Synthesis, Crystal Structure, Thermal Behavior and IR Characterization of Pentacarbonyl(4-methylpyridine)chromium(0) Complex

Abstract  Pentacarbonyl(4-methylpyridine)chromium(0) complex was isolated from n-hexane solution as yellow plate-like crystals and characterized by using X-ray crystallography. It crystallizes in the orthorhombic system with the space group Cmcm and Z = 4. The unit cell parameters are a = 11.737(1) ?, b = 12.857(2) ?, c = 8.465(1) ?. The single crystal X-ray structure of the complex shows that the coordination sphere around the chromium central atom is slightly distorted octahedron, involving the 4-methylpyridine (4-mp), ligand as a monodentate N-donor ligand and five carbonyl groups. The four equatorial CO groups in the complex, with the Cr–C2 distance of 1.886 Ǻ, are slightly bent away from the 4-methylpyridine ligand with the N–Cr–C2 angle of 91.69°. The pyridine ring plane makes an angle of 135.17° with the Cr–N–CO bond axis. The thermal analysis (differential thermal analysis and thermal gravimetry) and IR spectra of the complex indicated that the compound undergoes complete decomposition to form the Cr₂O₃ as the final decomposition product. Index Abstract  The crystal structure of pentacarbonyl(4-methylpyridine)chromium(0) complex has been determined and its thermal behavior has also been studied.      

1,3,5-三(羧基甲氧基)苯镍配位聚合物的合成、晶体结构及性质研究

采用溶剂热法,1,3,5-三(羧基甲氧基)苯为定向配体和乙酸镍反应构筑了一个新型的金属配位聚合物[Ni(TB)2(H2O)2]n·2H2O,其中H3TB=1,3,5-三(羧基甲氧基)苯,通过元素分析、IR及X射线单晶衍射对配合物结构进行表征,并研究其荧光性质、热稳定性及Hirshfeld表面作用力.单晶结构分析表明,该...     

孔道结构钒铝磷酸盐(NH3CH2CH2NH2)[(VO)Al(PO4)2]的水热合成及热稳定性

用XRD,TG-DTA,FT-IR和SEM对水热法合成的孔道结构钒铝磷酸盐(NH3CH2CH2NH2)[(VO)Al(PO4)2]进行了热性能表征.该化合物中有机组份的分解温度,在氧化气氛中为305～529℃,在惰性气氛中为411～593℃.有机组分的分解逸出导致了结构的破坏,但晶体的微形貌没有发生明显的变化;温度继续升高,发生相变.该化合物热稳定性较其它含有机模板的孔道结构钒磷酸盐要高,主要原因在于结构中存在[AlO4]和[PO4]共顶连接而成的一维链,这种链增加了骨架的强度.     

Synthesis,Characterization, Crystal Structure,and Thermal Analysis of 4-[(3-acetylphenyl)amino]-2-methylidene-4-oxobutanoic Acid

4-[(3-Acetylphenyl)amino]-2-methylidene-4-oxobutanoic acid (1) is synthesized by a ring opening reaction of itaconic anhydride with 3-aminoacetophenone and characterized by FT-IR, ¹H NMR, UV-Vis, TGA, DTA, and single crystal X-ray diffraction. The crystal of 1 belongs to triclinic unit cell in the P-1 space group with the unit cell dimensions a = 4.9485(3), b = 5.3614(6), c = 22.457(2) Å, α = 88.295(8), β = 89.379(7), γ = 84.495(7), and Z = 2 The crystal structure is solved by direct methods using single-crystal X-ray diffraction data collected at room temperature and refined by full-matrix least-squares procedures to a final R-value of 0.0467 for 1623 observed reflections. Intermolecular N&;sbnd;H?…O and O&;sbnd;H?…O hydrogen bonds links the molecules into chains along [010] direction. In addition the thermal stability of the 1 is determined by using DTA, TGA analysis, and wavelength absorption at λ_max = 297 nm is determined by UV-Vis spectrophotometer.     

