Bis(2-bromoethyl) selenium dibromide as the selenium-introducing reagent: One-pot preparation of 2,5-bis(alkoxymethyl)tetrahydroselenophenes by the cyclization of 1,5-hexadiene

The reaction of bis(2-bromoethyl)selenium dibromide (1a) with 1,5-hexadiene (2) in methanol or ethanol affords 2,5-bis(alkoxymethyl)tetrahydroselenophene-1,1-dibromides (R = CH₃ (3b), R = C₂H₅ (3c)) via 2,5-bis(bromomethyl)tetrahydroselenophene-1,1-dibromide (3a). The reaction of 1a with 2 in 1-propanol, 2-methyl-1-propanol or 1-butanol in the presence of sodium carbonate gave 2,5-bis(alkoxymethyl)tetrahydroselenophene (R = C₃H₇ (4a), R = (CH₃)₂CHCH₂ (4b) and R = C₄H₉ (4c)) via 3a. The ratios of the trans and cis isomers of 3a–3c are 3:2. In addition, the structure of trans-2,5-bis(methoxymethyl)tetrahydroselenophene-1,1-dibromide (trans-3b) was determined by X-ray crystallography.     

A New Two-dimensional Cd（Ⅱ） Coordination Polymer Constructed by Pyridine-2,5-dicarbohydrazide

A new two-dimensional Cd（Ⅱ） coordination polymer, [Cd（2,5-pdch）（H2O）]n·2n（ClO4）·nH2O （2,5-pdch = pyridine-2,5-dicarbohydrazide）, was prepared and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction analysis. The crystal belongs to monoclinic, space group P21/c with a = 10.905（2）, b = 11.602（1）, c = 15.034（2） A, β = 117.794 （10°, V = 1682.8（4A3, Z = 4, C7H13CdCl2NsO12, Mr = 542.52, Dc = 2.141 g/cm^3,/μ = 1.691 mm^-1, F（000） = 1072, 2（MoKa） = 0.71073A, the final R = 0.0608 and wR = 0.1329 for 2972 observed reflections with I 〉 2σ（I）. Single-crystal X-ray diffraction analysis reveals that the Cd（Ⅱ） atom displays a distorted pentagonal-bipyramidal geometry coordinated by three N atoms and three O atoms from three different 2,5-pdch ligands, and one water molecule. Interestingly, each two Cd（Ⅱ） atoms are bridged by two carbohydrazide groups of the 2,5-pdch ligands to form a dimeric unit, and such dimeric units are further connected by the 2,5-pdch ligand to generate a two-dimensional （4,4）-network.     

多齿配体2,5-二羟基-1,4-苯醌缩氨基脲 (C_6H_4O_3NNHCONH_2.CHON(CH3_)_2)的合成及晶体结构

报道了含1个溶剂DMF的多齿配体2,5-二羟基-1,4-苯醌缩氨基脲的合成和晶体结构。该化合物(C10N4O5H14)属正交晶系,其空间群为P212121 a=13.221(6),b=17.709(5),c=5.347(4)?, V=1252.0(1)3,Z=4,F(000)=568, Dx=1.434g/cm3,Mr=270.25, m (MoKα)= 1.16 cm-1, 结构由直接法解出,全矩阵最小二乘法修正,最终的偏离因子R=0.0319,wR=0.0748。结构测定表明溶剂DMF分子和2,5-二羟基-1,4苯醌缩氨基脲间形成很强的氢键,后者可看作是两条共轭链的偶合物。     

吡啶高三蝶烯的合成

2-溴-4-甲基吡啶（1）经氯代和碘代反应合成了2-溴-4-碘甲基吡啶（3）,3和蒽酮（4）反应生成10,10-二（2-溴-4-吡啶甲基）-9（10H）蒽酮（5）,5在3 MPa下与NaOCH3反应得到10,10-二（2-甲氧基-4-吡啶甲基）-9（10H）蒽酮（6）,6经硼氢化钠还原得到蒽醇（7）,7在对甲苯磺酸催化...     

