formyl）phenoxyl]methyl}benzene Perchlorate

The title compound, 1,4-dimethyl-2,5-di { [2′-（3-pyridylmethylaminoformyl）phenoxyl]- methyl}benzene perchlorate （C36H36Cl2N4O12, Mr = 787.59）, has been synthesized and structurally determined by single-crystal X-ray diffraction. The crystal crystallizes in the orthorhombic system, space group Pbca with a = 14.366（4）, b = 15.159（4）, c = 16.443（5）A, V = 3580.9（17）/A3 Z = 4, De = 1.461 g/cm^3, /t = 0.253 mm^-1, F（000） = 1640, R = 0.0618 and wR = 0.1525 for 1615 observed reflections （I 〉 2σ（I））. In the structure of the title compound, a two-dimensional supramolecular layer is formed via intermolecular hydrogen bonding interactions.     

Synthesis and Crystal Structure of 2-Methoxy-benzoic Acid 2-Oxo-3-（2,4,6-trimethyl-phenyl）-1-oxa-spiro[4.4]non-3-en-4-yl Ester

The new title compound 2-methoxy-benzoic acid 2-oxo-3-(2,4,6-trimethyl-phenyl)-1-oxa-spiro[4.4]non-3-en-4-yl ester(3,C25H26O5) has been synthesized by the condensation reaction of 4-hydroxy-3-(2,4,6-trimethyl-phenyl)-1-oxa-spiro[4.4]non-3-en-2-one(2) with 2-methoxylben-zoyl chloride,and characterized by 1H NMR and MS spectra.Its crystal structure was determined by single-crystal X-ray diffraction.The crystal is of monoclinic,space group P21/c with a = 10.6945(7),b = 12.8176(7),c = 16.4223(10) ,β = 103.5665(17)o,V = 2188.3(2) 3,Z = 4,Dc = 1.234 g/cm3,F(000) = 864.000,μ = 0.085 mm-1,the final R = 0.0520 and wR = 0.1132 for 2732 observed reflections with I 2σ(I).In the crystal structure,the C(1)-C(2)(1.478 ) bond is significantly shorter than the normal single C-C bond(1.53 ),suggesting that the carbonyl group on C(1) has formed a conjugated system with a double bond on C(2) and C(12).     

Chiral Phosphine Ligands Derived from Sugars. 14. Crystal Structure of Diphenyl(methyl 4',6'-O-benzylidene-3'-deoxy-α-D-altropyranoside-3-)phosphine Oxide

The crystal structure of the title compound, C26H27O6P, has been determined by single-crystal X-ray diffraction analysis. The crystal is orthorhombic with space group P212121, a=6.154(4), b=17.199(8), c=22.180(3)(A), V=2347.6(A)3, Dc=1.32 g/cm3, F(000)=984, μ=1.5cm-1, Z=4, and final R=0.075 and Rw=0.080 for 1417 reflections (I≥3σ(I)). The X-ray diffraction analysis revealed that the structure of the title compound s similar to that of its parent phosphine and the pyranose and 4, 6-O-benzylidene rings remain distorted chair conformations.     

Crystal Structure of 3-Methyl-4-methoxy-3-(3-methyl-4- methoxy-2-benzofuranyl) -2-H-benzofuranyl

1　ＩＮＴＲＯＤＵＣＴＩＯＮ3ｍｅｔｈｙｌ4ｈｙｄｒｏｘｙｂｅｎｚｏｆｕｒａｎｉｓａｎｉｎｔｅｒｍｅｄｉａｔｅｕｓｅｄｆｏｒｔｈｅｓｙｎｔｈｅｓｉｓｏｆｎａｔｕｒｅｐｒｏｄｕｃｔｓ[1].Ｉｔｈａｓｂｅｅｎｓｙｎｔｈｅｓｉｚｅｄｆｒｏｍ1,3ｄｉｈｙｄｒｏｘｙｂｅｎｚｅｎｅ[2-3].Ｔｏｓｙｎｔｈｅｓｉｚｅａｂｉｅｔａｎｅｑｕｉｎｏｎｅｄｉｔｅｒｐｅｎｏｉｄｓｗｉｔｈｉｔ[4,5],ｗｅｉｎｔｅｎｄｅｄｔｏｐｒｏｔｅｃｔｔｈｅｈｙｄｒｏｘｙａｔｔａｃｈｅｄｔｏｉｔｗｉｔｈＭｅ2ＳＯ4.Ｆｉｎａｌｌｙ,ｔｗｏｃｏｍｐｏｕ…     

