双脂肪胺钌卟啉的合成、结构表征和晶体结构

本文讨论了一系列双脂肪胺钌卟啉配合物,包括Ru(^Ⅱ)(Por)(H₂NR)₂和Ru(^Ⅱ)(Por)(HNR₂)₂［Por=四苯基卟啉(TPP),中位-四(对甲苯基)卟啉(TTP),中位-四(对氯苯基)卟啉(4-Cl-TPP);R=叔丁基,异丙基,环己基,正辛基,正十二烷基,R′=甲基和乙基］的合成,结构表征和晶体结构测定。钌羰基卟啉与间-氯过苯甲酸的反应混合物用过量的脂肪胺处     

Structural Evidence of Anion＇s Effect on the Ion Packing of [Ni2（teta）3]^4＋ in the View of H-bonding Interaction

Two dinuclear nickel（Ⅱ） complexes [Ni2（teta）3]Cl4＇2H2O1 and [Ni2（teta）3]（NO3）4 2 （teta = triethylenetetramine） were synthesized by a solvothermal method and structurally characterized. Complex 1： orthorhombic, Pbca, a = 13.791（3）, b = 13.078（3）, c = 18.323（4） ,A, V = 3304.8（12） A3, Z = 4, Mr= 733.98, Dc = 1.475 g/cm^3,μ = 1.500 mm^-1, F（000） = 1560, R = 0.0585 （I 〉 20（/）） and wR = 0.1243. Complex 2： orthorhombic, P212121, a = 7.8279（14）, b = 14.209（3）, c = 31.163（6）A, V = 3466.2（11）A3, Z = 4, Mr= 804.19, Dc = 1.541 g/cm^3,μ = 1.164 mm^-1 F（000） = 1704, R = 0.0401 and wR = 0.0840 for 5950 observed reflections （I 〉 2σ（I））. Two Ni^2＋ ions are connected by one linear bridging teta ligand, forming a dinuclear [Ni2（teta）3]^4＋ cation. Each Ni^2＋ ion in 1 and 2 takes a distorted octahedral geometry with six coordinated N atoms from two teta ligands. The effect of different anions on the arrangement of [Ni2（teta）3]^4＋ cations has been discussed in view of H-bonding interactions. Thermal stability of 1 and 2 was also investigated.     

Perfluorovinyl Morpholine and Perfluorovinyl Pyrrolidine with Nucleophiles and Electrophiles

In this study, both monofunctional and bifunctional nucleophiles, as well as the electrophile FNO, are reacted with perfluorovinyl amines. The perfluorovinyl amines CF?CF₂ and CF?CF₂ have been reacted with dimethylamine and diethylamine in the presence of small amounts of water to give CHFC(O)N(CH₃)₂ ( 1 ), CHFC(O)N(CH₃)₂ ( 2 ), and CHFC(O)N(C₂H₅)₂ ( 3 ). With perfluorovinyl pyrrolidine and perfluorovinyl morpholine, ethanolamine gives the cyclized products CHF ( 4 ) and CHF ( 5 ), respectively. Reaction of the vinyl amines with (CH₃)₃SiOCH₂CF₃ in the presence of catalytic amounts of CsF results in the formation of cis- ( 6 ) and trans- ( 7 ) CF?CF(OCH₂CF₃) and cis- ( 8 ) and trans- ( 9 ) CF?CF(OCH₂CF₃). The electrophile FNO reacts slowly with perfluorovinyl pyrrolidine and perfluorovinyl morpholine, and more rapidly with (CF₃)₃CCF?CF₂ to give CF(NO)CF₃ ( 10 ), CF(NO)CF₃ ( 11 ) and (CF₃)₃CF(NO)CF₃ ( 12 ), respectively. Single crystal X-ray analysis is used to confirm the identity of the product obtained from the controlled hydrolysis of the sultone of perfluorovinyl pyrrolidine as the sulfonic acid anhydride C(O)CF₂OS(O)₂OCF₂C(O) ( 13 ). The X-ray crystal structure of perfluorosuccinic acid monohydrate ( 14 ), which is obtained when the perfluorovinyl pyrrolidine sultone is hydrolyzed in excess water, is also reported for the first time.     