X/g-C3N4(X=g-C3N4、AlN及GaN)异质结光催化活性的理论研究

本文采用基于密度泛函理论的第一性原理平面波超软赝势方法,研究了单层g-C₃N₄以及X/g-C₃N₄(X=g-C₃N₄、AlN及GaN)异质结的稳定性、电子结构、功函数及光学性质。结果表明,X/g-C₃N₄异质结的晶格失配率和晶格失配能极低,说明X/g-C₃N₄具有优异的稳定性。与单层g-C₃N₄相比,X/g-C₃N₄的带隙均减小,态密度的波峰和波谷均大幅提高且出现了红移现象,处于激发态的电子数量增加,使得电子跃迁变得更为容易,表明构建异质结有利于提高体系对可见光的响应能力。此外,X/g-C₃N₄的功函数均减小且在界面处形成了内建电场,有效抑制了光生电子-空穴对的复合,这对载流子的迁移以及光催化能力的提高大有裨益。其中,GaN/g-C₃N₄的功函数最小,在界面处存在电势差形成了内建电场且红移现象最明显,可推测GaN/g-C₃N₄的光催化性能最好。因此,本文提出的构建异质结是提高体系光催化活性的有效手段。     

Y0.145Gd0.855Ca4O(BO3)3混晶的晶体生长和压电、热膨胀性能

利用提拉法成功生长出了Y0.145Gd0.855Ca4O(BO3)3(Y0.145Gd0.855COB)混晶.对其压电系数和热膨胀系数进行了测量,测得压电系数d26为9 pC/N,计算得到热膨胀系数α11,α22 α33分别为12.97×10-6/℃,5.94×10-6/℃,8.03×10-6/℃.通过与YCa4O(BO3)3和GdCa4O(BO3)3晶体的对比,分析了Re3+半径和Re3+、Ca2+的无序分布对于Y0.145 Gd0.855COB混晶的压电性能和热膨胀性能的影响.     

手性镝(III)-酒石酸配合物的合成、单晶转换及热稳定性研究

以2,3-二乙酰对甲苯-D-酒石酸(D-H₂DTTA)为原料,与金属Dy(III)盐反应,经过单晶-单晶转换,得到一种新的酒石酸(H₂tar)配合物[Dy(Htar)₃(H₂O)₃]_n(1),对该配合物用元素分析、红外光谱、X-射线单晶衍射、粉末衍射以及差热-热重等进行了表征。晶体结构分析表明,配合物1属三方晶系,R3空间群,晶胞参数为a=b=2.723 16(14) nm,c=0.762 75(6) nm,α=β=90.00°,γ=120.00°,V=4.898 5 (6) nm³,Z=3, 剑桥晶体数据库(Cambridge Crystallographic Data Centre, CCDC)编号为1498504。配合物中的金属Dy³⁺分别与三个酒石酸离子配体Htar^-上的六个氧原子和三个配位水分子上的三个氧原子配位,形成九配位三帽三棱柱构型。配合物1在c方向上通过O1和O5原子连接成一维链状结构,相邻Dy³⁺之间的距离为0.762 8(1) nm。配合物1是由[Dy(HDTTA)₃(CH₃OH)₃]_n经单晶-单晶转换过程得到,其转换过程包括酯基水解及水分子取代两类反应。配合物1具有一定的热稳定性,45~166 ℃失去配位水分子,高于166 ℃配合物骨架坍塌。     

N-(4-吡啶甲基)-L-丝氨酸铜配合物的合成、晶体结构和磁性

氨基酸还原希夫碱HL (N-(4-吡啶甲基)-L-丝氨酸)与CuCl2·2H2O在室温条件通过扩散法合成了配位聚合物{[Cu2(L)2(Cl)2]·H2O}n(I).采用元素分析、红外光谱、X-射线单晶衍射、粉末衍射和热重分析进行了表征.两个结晶学独立Cu(II) 包含于其晶体结构中,Cu1为变形八面体CuO2N2Cl2几何构型;Cu2则呈现略有变形的四方锥结构.Cu1和Cu2通过配体L-的吡啶氮原子以及氯离子的桥连作用连接为2D网状结构.变温磁化率实验表明在温度为2~300 K,配合物I表现为铁磁性耦合.     

Investigation of Bimetallic Thiocyanates belonging to ABTC Structure Type: ZnCd(SCN)4 and AHg(SCN)4 (A = Zn,Cd, Mn ) as Nonlinear Optical Crystal Materials

Bimetallic thiocyanate complexes crystal materials belonging to ABTC structure type: ZnCd(SCN)₄ and AHg(SCN)₄ (A = Zn, Cd, Mn ) which are potentially useful in second harmonic generation (SHG) have been prepared. Their structural, optical and physicochemical properties are characterized by infrared spectroscopy, X‐ray powder diffraction, vis/UV/NIR spectroscopy, SHG measurements and thermal analysis. The states of crystal growth solutions are discussed in this article. The crystals belong to tetragonal system with the space group I‐4 and exhibit SHG efficiencies over one order of magnitude higher than that of Urea. Their transparency cutoffs lie in the UV region, and they possess good physicochemical stabilities.     