Synthesis, crystal structures, and magnetism of cobalt coordination polymers based on dicyanamide and pyrazine-dioxide derivatives

Three coordination polymers of Co(II) with dicyanamide (dca) were obtained by adding coligands of 2,5-dimethylpyrazine-dioxide (2,5-dmpdo), 2,3,5-trimethylpyrazine-dioxide (2,3,5-tmpdo), or 2,3,5,6-tetramethylpyrazine-dioxide (2,3,5,6-tmpdo) to the binary system of Co-dca. Co2(dca)(4)(2,5-dmpdo)2 (1) crystallizes in the triclinic space group P with a=7.4962(2), b=9.0364(2), c = 10.4783(4) A, alpha = 72.567(1), beta = 72.557(1), gamma = 68.814(2) degrees , V = 616.61(3) A(3), Z = 1, and R1 = 0.0345. [Co3(dca)6(H2O)4].2(2,3,5-tmpdo) (2) is in the monoclinic space group C2/c with a = 29.477(1), b = 7.3735(2), c = 17.4631(7) A, beta = 93.652(1) degrees , V = 3787.9(2) A(3), Z = 4, and R1 = 0.0532. [Co(dca)2(H2O)2].2(2,3,5,6-tmpdo) (3) is in the monoclinic space group P2(1)/c with a = 9.4739(3), b = 11.3876(3), c = 12.1778(3) A, beta = 98.967(1) degrees , V = 1297.74(6) A(3), Z = 4, and R1 = 0.0481. 1 contains an unusual (4,4) Co-dca layer, representing a rare example of metal-dca coordination polymers with mixing 1,3-mu(2)- and 1,5-mu2-dca bridges. The Co-dca (4, 4) layers are connected by 2,5-dmpdo to give an alpha-Po-type network, which displays antiferromagnetic ordering below 10.8 K. 2 is a unique 3D framework composed of 2D twinned 1,5-mu2-dca bridged layers, which are connected by Co-H2O-Co linkages. The noncoordinated 2,3,5-tmpdo units and the coordination water molecules form hydrogen-bonded chains that thread the framework. 3 has alternating stacks of usual Co-dca (4, 4) layers through 1,5-mu2-dca bridges and organic layers of noncoordinated 2,3,5,6-tmpdo. Weak antiferromagnetic and weak ferromagnetic coupling was observed in 2 and 3, respectively.     

Stepwise formation of quasi-octahedral macrocyclic complexes of rhodium(III) and iridium(III) bearing a pentamethylcyclopentadienyl group

Reactions of [[MCl2(Cp*)]2] (1: M=Ir, 2: M=Rh) with bidentate ligands (L) such as 1,4-diisocyano-2,5-dimethylbenzene (a), 1,4-diisocyano-2,3,5,6-tetramethylbenzene (b), pyrazine (c) or 4,4'-dipyridyl (d) gave the corresponding dinuclear complexes [[MCl2(Cp*)]2(L)] (M=Ir: 3a, 3b, 5c, 5d; M=Rh: 4b, 6c, 6d), which were converted into tetranuclear complexes [[M2(mu-Cl)2(Cp*)2]2(L)2](OTf)4 (M=Ir: 7c, 7d, 9a, 9b; M=Rh: 8e, 8d, 10b) on treatment with Ag(OTf). X-ray analyses of 8c and 8d revealed that each of four pentamethylcyclopentadienyl metal moieties was connected by two mu-Cl-bridged atoms and a bidentate ligand to construct a rectangular cavity with the dimensions of 3.7 x 7.0 A for 8c and 3.7 x 11.5 A for 8d. Both the Rh2Cl2 and pyrazine (or 4,4'dipyridyl) ring planes are perpendicular to the Rh4 plane. Treatment of Cl-bridged complexes (7c, 7d, 8e, 8d, 9b, and 10b) with a different ligand (L') resulted in cleavage of the Cl bridges to produce two-dimensional complexes [[MCl(Cp*)]4[(L)-(L')]2](OTf)4 (11ac, 11bc, 11bd, 12bc, and 12bd) with two different ligand "edges". Complex 10b reacted readily with 1,4-diisocyano-2,3,5,6-tetramethylbenzene (b) to give a tetranuclear rhodium(III) complex 12bb. The structure of tetranuclear complexes was confirmed by X-ray analysis of 11bc. Each [MCp*] moiety is surrounded by a Cl atom, isocyanide, and pyrazine (or 4,4'-dipyridyl) and the dimensions of its cavity are 7.0 x 11.6 A.     