THE PHENOMENON OF CONGLOMERATE CRYSTALLIZATION. PART 53. THE CRYSTALLIZATION BEHAVIOR OF TWO COBALT(III) CARBONATO AMINE COMPOUNDS

Abstract

Two new cobalt(III) carbonato amine compounds were synthesized, and their crystal structures were determined.

Compound (I), Na₂[Co(tren)(CO₃)]₂(CIO₄)₄·3H₂O, Co₂C₁₄CI₄H₄₂N₈Na₂O 25, crystallized as a racemate in the orthorhombic system, space group Pcab (No. 61). The cell dimensions, obtained from the centering of 25 reflections, are a = 10.684(5)å, b = 18.559(8)å, c = 37.528(10)å, V= 7441(5)å³. FW= 1028.18, Z= 8, F(000) = 4203.87, dc = 1.836 Mg·m^?3, μ = 1.30 mm^?3, λ = 0.70930å. A total of 3457 data were collected over the range of 4° ≤2θ ≤40°; of these, 2377 (independent and I≥2.5σ(I)) were used in the structural analysis. The final RF and Rw residuals were 0.055 and 0.064.

Compound (II), [cis-β-Co(trien)(CO₃)](HCO₃)· H₂O, CoC₈H₂₁N₄O₇, crystallized as a conglomerate in the orthorhombic system, space group P2₁2₁2₁ (No. 19). The cell dimensions, obtained from the centering of 25 reflections, are a = 8.869(4)å, b = 12.032(8)å, c = 12.522(7)å, V = 1336(1)å³. FW = 344.20, Z = 4, F(000) = 713.62, dc = 1.701 Mg·m^?3, μ = 1.32mm^?1, λ = 0.70930å. A total of 3504 data were collected over the range of 4° ≤2θ ≤40°; of these, 2497 (independent and I≥ 2.5σ(I)) were used in the structural analysis. The final RF and Rw residuals were 0.049 and 0.059.     

一维链状银(Ⅰ)配合物的合成及结构表征

分别用间苯二胺和GgNO3,1,4-二(邻氨基苯氧基)丁烷和AgClO4进行配位反应得到了2个配合物[Ag(C6H8N2)(NO3)]n(1)和[Ag(C16H20N2O2)(ClO4)]n(2),并用元素分析,FTIR和X射线单晶衍射进行了表征.结果表明,配合物1属于正交晶系,空间群为Fdd2;配合物2属于单斜晶系,...     

Structural Evidence of Anion's Effect on the Ion Packing of [Ni2(teta)3]4+ in the View of H-bonding Interaction

Two dinuclear nickel(II) complexes [Ni2(teta)3]Cl4·2H2O 1 and [Ni2(teta)3](NO3)4 2 (teta = triethylenetetramine) were synthesized by a solvothermal method and structurally characterized. Complex 1: orthorhombic, Pbca, a = 13.791(3), b = 13.078(3), c = 18.323(4) , V = 3304.8(12) 3, Z = 4, Mr = 733.98, Dc = 1.475 g/cm3, μ = 1.500 mm-1, F(000) = 1560, R = 0.0585 (I > 2σ(I)) and wR = 0.1243. Complex 2: orthorhombic, P212121, a = 7.8279(14), b = 14.209(3), c = 31.163(6) , V = 3466.2(11) 3, Z = 4, Mr = 804.19, Dc = 1.541 g/cm3, μ = 1.164 mm-1, F(000) = 1704, R = 0.0401 and wR = 0.0840 for 5950 observed reflections (I > 2σ(I)). Two Ni2+ ions are connected by one linear bridging teta ligand, forming a dinuclear [Ni2(teta)3]4+ cation. Each Ni2+ ion in 1 and 2 takes a distorted octahedral geometry with six coordinated N atoms from two teta ligands. The effect of different anions on the arrangement of [Ni2(teta)3]4+ cations has been discussed in view of H-bonding interactions. Thermal stability of 1 and 2 was also investigated.     