Structure, thermal behavior, and IR investigations of (C6H9N2)H2PO4

Chemical preparation, X-ray single-crystal, thermal behavior, and IR spectroscopy studies of a new dihydrogenmonophosphate associated to an organic cation, the 3-(ammoniummethyl)pyridine dihydrogenmonophosphate (denoted as AMPP) are described. The AMPP crystallizes in the monoclinic system with P2₁/c space group. The unit cell dimensions are a = 5.8465(2) Å, b = 19.9776(9) Å, c = 7.3103(3) Å, = 90.848(3)° with V = 853.74(4) ų and Z = 4. The structure has been solved using direct method and refined to a reliability R factor of 0.0393. The structure of AMPP includes three types of hydrogen bonds. The first one, O H O, links the H₂PO₄ groups to form infinite inorganic chains [H₂PO₄]n ^n–, parallel to the c axis. The two other types, O H N and N H O assemble inorganic chains so as to build up a three-dimensional arrangement.     

Synthesis,spectral and thermal properties of non‐linear optical crystal ZnMg(SCN)4

Single crystals of zinc magnesium tetra thiocyanate [ZnMg(SCN)₄], a bimetallic thiocyanate complex, were grown by slow evaporation solution growth technique at room temperature. The bright, transparent and colourless crystals have well defined faces. The grown crystals were characterized through elemental analysis, powder X‐ray diffraction (XRD), thermogravimetric (TG) and differential thermal analysis (DTA), differential scanning calorimetric analysis (DSC), Fourier Transform Infra red (FTIR) and Optical studies. The elemental analysis confirms the stoichiometry of the synthesized crystals. The compound crystallizes under monoclinic structure with lattice parameters a = 10.055 Å, b = 7.44 Å, c = 6.00 Å and β = 90.113°. The TGA indicates 25 % weight loss at 205°C from which the decomposition pattern is formulated. The DSC study indicates that the crystal undergoes only first order phase transitions. The FTIR spectrum indicates among others the presence of metal‐nitrogen and metal‐sulphur bonds thus confirming the formation of the complex. The second harmonic‐generation (SHG) was confirmed by the emission of green radiation using Nd: YAG laser. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

4,5-Bis(benzylthio)-1,3-dithiole-2-thione compounds: crystal structures of [(p-XC6H4CH2)(p-XC6H4CH2)dmit: X=Y=OMe; X=Y=NO2; and X=OMe, Y=NO2]

4,5-Bis(benzylthio)-1,3-dithiole-2-thiones, [(p-XC₆H₄CH₂)(p-XC₆H₄CH₂)dmit: X=Y=OMe (2); X=OMe, Y=NO₂ (3); and X=NO₂] (4)] have been prepared from benzyl chlorides and [NEt₄]₂[Zn(dmit)₂]. Isostructural compounds, 2 and 3, crystallize in the triclinic space group (Z = 2) with a = 5.2920(10), b = 10.537(2), c = 18.961(4) Å, = 102.79(3), = 96.33(3), = 98.67(3)° for 2; a = 5.292(8), b = 10.528(12), c = 19.01(2) Å, = 102.74(9), = 96.26(11), = 98.56(11)° for 3. Compound 4 also crystallizes in the space group (Z = 4), with a = 9.296(8), b = 13.993(18), c = 16.186(4) Å, = 106.68(3), = 89.63(3), = 99.38(6)°. Molecular differences between 2 and 3, on one hand, and 4, on the other, arise in the disposition of the aryl rings relative to the dmit group. Short S---S contacts in 2 of 3.320(2) Å [S3---S3 ⁱ (symmetry operation: i: –x + 1, –y + 1, –z)] and in 3 of 3.314(5) Å [S3---S3 ⁱ (symmetry operation: i: –x + 1, –y, –z + 1)] link molecules into pairs. In 4, an S5A---S2B contact of 3.516(5) Å links two independent molecules, A and B, into bimolecular units, which are further connected into chains by S2A---S5B ⁱ contacts (symmetry operation: i: x, y, z – 1) at 3.569(5) Å. C–H---O hydrogen bonds are also present in 3 and 4.     

Synthesis,thermal reactivity and structure of 1,2-bis(4-hydroxy-3-methoxyphenylethynyl)benzene

The crystal structure of the new enediyne 3 was determined by X-ray diffraction. 3 crystallizes in the orthorhombic space group Pbca (No. 61) with a = 12.7148(9) Å, b = 7.4872(8) Å, c = 38.890(4) Å, = = = 90 and Z = 8. The three-dimensional structure is characterized by an 8-membered cyclic array linking four molecules of 3 by hydrogen bonding between phenolic and methoxy groups. Furthermore, stabilization by –-stacking and CH s interactions is present. The important cd distance (between the two terminal acetylene carbons of the enediyne) which is relevant for the Bergman cyclization, was determined to 401 pm, being in good agreement with the high cyclization barrier ( G = 147.9 kJ mol^–1 at 220C) that was determined by differential scanning calorimetry (DSC).     

