Synthesis and Crystal Structure of a New Macrocycle Based on Diethoxycarbonyl Glycoluril: C_(26)H_(30)N_6O_(10)

A new macrocycle based on diethoxycarbonyl glycoluril 3,C26H30N6O10,has been synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic,space group P21/c with a = 12.7291（10）,b = 25.157（2）,c = 8.5489（7） A,β = 104.4760（10）°,V = 2650.7（4） A^3,Z = 4,C26H30N6O10,Mr = 586.56,F（000） = 1232,T = 292（2） K,Dc = 1.470 g/cm^3,μ = 0.115 mm^-1,the final R = 0.0590 and wR = 0.1299 for 4918 observed reflections with I 〉 2σ（I）. In the structure of the title compound,a three-dimensional microporous architecture is formed via intermolecular hydrogen bonding interactions.

Synthesis and Crystal Structure of a Novel Bis(ethoxycarbonyl)glycoluril Macrocycle

A novel [2＋4＋2]-macrocyclic compound 3（C52H69N16O12, Mr = 1109.53） con- taining bis（ethoxycarbonyl）glycoluril groups was synthesized via the Mannich three-component reaction in one pot and its structure was characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 10.077（3）, b = 10.642（3）, c = 15.324（5） , α = 96.704（5）, β = 102.304（5）, γ = 104.546（5）°, Z = 2, V = 1528.7（8）3, Dc = 1.283 g/cm3, μ = 0.097 mm-1, F（000） = 628, R = 0.0818 and wR（I 〉 2σ（I）） = 0.2346 for 3034 observed reflections.

Synthesis and Crystal Structure of 2,3-Diethoxycarbonyl-4-phenyl-5-morpholinyl Thiophene

The title compound 2, 3-diethoxycarbonyl-4-phenyl-5-morpholinylthiophene (C20H23NO5S, Mr=389. 47) was obtained by the reaction of a-thiobenzoylth-ioformmorpholine with diethyl acetylene dicarboxylate - The crystal is prismatic, spacegroup P1 ( 2), with unit cell constants 2337 observed reflections . X-ray analysis reveals that interatomic dis-tances for C(1 ) -C(2) and C(3) -C (4) are 1. 393 (4), 1. 370 (4) , respectively,which show that they are C=C double bond. The atoms of C(1 ), C(2), C(3), C(4)and S form a thiophene ring. The dihedral ang1es between thiophene ring and C(5) -C(6) -C(7) -C(8) plane, phenyl ring are 31. 42 and 43. 78, respectively. The mor-pholine ring adopts chair conformation.

Synthesis and Crystal Structure of Bis(dicyanamide) (5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane) Nickel(Ⅱ)

The nickel(Ⅱ)complex [Ni(teta){N(CN)2}2] (teta = 5,7,7,12,14,14-hexamehyl-1,4, 8,11-tetraazacyclotetradecane) was synthesized and its structure has been determined by single- crystal X-ray diffraction. Crystal data: C20H36N10Ni, monoclinic, space group P21/c, a = 9.632(2), b = 11.833(2), c = 10.613(2) ? b = 93.46(3), V = 1207.4(4) ?, Mr = 475.30, Z = 2, Dc = 1.307 g/cm3, F(000) = 508, m(MoKa) = 0.831 mm-1, R = 0.0446 and wR = 0.1274 for 2423 observed reflections with I > 2s(I). The center nickel ion is coordinated by six nitrogen atoms, four from the macrocyclic ligand teta and the other two from two dicyanamides. The dicyanamide is coordinated to the metal atoms as uni-dentate manner via nitrile nitrogen atom.