Synthesis and Crystal Structural Characterization of a Thiosemicarbazone Derived from 4-Acylpyrazolone

1 INTRODUCTION Pyrazol-5-one derivatives form an important class of organic compounds due to their structural che- mistry and biological activities as analgesic, antipy- retic, anti-inflammatory and hyperglycemic agents[1～4]. Even the simplest pyrazol-5-one derivatives like antipyrine and amidopyrine are widely used in anal- gesic medicine[5, 6]. On the other hand, thiosemicar- bazones, especially heterocyclic thiosemicarbazones, have been the subject of extensive investigations be- cause…     

Synthesis, structure, magnetic properties and molecular mechanics study on the dinuclear copper (II) with biradical

Dinuclear copper complex with biradicals [Cu(hfac)2]2PhBNM(PhBNM = 2,5-bimethyl-1,4-bis(4,4,5,5-tetramethyllimidazoline-1-oxyl-3-oxide)phenyl,hfac=hexafluoroacetylacetonate) has been synthesized and characterized. It crystallized in the monoclinic system, with space group C2/c, a=1.9012(4), b=1.3718(3), c=2.1620(4) nm, β=97.55(3)°, Z=4. The X-ray structure analysis shows that the molecular structure consists of two kinds of conformations. The ratio of them is 7:3. The energy of two conformations, calculated with molecular mechanics, are different, E1=740 kJ/mol, and E2=771 kJ · mol-1. The CNDO/k results on the complex indicate that the orbital energy of low spin state is lower than that of high spin state, which correspond with the results of magnetic measurement.     

Synthesis and Crystal Structure of 4-（2-Bromophenyl）-3,4,7,8-tetrahydro- 7,7-dimethyl-1-p-tolylquinoline-2,5（1H,6H）-dione

The title compound 4-（2-bromophenyl）-3,4,7,8-tetrahydro-7,7-dimethyl-1-p-tolylquinoline-2,5（1H,6H）-dione 1 （C24H24BrNO2, Mr = 438.35） was synthesized and characterized by IR, 1H NMR and elemental analysis. The crystal belongs to monoclinic, space group C2/c with a = 27.565（14）, b = 10.079（5）, c = 15.917（8） A,β = 111.059（9）°, Z = 8, V = 4127（4）A3, Dc = 1.411 g·cm^-3,μ（MoKa） = 2.011 mm^-1, F（000） = 1808, the final R = 0.0417 and wR = 0.1032 for 2393 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that the pyridine ring adopts a distorted boat conformation, while another six-membered ring takes a half-chair conformation. In addition, there are non-classical hydrogen bonds of C-H…O and C-H…Br in the structure. The short distance （3.481A） between the adjacent 2-bromophenyl rings indicates the existence of π-π interaction.     

Strandberg型杂多化合物(C_6H_(11)NH_3)_5H(P_2Mo_5O_(23))4H_2O的水热合成及结构

利用水热合成法合成了分子组成为(C6H11NH3)5H(P2Mo5O23)4H2O的杂多化合物, 用单晶X-ray衍射方法测定了它的结构,该晶体属于单斜晶系,空间群P21/c, a = 12.830(3), b = 14.848(3), c = 25.258(5) ? b = 92.95(3), Mr = 1483.62, V = 4805.1(17) 3, Z = 4, Dc = 2.051 g/cm3, m = 1.431 mm-1, F(000) = 3000, I >2s(I) 的可观察衍射点4426个, 最终结构偏差因子R = 0.0464, wR = 0.0801, S = 0.731。在[P2Mo5O23]6-杂多阴离子中5个MoO6八面体通过共边和共角相连, 形成1个近似的五角平面骨架, 2个PO4四面体加在五角平面的两侧。热性质研究表明杂多阴离子骨架在547.4 ℃左右分解。     