Locking the Absolute Configuration of Achiral Amine Ligand: A Strategy for Helicity Introduction in Coordination Polymers

A novel coordination polymer {[Mn（m-cpdba）（H2O）4]·H2O}n 1 has been synthesized and characterized. Single-crystal X-ray diffraction analysis reveals that compound 1 contains one-dimensional single-stranded helical chains, in which the chirality of a stereochemically labile amine of the ligands can be locked by the Mn（II） ion via coordination bonds and transferred to the whole coordination polymeric chain, exhibiting an identical absolute configuration. Crystal data for 1： C14H17Mn1N3O13, Mr = 490.25, space group C2/c, a = 18.5177（18）, b = 6.6194（5）, c = 31.563（4）A, β = 105.046（5）°, Z = 8, V = 3736.2（7）A^3, Dc = 1.743 g/cm^3, F（000） = 2008 and μ = 0.786 mm^-1.     

POLYMERIC PHOTOSTABILIZERS CONTAINING TWO KINDS OF PHOTOSTABILIZING GROUPS Ⅱ. SYNTHESIS AND PHOTOSTABILITY OF COPOLYMERS OF 2,2,6,6-TETRAMETHYL-4-PIPERIDINYL METHACRYLATE AND β-HYDROXY-γ-(ORTHO-HYDROXY BENZOXY) PROPYL METHACRYLATE

A new kind of photostabilizers, eopolymer of 2, 2, 6, 6-tetramethyl-4-piperidinyl methacrylate and β-hydroxy-γ-(ortho-hydroxy benzoxy) propyl methacrylate, has been synthesized. The spectral behaviors of these copolymers were studied in detail. In the presence of salicylyl group a strong absorption in the region of 280—330 nm could be observed, and an unusual Stoke's shift appeared in the fluorescence spectrum excited by 310nm. The photostabilization ability of these copolymers in the process of photodegradation of cis-poly(butadiene)was studied.Results indicated that these compounds possess excellent photostabilization ability.     

新型环蕃二茂铁二甲酸二羟乙苯胺酯的合成及表征

以二茂铁为原料, 通过合成1,1'-二乙酰基二茂铁、1,1'-二茂铁二甲酸、1,1'-二茂铁二甲酰氯, 在高度稀释条件下与4种二羟乙基苯胺进行酯化反应得到了1,9-二羰基-2,8-二氧-5-(4-氟)苯基氮[9]二茂铁酯环蕃a, 1,9-二羰基-2,8-二氧-5-(4-甲基)苯基氮[9]二茂铁酯环蕃b, 1,9-二羰基-2,8-二氧-5-(4-甲氧基)苯基氮[9]二茂铁酯环蕃c, 1,9-二羰基-2,8-二氧-5-(4-硝基)苯基氮[9]二茂铁酯环蕃d. 用UV、¹H NMR、FT-IR、元素分析和基质辅助激光解析电离-飞行时间质谱(MALDI-TOF)对这些化合物进行了表征. 培养了二茂铁酯环蕃a的单晶, 并对其结构进行了解析.     

Crystal Structure and Anticancer Properties of Cinobufagin 3-Hemisuberate Methyl Ester

The title compound cinobufagin 3-hemisuberate methyl ester(1) was isolated from the venom of Bufo bufo gargarizans CANTOR. The crystal structure of 1, C35H48O9, was determined by single-crystal X-ray diffraction analysis. It belongs to orthorhombic, space group P212121 with a = 8.9338(3), b = 16.2970(4), c = 22.4019(6) , V = 3261.59(16) 3, Mr = 612.73, Z = 4, Dc = 1.248 g/cm3, μ = 0.725 mm-1, F(000) = 1320, S = 1.040, the final R = 0.0374 and wR = 0.0412 for 4458 unique reflections, of which 4088 were observed(I 2σ(I)). In the solid state, short intermolecular C-H...O interactions involving a methine and the ester carbonyl group in cinobufagin moiety and a methyl in the suberate moiety linked adjacent molecules into a three-dimensional network. Detailed analysis of the 1H-NMR data showed that X-ray structure of 1 would be expected to closely resemble the solution conformation in chloroform. Compound 1 was inactive for the inhibition of PC3 and HepG2 cancer cells, but the parent compound cinobufagin showed potent inhibition with IC50 values of 0.145 and 5.48 μM, respectively, indicating that esterification at C(3) decreased the cytotoxic effect of 1.     