Synthesis and Crystal Structure of Dicyanamide (5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetraazacyclo- tetradecane) Copper(II) Percholatehydrate

The copper(II) complex [Cu(teta)N(CN)2](ClO4)H2O (teta = 5,7,7,12,14,14- hexamethyl-1,4,8,11-tetraazacyclotetradecane) has been synthesized and the crystal structure was determined by single-crystal X-ray diffraction. Crystal data: C18H38ClCuN7O5, monoclinic, space group P21/n, a = 8.796(3), b = 11.885(4), c = 23.054(9) , b = 97.540(4)o, V = 2389.3(15) 3, Mr = 531.54, Z = 4, Dc = 1.478 g/cm3, F(000) = 1124, ?= 1.070 mm-1, the final R = 0.0566 and wR = 0.1162 for 4749 observed reflections (I > 2s(I)). The center copper ion is coordinated by five nitrogen atoms in a square pyramidal geometry, with four from the macrocyclic ligand teta and the other one from a nitrile nitrogen atom of dicyanamide which is coordinated to the metal atoms as uni-dentate manner via nitrile nitrogen atom.

Synthesis and Crystal Structure of 1,6:3,4-Bis(1,2-xylyiene) tetrahydro-imidazo[4,5-d]imidazole-2,5(1H,3H)-dione

The compound 1,6∶3,4-Bis(1,2-xylyiene)tetrahydro-imidazo[4,5-d]imidazole-2,5(1H,3H)-dione(C20H18N4O2, Mr=346.38) has been synthesized for the first time. Complete assignments were achieved by 1H NMR, IR, EI-MS, elemental analysis and single-crystal X-ray diffraction technique. The crystal belongs to monoclinic, space group P2(1)/n with a=10.266 0(16), b=11.298 5(18), c=1.452 20(20) nm, β=97.923(3), V=1.668 4(5) nm3, Z=4, Dc=1.379 g/cm3, μ(MoKα)=0.092 mm-1, F(000)=728, R=0.053 2 and wR=0.112 3 for 3632 observed reflections with I>2σ(I). X-ray analysis reveals dimeric aggregates are formed through hydrogen bond and offset π-π stacking. In addition, the compound assembles to a three-dimensional networking structure by other hydrogen bond.

Template Syntheses and Crystal Structures of Hexaaza Macrocyclic Complexes with C-Methyl Substituents

Two new macrocyclic complexes with C-methyl substituents on the framework, namely, [CuL]（ClO4）2 （L = 5,12-dimethyl-1,8-dihydroxyethyl-1,3,6,8,10,13-hexaazacyclotetradecane） 1 and [NiL]（ClO4）2 2, have been synthesized and structurally characterized through X-ray diffraction analysis. Also, crystal structure of [CuL^1]（ClO4）2 （L^1 = 1,8-dimethyl- 1,3,6,8, [ 0,13- hexaazacyclotetradecane） 3 has been determined. Crystal data for 1： C14H32C12CuN6O10, Mr = 578.90, monoclinic, P2 1/n, α = 8.3529（11）, b = 10.8105（17）, c = 13.3709（17） ,A, β = 105.189（10）°, V= 1165.2（3） A3, Z = 2, Dc = 1.650 g/cm^3, F（000） = 602, λ（MoKct） = 0.71073 A,μ = 1.229 mm ^-1, R = 0.0474 and wR = 0.0895 for 2771 observed reflections （I 〉 2σ（Ⅰ））. Crystal data for 2： C14H32C12N6NiO10, Mr = 574.07, monoclinic, P2 1/c, a = 8.3636（12）, b = 12.997（2）, c = 10.764（2） A, β = 99.31（2）°, V = 1154.7（3） A^3, Z = 2, DC = 1.651 g/cm^3, F（000） = 600, λ（MoKa） = 0.71073 A,μ = 1. 134 mm^-1, R = 0.0380 and wR = 0.0796 for 2670 observed reflections （i 〉 2σ（Ⅰ））. Crystal data for 3： C 10H26Cl2CuN6O8, Mr = 492.81, monoclinic, P2 1/n, a = 8.4860（17）, b = 8.6320（17）, c = 12.662（3） ,A,β = 103.40（3）°, V = 902.2（3）A^3, Z = 2, Dc = 1.814 g/cm^3, F（000） = 510, λ（MoKa） = 0.71073A, μ = 1.562 mm^-1, R = 0.0505 and wR = 0.1061 for 1967 observed reflections （I〉 2σ（Ⅰ））. Complexes 1 and 2 are isostructural with the metal ions situated at the inversion center/Hydrogen bonds between O atoms of pendant and perchlorate anion give rise to a two-dimensional supramolecular layer. The Cu（Ⅱ） ions of compounds 1 and 3 adopt distorted axially-elongated octahedral coordinate geometry, and the nickel（Ⅱ） ion in complex 2 is four-coordinated with a square-planar configuration.