Syntheses and Crystal Structures of 3,3'-(9,10-Anthrylene)bis-pentane-2,4-dione and 3-(2-Methoxy-1-naphthalenyl)-pentane-2,4-dione

1 INTRODUCTION 3-Substituted pentane-2,4-diones, as a series of chelating ligands to coordinate with many metal ions, have been extensively studied in coordination chemistry. These compounds can also act as valuable intermediates in the synthesis of calamitic derivatives both with or without metal ion[1]. However, compared to the 3-alkylation of 2,4-pentanediones, the direct synthesis of 3-aromatic pentane-2,4-diones from pentane-2,4- diones is much difficult. Previous methods to direc…     

Influence of steric hindrance of organic ligand on the structure of Keggin-based coordination polymer

Five Keggin-based 3D coordination polymers, namely, [Cu3(pz)3(PW12O40)] (pz = pyrazine) (1), [Cu3(2,3-Me2pz)3(PW12O40)] (2,3-Me2pz = 2,3-dimethylpyrazine) (2), [Cu2(2,5-Me2pz)(1.5)(2,5-HMe2pz)(PW12O40)] (2,5-Me2pz = 2,5-dimethylpyrazine) (3), [Cu3(2,3-Me2pz)3(PMo12O40)] (4), and [Ag3(pz)3(PW12O40)].0.5H2O (5), were synthesized and structurally characterized. Crystal data are as follows: trigonal, space group R3c, a = 18.4070(14) angstroms, c = 22.544(3) angstroms, gamma = 120 degrees, and Z = 6 for 1; orthorhombic, space group Pccn, a = 16.599(2) angstroms, b = 20.470(3) angstroms, c = 14.3757(18) angstroms, and Z = 4 for 2; triclinic, space group P1, a = 10.667(2) angstroms, b = 11.147(2) angstroms, c = 20.207(4) angstroms, alpha = 90.983(4) degrees, beta = 108.128(3) degrees, gamma = 92.150(4) degrees, and Z = 2 for 3; orthorhombic, space group Pccn, a = 16.450(3) angstroms, b = 20.170(4) angstroms, c = 14.244(3) angstroms, and Z = 4 for 4; and rhombohedral, space group R32, a = 18.2047(13) angstroms, c = 23.637(3) angstroms, gamma = 120 degrees, and Z = 6 for 5. Their structural differences were investigated using crystal structure analysis, revealing that the influence of steric hindrance of organic ligand on the structures of Keggin-based coordination polymers is realized through changing the number of metal-organic units surrounding the POM anion.     

CRYSTAL STRUCTURE OF 1-METHYL-6-(E-ETHOXYCAR-BONYLVINYL)-8-BENZOYL-2, 3-DIHYDRO-1H-IMIDAZO[1, 2-a] PYRIDIN-5-ONE

<正> The title compound C20H20N2O4(Mr=352.39)belongs to mono-clinic space group C2/c with a=9.208(4),b=11.714(3),c=32.336(8)A,β=100.83(2)°,V=7146.2(6)A3,Z=16,Dc=1.35 g/cm3,μ(Moka)=1.03 cm-1 and final R=0.06 for 1781 reflections with F≥2.5(F).There are two independent molecules in an asymmetric unit.Neither pyridinone nor phenyl ring is coplanar with the ketonic carbonyl group in the molecule.     

N,N'-双苯基-3,6-二甲基-1,4-二氢-S-四嗪-1,4-二甲酰胺的晶体结构

苯基异氰酸酯与3,6-二甲基-1,6-二氢-S-四嗪反应生成标题化合物（C18H18N6O2,Mr=350.38）。经X-射线单晶结构分析表明此晶体属于单斜晶系,P21/c空间群,a=9.348（2）,b=6.860（6）,c=27.929（7） A,β=94.57（2）°,V=1785.3A3,Z=4,μ=0.090mm-1,Dc=1.304g/cm3,F（000）=736。结果表明该化合物的2个酰胺基接在S-四嗪环的1,4位,而四嗪环本身呈船式构象,不具有同芳香性,分子间存在氢键相互作用。     