Synthesis and Crystal Structure of a [Cu(HTren)Cl2]ClO4·H2O Complex (Tren = Tris(2-aminoethyl)amine)

The title complex [Cu(HTren)Cl2]ClO4·H2O (Tren = tris(2-aminoethyl)amine) was crystal (CuC6H21Cl3N4O5) is of triclinic, space group P-1, with a = 8.2689(2), b = 8.4503(3), c=11.6801(4)(A), a = 96.9350(10), β= 108.2440(10), γ = 90.7550(10)°, V= 768.32(4)(A)3, Z= 2, Mr=399.16, Dc= 1.725 g/cm3,μ= 1.962 mm-1, F(000) = 410, T= 293(2) K, the final R = 0.0479 and wR = 0.1339 for 2659 observed reflections with I ＞ 2σ(I). X-ray single-crystal structure analysis reveals that the copper(Ⅱ) atom adopts a slightly distorted square-pyramidal geometry. The distances between Cu and N atoms (N(1), N(2), N(3)) range from 1.975(4) to 2.116(3)(A). The bond lengths of Cu-Cl(1) and Cu-Cl(2) are 2.309(10) and 2.591(10) (A), respectively. The whole crystal presents a three-dimensional network structure by hydrogen bonds.     

Crystal and molecular structure of two new Schiff bases: Paeonol-ethylenediamine and paeonol-1,3-propylenediamine

Two new Schiff bases were prepared by the condensation reaction of paeonol with ethylenediamine (for compound 1) and 1,3-propylenediamine (for compound 2). The compounds were studied with single crystal X-ray diffraction method. Compound 1 is monoclinic, space group P2₁/c, a = 10.956(15) Å, b = 6.767(10) Å, c = 12.494(18) Å; β = 104.66(2)°, V = 896(2) ų, Z = 2. Compound 2 is triclinic, space group P-1, a = 6.878(2) Å, b = 12.141(4) Å, c = 12.414(4) Å; α = 101.023(6)°, β = 103.415(6)°, γ = 102.337(6)°, V = 952.8(6) ų, Z = 2. The molecular structures of 1 and 2 are similar; the molecule being centrosymmetric in 1 but asymmetric in 2.     

一水合高氯酸三（2—苯并咪唑亚甲基）胺合钴（Ⅱ）配合物的合成 …

合成了一水合高氯酸三(2-苯并咪唑亚甲基)胺合钴(Ⅱ)配合物,用单晶X- 射线衍射方法测定了它们的晶体结构.测定结果表明,该配合物属正交晶系,Pbcn(No.60) 空间群.晶胞参数a=19.393(9),b=18.232(8),c=17.052(8),α=β=γ=90.000(1)°,V=602 9.33,Z=8,最终偏离因子R1=0.156.配合物中的金属Co(Ⅱ)原子与配体NTB分子中的四个氮原子和高氯酸根中的一个氧原子形成扭曲三角双锥构型.     

(2S,4R)-2-(溴甲基)-2-(2,4-二氯苯基)-1,3-二氧环戊环-4-甲基苯甲酸酯的合成及晶体结构

合成了标题化合物并测定了其晶体结构。该化合物的化学式为C18H15O4BrCl2, Mr = 446.12。晶体为正交晶系, P212121空间群, 晶胞参数为: a = 7.1540(7), b = 23.367(1), c = 11.161(2) , V = 1865.7(3) 3, Z = 4, Dc = 1.588 g/cm3, F(000) = 896, (MoK? = 2.515 cm-1, R = 0.037, wR = 0.074, Flack系数为0.14(1)。晶体结构显示, 化合物中有2个手性碳原子, 为(2S,4R)构型, 整个分子呈沿b轴排列的波浪形的链状结构。     