Synthesis, characterization, and crystal structure of 1-(4-chloro-benzoyl)-3-naphthalen-1-yl-thiourea

1-(4-Chloro-benzoyl)-3-naphthalen-1-yl-thiourea has been synthesized and characterized by elemental analysis, IR spectroscopy, and mass spectrometry. The crystal and molecular structure of the title compound has been determined from single crystal X-ray diffraction data. It crystallizes in the triclinic space group P-1, with a = 6.962(1) Å, b = 10.770(3) Å, c = 11.738(2) Å, = 65.76(2)°, = 80.03(1)°, = 84.86(2)°, and D _calc= 1.432 g cm^–1 for Z = 2. The thermal behavior of the compound has been studied by DTA and TG. The antibacterial activities of the title compound were investigated for three Gram (+) and two Gram (–) bacteria by employing broth microdilution method and subsequently, inhibitory activity against yeast-like fungi was also determined.     

Synthesis,Characterization and Crystal Structure of 1-Phenyl-3-methyl-4-(salicylidene hydrazide)-phenylethylene-pyrazolone-5

Abstract A new compound 1-phenyl-3-methyl-4-(salicylidene hydrazide)-phenylethylene-pyrazolone-5 (PMPeP-SHZ) has been synthesized and characterized by elemental analysis, IR spectrum, MS and single crystal X-ray diffraction. The compound crystallizes in a monoclinic, space group P2(1)/c with cell parameters: a = 10.8275(19) ?, b = 24.689(4) ?, c = 9.7167(16) ? and β = 95.127(4)°, Z = 4, S = 1.097. In the crystal structure, the compound presents in the diketo form. The structure exhibits both intra- and intermolecular hydrogen bonding and the molecules are interlinked through hydrogen bonds forming an infinite 2D network. The fluorescent result shows blue emission at room temperature in solid state. Graphical Abstract Synthesis, Characterization and Crystal Structure of 1-Phenyl-3- methyl-4-(salicylidene hydrazide)-phenylethylene-pyrazolone-5 Li Zhang, Guan-Cheng Xu, Lang Liu, Guang-Fei Liu, and Dian-Zeng Jia* Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Synthesis,Characterization and Crystal Structure of Ethyl 2-amino-4-(4-fluorophenyl)-6-phenylcyclohexa-1,3-diene-1-carboxylate

Ethyl 2-amino-4-(4-fluorophenyl)-6-phenylcyclohexa-1,3-diene-1-carboxylate was synthesized from ethyl 6-(4-bromophenyl)-4-(4-fluorophenyl)-2-oxocyclohex-3-ene-1-carboxylate and ammonium acetate in glacial acetic acid. The synthesized compound was characterized by elemental analysis, FT-IR, thermogravimetric analysis (TGA), differential thermal analysis (DTA), UV-Visible, and single-crystal X-ray diffraction. The title compound, ethyl 2-amino-4-(4-fluorophenyl)-6-phenylcyclohexa-1,3-diene-1-carboxylate, C₂₁H₂OFNO₂, crystallizes in the orthorhombic space group Pbca with the following unit-cell parameters: a = 17.417(2), b = 9.7287(9), c = 21.014(2) Å, and Z = 8. The crystal structure was solved by direct methods using single-crystal X-ray diffraction data collected at room temperature and refined by full-matrix least-squares procedures to a final R-value of 0.0644 for 1616 observed reflections. An intramolecular N–H…O hydrogen bond generates an S(6) graph-set motif. In the crystal, molecules are linked by N–H…O hydrogen bonds, forming a two-dimensional network.     

Synthesis, characterization, peripheral studies, and structural analysis of E-4-(N-methylanilino)-3-pentene-2-one, C12H15NO

Crystallographic structural refinement of E-4-(N-methylanilino)-3-pentene-2-one (I) has been carried out by means of three-dimensional single-crystal X-ray diffractometry. The title compound crystallizes in space group C2 (No. 5,Z = 4). The lattice constants are a = 21.543(4), b = 6.433(1), c = 8.019(2) Å, and = 97.82(3)°. Characterizations include physical property determinations and spectrometric identifications employing IR, ¹H and ¹³C NMR, and X-ray powder analyses. The molecules in the crystal lattice are held together by van der Waals forces. Selected bond distances and angles are presented and discussed as well as synthesis and peripheral studies.     