Syntheses and Crystal Structures of Two New Macrocyclic Compounds

Two new macrocyclic compounds, [Cu2（L）2]（ClO4）4·2CH3OH （1） and [Cu（L）]（ClO4）2·2H2O （2） （L = 1,3,10,12,15,18-hexaazatetracyclodocosane） were synthesized by condensation reactions involving amines and formaldehyde in the presence of copper anion. Compound 1 crystallizes in triclinic, space group Pí with a = 10.442（2）, b = 14.197（3）, c = 17.388（4）, α = 91.218（4）, β = 90.69（3）, γ = 93.756（4）o, V = 2520.4（9）3, Z = 2, F（000） = 1260, Dc = 1.589 Mg/m3, Mr = 1205.92, μ = 1.137 mm-1, λ = 0.71073, the final R = 0.0668 and wR = 0.1573 for 9703 observed reflections with I 2σ（I）. Compound 2 crystallizes in monoclinic, space group C2/c with a = 16.911（2）, b = 11.4172（15）, c = 27.059（4）, β = 107.787（2）o, V = 4974.7（12）3, Z = 8, F（000） = 2504, Dc = 1.610 Mg/m3, Mr = 602.92, μ = 1.155 mm-1, λ = 0.71073, the final R = 0.0419 and wR = 0.1131 for 4374 observed reflections with I 2σ（I）.

One-pot synthesis of [1+1] and 62-membered [2+2] Schiff base macrocycles

New [1＋1] and 62-membered [2＋2] Schiff base macrocycles containing a 2,6-diamidopyridine subunit have been synthesized by condensation reaction of the precursors pyridine-2,6-dicarboxamide and 1,10- bis（2＇-formylphenyloxy）decane in the presence of phosphoric acid via a one-pot process. The cyclo- condensed products were effectively isolated by gel column chromatography and characterized by 1H NMR, FTIR, mass spectrometry and X-ray analysis. The two macrocycles have a twisted structure, and not an open ＇circular＇ conformation in the solid state.

The Crystal and Molecular Structure of a New Macrocyclic Ligand, (H_6BDBPH)Br_6·4H_2O

The hexahydro\|bromide salt of a new 24\|membered hexaaza diphenol macrocyclic ligand, （H6BDBPH）Br6·4H2O （C 26H 56N6O6Br6, Mr= 1028.23）, crystallizes in the monoclinic system, space group P21/c, with cell parameters: a=14.441（5）, b=11.482（4）, c=12.090（6）, β=96.92°, V= 1990 （1）3, Z=2, Dc=1.716 g/cm3; F（000） =1024. MoKα radiation, λ= 0.71013), R = 0.0643 and wR = 0.1356 for 3507 independent reflections with I>2σ（I）. The macrocyclic ligand adapts chair form, and the crystallographic inversion center is located in the macrocyclic cavity, and the six bromide ions and four water molecules are situated symmetrically outside the macrocyclic cavity.

Syntheses and Crystal Structures of Lanthanide Complexes of New 15-Membered Macrocyclic Ligands with Three Pendant Acetato Groups

Two new 15-membered functionalized macrocycles, dioxo^polyazacycloalkanes with three pendant acetato groups, have been synthesized by the condensation reaction of DTPA dianhydride (DTPA=diethylenetriaminepentaacetic acid) with 1,2-diaminopropane, (15-DTPA-1,2-pn), or 1,2-diaminocyclohexane, (15-DTPA-1,2-cy). Their lanthanide complexes [Ln(15-DTPA-1,2-pn)(H 2O)] 2 [Ln=Eu (1), Gd (2)] and [Ln(15-DTPA-1,2-cy)(H 2O)] 2 [Ln=Eu (3), Gd (4)] were also prepared. Single crystal X-ray diffraction analyses of complexes 2 and 4 show that they have dimeric structures in solid state; each metal ion is nine-coordinated in a distorted tricapped-trigonal prism. In complex 4, the coexistence of two diastereoisomeric molecules in the crystal lattice was observed.