Dicopper(I) complexes with reduced states of 3,6-bis(2'-pyrimidyl)-1,2,4,5-tetrazine: crystal structures and spectroscopic properties of the free ligand, a radical species, and a complex of the 1,4-dihydro form

The complexes [(mu-bmtz(*-))[Cu(PPh(3))(2)](2)](BF(4)) (1) and [(mu-H(2)bmtz)[Cu(PPh(3))(2)](2)](BF(4))(2) (2) (bmtz = 3,6-bis(2'-pyrimidyl)-1,2,4,5-tetrazine and H(2)bmtz = 1,4-dihydro-3,6-bis(2'-pyrimidyl)-1,2,4,5-tetrazine) were obtained as stable materials that could be crystallized for structure determination. 1.2 CH(2)Cl(2): C(84)H(70)BCl(4)Cu(2)F(4)N(8)P(4); monoclinic, C2/c; a = 26.215(7) A, b = 22.122(6) A, c = 18.114(5) A, beta = 133.51(1) degrees; Z = 4. 2.CH(2)Cl(2): C(83)H(70)B(2)Cl(2)Cu(2)F(8)N(8)P(4); triclinic, P1; a = 10.948(2) A, b = 12.067(2) A, c = 30.287(6) A, alpha = 93.82(3) degrees, beta = 94.46(3) degrees, gamma = 101.60(3) degrees; Z = 2. Bmtz itself was also structurally characterized (C(10)H(6)N(8); monoclinic, P2(1)/c; a = 3.8234(8) A, b = 10.147(2) A, c = 13.195(3) A, beta = 94.92(3) degrees; Z = 2). Whereas the radical complex ion contains a planar tetrazine ring in the center, the 1,4-dihydrotetrazine heterocycle in the corresponding complex of H(2)bmtz is considerably folded. Both systems exhibit slight twists between the tetrazine and the pyrimidine rings. The intra-tetrazine distances are characteristically affected by the electron transfer, as is also evident from a comparison with the new structure of free bmtz; the bonding to copper(I) changes accordingly. Spectroscopy including X- and W-band EPR of the radical species confirms that the electron addition is mainly to the tetrazine ring.     

Hydrothermal Synthesis and Crystal Structure of a Cadmium(Ⅱ) Polymer with One-dimensional Chain Structure: [Cd(MDPPz)(BDC)(H2O)]n

A metal-organic coordination compound formulated as [Cd(MDPPz)(BDC)(H2O)]n 1 (MDPPz = 11-methyldipyrido[3,2-a:2',3'-c]phenazine, BDC = 1,4-benzenedicarboxylate) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, fluorescence spectrum and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group C2/c, with a = 30.673(8), b = 9.623(3), c = 20.784(6) (A), β = 98.646(3)o, V = 6065(3) (A)3, C27H17CdN4O5, Mr = 589.85, Dc = 1.292 g/cm3, μ(MoKα) = 0.757 mm(1, F(000) = 2360, Z = 8, the final R = 0.0381 and wR = 0.0855 for 4191 observed reflections (I＞2σ(I)). 1 exhibits blue fluorescence property at room temperature.     

一维链状卤化亚铜化合物的溶剂热原位合成、 结构及性质

采用溶剂热原位反应合成了一例具有一维铜卤链结构的化合物(C₁₀H₂₂N₂)₃[Cu₉I₁₄Br](C₁₀H₂₂N₂=N,N'-二乙基三乙烯二胺阳离子). 利用X射线单晶衍射、 元素分析、 粉末X射线衍射及红外光谱等测试手段对化合物进行了表征. 测试结果表明, 化合物属于单斜晶系, C2/c空间群, a=2.6233(5)nm, b=1.6299(3)nm, c=1.6707(3)nm, β=117.31(3)°, V=6.347(2) nm³. 化合物的结构由一维的铜卤链和有机模板剂构成, 其中有机模板剂是通过三乙烯二胺和乙醇烷基化反应得到的有机季铵盐阳离子. 该化合物在室温下表现出较好的光致发光性质.     