Studies on novel peptidomimetics having bi-directional dispositions of hydroxylated D-Pro-Gly motifs anchored on a C(2)-symmetric iminosugar-based foundation

A rigid pyrrolidine based scaffold comprising of 2,5-dideoxy-2,5-imino-D-idaric acid (1) is developed. Attachment of peptide strands to the carboxylic groups at both ends of this novel template led to the peptidomimetics 2 and 3. Conformational analysis by NMR studies revealed that compounds 2b, 3b and 2c, 3c take interesting turn structures (C(2) symmetric for 2c and 3c) in DMSO-d(6) consisting of identical intramolecular hydrogen bonds at two ends between LeuNH --> sugar-OH as depicted in structure A, whereas 2a and 3a display structures with regular beta-turns with hydrogen bonds between LeuNH --> Boc-C=O in one-half of their molecular frameworks (structure B), characteristic of the turn structures commonly observed in "D-Pro-Gly"-containing peptides. These results suggest that a cis hydroxyl group at the 3-position of the proline residue favors a pseudo beta-turn-like nine-membered ring structure in hydroxyproline-containing peptides involving an intramolecular hydrogen bond between the hydroxyl and the i + 2 backbone amide.     

C(3)-酯基取代的1,5-苯并硫氮杂卓的合成、晶体结构及抑菌和构效关系的研究

设计、合成了三类C(3)酯基取代的1,5-苯并硫氮杂卓衍生物: 2,3/2,5-二氢和2,3,4,5-四氢-1,5-苯并硫氮杂卓-3-甲酸乙酯, 采用元素分析、IR、MS、1H NMR及X射线衍射法确定了标题化合物的分子结构．结构分析表明, 2,5-二氢-1,5-苯并硫氮杂卓-3-甲酸乙酯属单斜晶系, C2/c空间群, 晶胞参数为: a＝2.0319(4) nm, b＝1.4985(3) nm, c＝1.3659(3) nm, α＝90°, β＝120.49(3)°, γ＝90°, V＝3.5840(12) nm3, Z＝8, Dc＝1.397 g/cm3, μ＝0.351 mm－1, F(000)＝1560, R＝0.0478, Rw＝0.1304; 研究了2,3/2,5-二氢-1,5-苯并硫氮杂卓的合成反应条件, 发现该两种互变异构体分别是速度控制产物和平衡控制产物; 抑菌活性及抑真菌构效关系研究表明, 亚胺型的2,3-二氢-1,5-苯并硫氮杂卓具有明显的抑菌活性, 亚胺官能团是其抑真菌的药效团．     

5-苯基-3,5-二乙氧基-2(5H)-呋喃酮的晶体结构

标题化合物C14H16O4的晶体结构用X-射线单晶衍射法测定。晶体属三斜晶系,P空间群,晶胞参数a =8.696(2), b=8.943(2) , c=9.379(2) ?, ( = 69.28(3), ( =76.67(3), ( =80.28(3)o, V=660.8(3) ? 3, Z=2, Mr=248.28, Dx=1.248 g/cm3, F(000)=264, μ(MoK()=0.0851 mm—1。晶体结构用直接法解出,经全矩阵最小二乘法对原子参数进行修正,最终的偏离因子为R=0.061, wR=0.089。标题化合物有2个环：呋喃酮环和苯环。由C(1),C(2),C(3),C(4),O(4)构成的五元呋喃酮环的5个原子较好地处于1个平面上,平均偏差为0.0078?。O(2),O(3) 两个原子与呋喃酮环共平面。呋喃酮环和苯环之间的两面角为79.39o。     