双酚大环配体硝酸铕三元配合物的合成、晶体结构与荧光性质

在硝酸铕模板下用丙二胺和2,6-二甲酰基-4-甲基苯酚通过[2+2]缩合反应,合成了一个新的双酚亚胺大环配体硝酸铕三元配合物[Eu(H2L)(NO3)3](L表示大环配体),并进行了系统的物理表征.晶体结构研究表明:配合物为中性分子,由一个Eu3+,一个中性大环配体(H2L)和三个配位硝酸根组成.晶体结构属单斜晶系,P21/c空间群,晶胞参数a=1.57296(11)nm,b=0.96957(7)nm,c=1.91196(13)nm,β=104.445(1)°,V=2.8237(3)nm3,Z=4,R=0.0507,wR=0.1168,Eu3+为10配位,呈扭曲的双冠四方反棱柱配位构型.在低温下(77K),配合物在甲醇溶液中以紫外光激发产生了Eu3+离子特征的荧光发射.

Cu(II)-四氮杂十四环-NCS配合物的合成及其晶体结构

The compound 2,4,4,9,11,11-hexamethyl-1,5,8,12-tetraazacyclotetradecane-1,8-diene(1) was synthesized by new method with high yield(95.2%),and its complex with Cu(II) and SCN-was also obtained.The structures of both the ligand and the complex were characterized by IR,elemental analysis,and X-ray diffraction.The crystal of the title compound(2) belongs to monoclinic system,space group P21/n,Mr=501.53,a=1.28883(11) nm,b=1.13462(10) nm,c=1.58128(13) nm,β=102.7430(10)°,V=2.2554(3) nm3,Z=4,d=1.477g/ cm3,F(000)=1052.R1=0.0360,wR2=0.0976[I>2σ(Ⅰ)].The copper atom is five–coordinated with four nitrogen atoms from compound 1 and one nitrogen atom from thiocyanate to form a tetragonal pyramid structure.

一种新型十元噻吩大环化合物的合成及晶体结构

以2,2′-二溴-5,5′-二(三甲硅基)-[3,3′]联噻吩为原料,在无水无氧低温条件下制备出一种新的十元大环低聚噻吩化合物,并用核磁共振、红外光谱以及高分辨质谱对其结构进行了表征.X射线单晶衍射分析确定了其晶体属于单斜晶系,C2/c空间群,分子中心为十元大环结构呈"扭船型"构象,平均内径约为0.3970 nm.

基于联萘酚的水溶性手性大环荧光传感器的合成与晶体结构

以R-联萘酚、氯氰胺、间苯二胺、1,2二苯基乙二胺、乙二胺为原料合成了3个水溶性手性大环荧光传感器;利用核磁共振(1 H NMR和13 C NMR)、质谱、红外光谱验证了合成产物的结构,利用元素分析仪测定了其组成,并利用X射线衍射分析确定了单晶R-3的晶体结构.结果表明,R-3属于单斜晶系,P2(1)/n空间群,晶胞参数为:a=1.128 6nm,b=1.566 1nm,c=2.293 9nm,β=90°,Z=4,Dc=1.328g.cm-3,F(000)=1 684.

大环多胺配体BDBPH的设计合成及其晶体结构

用 Pb( SN) 2 作模板 ,2 ,6-二甲酰基对甲苯酚与二亚乙基三胺通过 [2 +2 ]缩合反应 ,经 Na BH4 还原、脱 Pb2 +、酸化等操作 ,得晶体 BDBPH· 6HBr· 4 H2 O.晶体属单斜晶系 ,P2 1/ c空间群 ,晶体学参数 :a=1 .4 441 ( 5) nm,b=1 .1 4 82 ( 4) nm,c=1 .2 0 90 ( 6) nm,α=90°,β=96.92°,γ=90°,V=1 .990 0 nm3 .大环分子采取椅式构型 ,6个 Br-和 4个 H2 O分子对称分布于大环两侧 .该大环配体结构新颖 ,可用于多种金属配合物的研究 ,对进一步了解金属酶活性中心的结构及其催化作用机理具有重要价值 .