以2-甲基-丙烯酸,4-(吡啶-4-偶氮)-苯酯为配体的四个配位化合物的合成、晶体结构和紫外吸收

4个单核配位化合物,[Zn(Maape)2(H2O)2(NO3)2] (1, 单核), [Cu(Maape)2(H2O)2(NO3)2] (2, 单核), [Zn(Maape)2Cl2] (3, 单核), [Zn(Maape)(H2O)4SO4] (4, 单核),都是用过渡金属盐和配体2-甲基-丙烯酸,4-(吡啶-4-偶氮)-苯酯合成的.四个化合物由单晶X-射线衍射和结构分析表明都是单核化合物.另外,还通过红外和元素分析对其进行表征.配位化合物的结构不仅受配位金属离子的影响还受不同配位阴离子的影响.化合物1和2的结构都是由一个金属离子中心、2个配位硝酸根离子和2个配体分子组成的单核配合物.化合物3的单核结构中包含一个Zn(II)、2个氯离子和2个配体分子.而化合物4的不对称单元[Zn(Maape)(H2O)4SO4]中Zn(II)中心位于二重对称轴上.在本文中,配体和4个化合物都在323 nm处有最高紫外吸收峰.     

Synthesis,Characterization, Crystal and Molecular Structure Analysis of 2,6-Dimethyl-3-acetyl-5-carbomethoxy-4-(3-nitrophenyl)-1,4-dihydropyridine

Abstract  A novel unsymmetrical dihydropyridine, possessing carboxymethyl and carbomethoxy groups at C(3) and C(5), respectively, has been produced using a modified Hantzsch synthesis, under solvent free conditions, in a domestic microwave oven. The product obtained was characterized by spectroscopic techniques and finally confirmed by X-ray diffraction studies. The title compound C₁₇H₁₈N₂O₅ crystallizes in the monoclinic system in the space group P2₁/c with cell parameters a = 12.860(2) ?, b = 7.4950(6) ?, c = 16.734(3) ?, β = 94.436(3)°, Z = 4 and V = 1608.1(4) ?³. The 1,4-dihydropyridine ring in the structure is in a flattened boat conformation. The molecule possesses a chiral center at C4. The 3-nitrophenyl ring is nearly orthogonal to the 1,4-dihydropyridine ring. The carbonyl groups at C3 and C5 are oriented in −antiperiplanar and +synperiplanar conformations, respectively. The structure exhibits both inter and intramolecular hydrogen bonds of the type N–H···O and C–H···O. Index Abstract  A novel unsymmetrical dihydropyridine, possessing carboxymethyl and carbomethoxy groups at C(3) and C(5) respectively, has been produced using a modified Hantzsch synthesis, under solvent free conditions, in a domestic microwave oven. The product obtained was characterized by spectroscipic techniques and finally confirmed by X-ray diffraction studies. The title compound C₁₇H₁₈N₂O₅ crystallizes in the monoclinic system in the space group P2_1/c with cell parameters a  =  12.860(2) ?, b  =  7.4950(6) ?, c  =  16.734(3) ?, β = 94.436(3)°, Z = 4 and V = 1608.1(4) ?³. The 1,4-dihydropyridine ring in the structure is in a flattened boat conformation. The molecule possesses a chiral center at C(4). The 3-nitrophenyl ring is nearly orthogonal to the 1,4-dihydropyridine ring. The carbonyl groups at C(3) and C(5) are oriented in −antiperiplanar and +synperiplanar conformations respectively. The structure exhibits both inter and intramolecular hydrogen bonds of the type N–H···O and C–H···O.

超分子化合物(C_(12)H_(10)N_4)(C_7H_6O_3)_2的合成、晶体结构及荧光性质

合成了超分子化合物(C_(12)H_(10)N_4)(C_7H_6O_3)_2,并进行了元素分析、红外光谱、紫外光谱表征和单晶X射线衍射分析.构筑单元之间通过多重氢键和π-π堆积作用的协同效应形成超分子化合物,并研究了化合物的固体荧光性能.研究表明:该晶体属于单斜晶系P2_1/c空间群,晶胞参数为:a=0.3974(1) nm,b=2.0330(2) nm,c=1.4343(1) nm, β=94.892(2)°,V=1.15440(19) nm~3,d_c=1.400 g/cm~3,Z = 2,μ= 0.102 mm~(-1),F_((000))=508,R_1=0.0359,wR_2=0.0893 [I>2σ(I)].