两个环己烷螺含氮杂环化合物的合成和晶体结构

环己酮与硫代碳酰肼在不同介质中的反应，合成出两个不同的环己烷螺含氮杂环化合物。经Ｘ－射线结构分析确定它们分别为１，２，４，５－四氮螺［５，５］十一烷－３－硫酮，Ｃ＿７Ｈ＿（１４）Ｎ＿４Ｓ（Ⅰ）和１，２，４，－三氮螺［４，５］癸－１－烯－４－氨基－３－硫酮。Ｃ＿７Ｈ＿（１２）Ｎ＿４Ｓ＿ｘ（Ｓ＿ｘ＝０．８Ｓ＋０．２Ｏ）（Ⅱ）。晶体学参数分别为（Ⅰ）：Ｐ２＿１／ｃ，ａ＝１２．０２６（４），ｂ＝２６．８１７（６），ｃ＝１２．０４２（３），β＝１１５．９４（２）°，Ｚ＝４，Ｖ＝９３３．４（１０），Ｍ＿ｒ＝１８６．２８；（Ⅱ）：Ｐ２＿１／ｍ，ａ＝６．５９５（７），ｂ＝６．８１７（６），ｃ＝１０．５７２（６），β＝１０６．３（１）°，Ｖ＝４５６（１），Ｚ＝２，Ｍ＿ｒ＝１８１．０５。最终一致因子分别为Ｒ＝０．０５４，Ｒ＿ｗ＝０．０６５和Ｒ＝０．０８９，Ｒ＿ｗ＝０．０９６。两个化合物中，环己烷都为椅式构型，它与其螺联的６员氮杂环，５员氮杂环的最小二乘平面间的夹角分别为６８．９４和９０°。并对合成反应途径作了初步讨论。     

Organometallic coordination polymers generated from bent Bis(acetylenylphenyl)oxadiazole ligands and Ag(I) salts

Two new bent oxadiazole bridging benzoacetylene ligands 2,5-bis(4-ethynylphenyl)-1,3,4-oxadiazole (L9) and 2,5-bis(3-ethynylphenyl)-1,3,4-oxadiazole (L10) were synthesized. The coordination chemistry of them with various inorganic Ag(I) salts has been investigated. Seven new coordination polymers were prepared by solution reactions and fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. [Ag2(L9)](SO3CF3)2 (1) (triclinic, P; a =10.292(4), b = 10.794(4), c = 11.399(5) A; alpha = 98.894(5), beta = 102.360(6), gamma = 90.319(5) degrees ; Z = 2), [Ag(L9)]SbF6 (2) (orthorhombic, Cmca; a = 19.059(9), b = 12.922(6), c = 15.609(7) A; Z = 8), [Ag(L9)]BF4 (3) (orthorhombic, Cmca; a = 19.128(3), b = 12.6042(18), c = 28.003(4) A; Z = 16), [Ag(L9)]ClO4 (4) (monoclinic, P2(1)/c; a = 8.5153(16), b = 19.722(4), c = 10.320(2) A; beta = 105.307(3) degrees ; Z = 4), [Ag(L10)]SO3CF3 (5) (triclinic, P; a = 9.0605(13), b = 10.4956(15), c = 10.8085(16) A; alpha = 101.666(2), beta = 109.269(2), gamma = 100.944(2) degrees ; Z = 2), [Ag(L10)(H2O)(0.5)]BF4.0.5H2O (6) (monoclinic, C2/m; a = 32.180(6), b = 17.027(3), c = 8.1453(15) A; beta = 102.541(3) degrees ; Z = 8), and {[Ag2(L10)2(H2O)](ClO4)2}.o-xylene (7) (monoclinic, P2(1)/c; a = 8.1460(10), b = 17.326(2), c = 30.345(4) A; beta = 97.71 degrees ; Z = 4) were obtained by the combination of L9 and L10 with various Ag(I) salts in a benzene/methylene chloride mixed solvent system. In addition, the luminescent and electrical conductive properties of these new compounds were investigated.     

Syntheses and Crystal Structures of 4-Amino-3- （3-hyd roxyp ropyl）- 1H-1,2,4-triazole-5（4H）-thione and 6-（4-Biphenylyl）-3-（3-hydroxypropyl）-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazine

1INTRODUCTION It has been reported that3,6-disubstituted-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazines have a broad spec-trum of bioactivities,such as antimicrobial[1],antibac-terial,antifungal[2],anti-inflammatory[3],diuretic[4],an-thelmintic and analgesic[5].They can also be used as plant-growth regulating agents[6],photographic coup-lers,dyes for improved preservability and absorption characteristics,and inhibitors of malignant cellularZOU K.H.et al.:Syntheses and Crystal Structures o…