新型大环配体-BDBPH合成及其晶体结构

目的 利用分子设计 ,合成新型大环多胺配体BDBPH ,研究其合成工艺及晶体结构。方法 2 ,6 二甲酰基对甲苯酚 ,二亚乙基三胺 ,Pb(SCN) 2 三种化合物在CHCl3溶液中 50～ 6 0℃反应 18h ,随后经NaBH4 还原、脱Pb2 + 等操作 ,得晶体产品BDBPH ,用1HNMR、FAB—MS、元素分析确定了其结构 ,用单晶X 射线衍射法测定其晶体结构。结果 1HNMR(D2 O) ,δ(ppm) :2 .13(s , CH3,6H) ,3.35(q ,ethylene ,16H) ,4 .2 1(s , CH2 ,8H) ,7.16 (s ,Ary1,4H) ;FAB MS :4 71(M +H ) ;元素分析 ,计算值 (BDBPH·6HBr·4H2 O) :C 30 .35,H 5.4 4 ,N 8.17,实测值 :C 30 .2 2 ,H 5.4 6 ,N7.98。晶体属单斜晶系 ,P2 1/C空间群 ,晶体学参数 :a =14.4 4 1(5) ,b =11.4 82 (4 ) ,c =12 .0 90 (6 ) ,α =90 ,β =96 .92 (3) ,γ =90℃ ,V =1990 .0 (14) 3。大环分子采取椅式构型 ,6个Br- ,4个H2 O分子对称分布于大环两侧。结论 该大环配体合成工艺先进 ,晶体结构新颖 ,可用于多种金属配合物的研究 ,对进一步了解金属酶的结构及其催化作用机制具有重要意义。

新型大环Schiff碱化合物的合成及其晶体结构

以间苯二酚和二乙烯三胺为原料,经缩合成环作用得到一新型Schiff碱大环化合物1.单晶X射线衍射结果表明,该化合物属于单斜晶系,P21/c空间群,晶胞参数为a=0.81977(9)nm,b=1.27817(14)nm,c=1.60193(17)nm,α=90°,β=93.34(3)°,γ=90°,V=1.6757(3)nm3,Z=4,R1=0.0553,wR2=0.1603.在分子的大环结构中形成了四个N+—H…O-离子型氢键,化合物分子呈现为一四边形结构框架,两个相互平行的苯环间存在较强π-π相互作用.

一种新大环草酰胺-镍(Ⅱ)配合物的合成与表征

合成了一种新的大环草酰胺-镍(Ⅱ)配合物,通过红外光谱、元素分析和X-射线单晶衍射分析对其结构进行了表征。结果表明,该配合物具有零维结构,零维单元通过分子间氢键连接成二维网络结构;该配合物具有未被使用的配位基,可作为配体制备多核配合物或配位聚合物。

菲罗啉大环双核Fe3+配合物的合成及其荧光性质

根据文献方法合成大环配体L,通过溶剂法与金属盐Fe(ClO4)2·6H2O反应合成了两个新的菲罗琳大环双核Fe^3+配合物[Fe2(L)(μ-O)(DMF)4]·4ClO4(1,CCDC:1834054)和[Fe2(L)(μ-O)(SCN)4]·4ClO4(2,CCDC:1834055),其结构经IR和元素分析表征。晶体结构解析表明:1属三斜晶系,2属单斜晶系。配合物中两个铁原子通过一个氧桥进行连接,由于氧桥的连接使得配体发生折叠进而产生了π-π堆积。配体荧光滴定实验显示,配体L对过渡金属存在响应,随着过渡金属离子的加入,配体的荧光强度不断减弱。