Synthesis and Crystal Structure of N-[(3aR,4R,4aR,5aS,6S,6aS)-1,3-Dioxooctahydro-4,6-ethenocyclopropa[f]isoindol-2(1H)yl]-4-(trifiuoromethyl)phenylmethanimine Monohydrate

The crystal structure of the title compound (C19H17F3N2O4,Mr=394.35) was determined by single-crystal X-ray diffraction.The crystal belongs to monoclinic,space group C2/c with a=28.383(6),b=10.355(2),c=12.799(3)(A),β=111.74(3)°,V=3493.8(12)(A)3,Z=8,De=1.499 g/cm3,λ(MoKα)=0.71073,F(000)=1632,μ= 0.127 mm-1,R=0.0412 and wR=0.1019.In the title compound,there exist three intennolecular hydrogen interactions (O(4)...O(1),O(4)...O(3) and O(4)...N(1)) between water.The neighboring molecules are linked to each other generating a two-dimensional network structure via the three intermolecular hydrogen bonds and π-π interactions shaped by phen-phen with centroid distance of 4.049 (A).     

Hydrothermal Synthesis and Crystal Structure of a Nickel（Ⅱ） Polymer with a One-dimensional Chain Structure：[Ni（cbba）_2（bipy）（H_2O）_2]_n

A metal-organic coordination polymer formulated as [Ni(cbba) 2 (bipy)(H 2 O) 2 ] n 1 (H 2 cbba=2-(4-chlorine-benzoyl)benzoic acid,bipy=4,4-bipyridine) has been hydrothermally synthesized and structurally characterized by elemental analysis,IR spectrum,TG and single-crystal X-ray diffraction.The title compound crystallizes in the triclinic system,space group P1 with a=5.4550(4),b=11.4099(8),c=15.3135(11),α=68.7680(10),β=81.3470(10),γ=79.3450(10)o,V=869.48(11) 3,C 38 H 28 Cl 2 N 2 NiO 8,M r=770.23,D c=1.471 g/cm 3,μ(MoKα)=0.768 mm 1,F(000)=396,Z=1,the final R=0.0456 and wR=0.1171 for 2477 observed reflections (I > 2σ(Ⅰ)).It exhibits a one-dimensional chain-like structure.     

Synthesis and Crystal Structure of {4-[2-（9- Hexyl-9H-carbazol-3-yl）vinyl]phenyl} Dimethylamine

The title compound {4-[2-(9-hexyl-9H-carbazol-3-yl)vinyl]phenyl} dimethylamine has been synthesized by the well known Wittig reaction, and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/c with a = 47.87(2), b = 10.222(4), c = 9.612(4) , β = 92.401(9)o, V = 4699(3) 3, Z = 8, C28H32N2, Mr = 396.56, Dc = 1.121 g/cm3, F(000) = 1712 and μ(MoKa) = 0.065 mm-1. The final R and wR are 0.0793 and 0.1983, respectively for 3524 observed reflections with I > 2σ(I). In the title compound, the bond lengths are normal, and the crystal is stabilized by Van der Waals’ forces.     

Synthesis and Structural Characterization of {[Mn(phen)_2(OAc)(H_2O)]ClO_4}_2H_2O

1 INTRODUCTION Chemistry of manganese cluster has become an attractive research field because of the involvement of manganese in several biological redox-active sys- tems[1,2], especially in the oxygen-evolving complex (OEC) of photosystem Ⅱ (PSⅡ) in green plants[3]. It was thought that the coordination environment of Mn in OEC contains O and N donors, and the bind- ing of aqua to the Mn site may be important to the oxidation of aqua for the evolution of dioxygen[4, 5]. In recent …     

Synthesis and Crystal Structure of 2-p-Methyloxyphenyl- 3a-（2-phenyl-1,2,3-triazole-4-yl）-3,4-dihydro-1,2,4- oxa-diazolo[4,5-d][1,5] Benzothiazepine

The title compound2-p-methyloxyphenyl-3a-(2-phenyl-1,2,3-triazole-4-yl)-3,4- dihydro-1,2,4-oxa-diazolo[4,5-d][1,5] benzothiazepine (C31H25N5O2S, Mr = 531.63) has been syn- thesized and its structure was determined by single-crystal X-ray diffraction. The crystal belongs to triclinic, space group P1 with a = 10.888(2), b = 15.115(3), c = 16.702(3), α = 99.90(3), β = 95.21(3), γ = 100.41(3)o, V = 2642.1(9) nm3, Dc = 1.336 g/cm3, Z = 4, F(000) = 1112, μ = 0.162 mm-1 ,λ(MoKα) = 0.071073 nm, R = 0.0357 and wR = 0.1126 for 10620 observed reflections with I > 2σ(I). X-ray analysis reveals that the molecular backbone consists of a tricyclic system with the central seven- membered ring in a twisted boat-like conformation.     

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.