O,O-二(β-叠氮乙基)-a-对甲苯磺酰胺基-对甲氧基苄基磷酸酯的合成与晶体结构

合成了标题化合物 C19H24N7O6PS,通过元素分析、IR和1H NMR对化合物进行了表征,用X-射线单晶衍射法测定了该化合物的晶体结构。结果表明,晶体属三斜晶系,P`1空间群,a = 9.236(1), b = 10.805(1), c = 14.113(1)? a = 109.29(1), b = 98.16(1), g = 106.30(1), V = 1232.3(2)?, Mr = 509.48, Z = 2, Dc = 1.373g/cm3, m (MoKa) = 0.24mm-1, F(000) = 532, 0 < 2q < 50范围内收集3238个独立衍射点,其中可观测衍射点3121个(F2≥8.0sF2)。晶体结构用直接法解出,经全矩阵最小二乘法修正,最终偏离因子R = 0.073,Rw = 0.074。化合物的分子中,2个取代苯环位于分子主链的同一侧,2苯环平面近于平行。2个取代的叠氮乙基分别位于分子主链的两侧,几乎相互垂直地指向同一个点,形成一种“钳式”构型。2个独立的分子之间以一对NH…O氢键连接形成中心对称的二聚体,成为晶体结构的基本重复单元。     

Tosyiate of ethyl 3-amino-2-phenyliodoniocrotonate: Synthesis, crystal structure, and synthesis of heterocyclic compounds based on it

Ethyl 3-aminocrotonate, when reacted with hydroxy(tosyloxy)iodobenzene, forms the tosylate of ethyl 3-amino-2-phenyliodoniocrotonate which crystallizes well in up to 80% yield. X-ray analysis confirms the structure of the phenyliodonium salt, revealing intramolecular and unusual intermolecular hydrogen bonds, stabilizing the compound in the crystalline state. Reaction with pyridine, its 4-substituted derivatives, and 4,4-bipyridine yields tosylates of 2-pyridinio-substituted ethyl 3-aminocrotonates.¹H NMR and IR spectra support formation of an intramolecular hydrogen bond for the E-isomer, and iodonium salts in the case of pyridinium salts for the Z-isomer. The UV spectra of the pyridinium salts show an intramolecular charge transfer band.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 770–777, June, 2000.     

Synthesis,Crystal Structure and Antimicrobial Study of a New Schiff Base 2-{(2'-Benzyl)iminoethyl}-5-methoxyphenol

1 INTRODUCTION 2-Hydroxyl-4-methoxyacetophenone, paeonol, is the effective component of many traditional Chinese medi- cines. It is proved that in modern medicine paeonol has various effects including antibacteria, antiinflammation, relieving pain, antisensitive and strengthing immune sys- tem[1~3]. The ramifications of paeonol have attracted con- siderable attention also because of their potential bio- logical properties and catalytic activity[4~6]. Recently, a few new derivatives of pae…     

Coordination Triangular Prism of Bisilver Complex with Triply—bridged of Bis（diphenylphosphino）amine

1 INTRODUCTION Recently coinage metal complexes of poly- dentate phosphines are of great interest owing to the applications in diverse areas such as supramolecular design, photophysics and catalysis[1～4]. It is well- known that the binuclear coinage metal complexes of diphosphine [M2(diphosphine)2(MeCN)2]2+ (M = Cu, Ag, Au)[5～16] are excellent precursors for the design of polynuclear or polymeric materials with desired properties due to the easy substitution of weakly coordinated ac…     

SYNTHESIS AND CRYSTAL STRUCTURE OF NICKEL COMPLEX WITH TRIS(3-AMINOPROPYL)AMINE

Abstract

The crystal structure of [Ni(trpn)(NCS)₂] (trpn = tris(3-aminopropyl)amine) has been determined, in which the nickel(II) complex is octahedral. The complex forms a three-dimensional network through weak intermolecular hydrogen bonds S_NCS … H-N_amine and S … S contacts.