Synthesis, Crystal Structure, Spectroscopic and Thermal Investigations of a Novel 2D Sodium(I) Coordination Polymer Based on 2-Aminoterephthalic Ligand

The reaction of sodium hydroxide with 2-aminoterephthalic acid leads to the formation of a complex of the general formula: [Na₂(atpt)(H₂O)₅]·H₂O, where atpt?=?[NH₂C₆H₃(COO)₂]^2?. Sodium 2-aminoterephthalate was synthesized and characterized by single-crystal X-ray diffraction, FT-IR spectroscopy, thermal analysis and coupled TG–FT-IR technique. Crystallographic study of the sodium complex reveals that the compound crystallizes in the triclinic system, the space group P-1 with a?=?7.983(3) ?, b?=?8.405(3) ?, c?=?11.311(5) ?, α?=?70.74(3)°, β?=?76.57(3)°, γ?=?83.12(3)° and V?=?696.1(5) ?³. On heating in air atmosphere the compound in question loses all water molecules in two steps in the temperature range 30–205?°C. The anhydrous form of the complex is stable up to 370?°C and then decomposes to sodium carbonate.     

含能配合物Ni（C5N5O5H-4）2（by）2的晶体结构和热分解性能

培养了含能配合物Ni(C5N5O5H42)(by2)(by=吡啶)晶体,用X射线单晶衍射法测定了其分子结构。其晶体属于单斜晶系,空间群为P21/C,a=9.0070(18)nm,b=10.002(2)nm,c=19.445(4)nm,β=93.69(3),V=1748.1(6)nm3,μ=0.633mm-1,Z=4,S=1.00,最终残差因子[I>2σ(I)]R1=0.0530,WR2=0.1162,对于全部数据R1=0.0965,WR2=0.1358。用DSC、TG-DTG对该配合物的热分解过程进行了研究。结果表明,该配合物的热分解过程仅由1个剧烈的放热峰组成,剩余残渣量约5.508%。用Kissinger法和Ozawa-Doyle法计算出配合物热分解过程中的表观活化能和指前因子分别为224.30kJ/mol和7.32×1019s-1。     

Preparation,Crystal Structure,Thermal Decomposition,and Explosive Properties of [Cd(en)(N3)2]n

A new multi‐ligand coordination polymer of cadmium(II) ethylenediamine azide, [Cd(en)(N₃)₂]_n (en=ethylenediamine), was synthesized and characterized by using elemental analysis and FT‐IR spectrum. Its crystal structure was determined by means of X‐ray single crystal diffraction. The obtained results show that this crystal belongs to monoclinic, P2₁/n space group, a=0.6548(1) nm, b=1.0170(2) nm, c=1.2246(2) nm, β=90.23(1)°, V=0.8156(2) nm³, D_c=2.090 g⋅cm⁻³, Z=4, R₁=0.024, wR₂ (I>2σ(I))=0.0416 and S=0.998. The Cd(II) ion is six‐coordinated with four azido ligands by μ‐1, 1 azido bridges, and two ethylenediamine molecules which serve as bidentate ligands through the nitrogen atoms. The thermal decomposition mechanism of the title complex was studied by using differential scanning calorimetry (DSC) and thermogravimetry‐differential thermogravimetry (TG–DTG) techniques. Under nitrogen atmosphere with a heating rate of 10 K⋅min⁻¹, the thermal decomposition of the complex contains two main successive exothermic processes between 519 and 701 K in the DSC curve, and the final decomposed residue at 725 K is Cd. The non‐isothermal kinetics parameters were calculated by using the Kissinger's method, Ozawa–Doyle's method, pervasive integration method, and differential method, respectively. The sensitivity properties of [Cd(en)(N₃)₂]_n were also determined with standard methods.     

超分子化合物[Co(HL)(2,2'-bipy)2]·9.5H2O的合成、晶体结构和热性质

合成了超分子化合物[Co(HL)(2,2'-bipy)2]·9.5H2O(H3L=对羧基苯磺酰甘氨酸,2,2'-bipy=2,2'-联吡啶),并通过单晶X射线衍射确定了晶体结构,晶体结构分析表明化合物C29H42CoN5O15.5S属单斜品系,C2/c空间群.Co(Ⅱ)离子为6配位的八面体结构,对羧基苯磺酰甘氨酸作为双齿配体与Co(Ⅱ)离子配位,2,2'-联吡啶和co(Ⅱ)离子双齿螯合配位.配合物通过氧键和π-π堆积作用形成三维结构,配合物中含有一个由18个水分子组成的独立水簇.在氮气气氛中对该化合物进行了热重分析,结果表明:该化合物在30.1℃时开始失重,440℃时分解完全.     

Synthesis,Crystal Structure,Spectroscopic and Thermal Analysis of Strontium Pyrophosphate Dihydrate Nanoparticles

Various pyrophosphates are very useful as bioceramics; for instance, strontium pyrophosphate is one of the emerging forms of alkaline phosphate. Strontium pyrophosphate dihydrate (Sr₂P₂O₇2H₂O) nanoparticles were synthesized by the surfactant‐mediated approach and characterized by different techniques. From the powder XRD study, the average crystallite size was evaluated by applying Scherrer's formula, which was found to be 33.57 nm. The average crystallite size and internal strain were also evaluated using Williamson–Hall (W‐H) method. The FT‐IR spectroscopy study confirmed the presence of symmetric and asymmetric stretching vibrations of P–O–P and PO₃. The UV‐NIR absorption spectroscopy over the spectral range of 210–1200 nm was employed, and the energy band gap was calculated from Tauc's plot which was found to be 4.9 eV. Thermogravimetric analysis (TGA) confirmed the presence of two water molecules in the sample. From TGA, it was found that the sample become anhydrous and on heating above 410–800°C, the sample remained almost stable with slight weight gain due to adsorption of purged gas. Various kinetic parameters and thermodynamic parameters were evaluated for dehydration process.     

Interaction of [Rh(2)(O(2)CCH(3))(4)(H(2)O)(2)] and [Rh(2)(O(2)CCH(OH)Ph)(2)(phen)(2)(H(2)O)(2)](O(2)C-CH(OH)Ph)(2) With Sulfhydryl Compounds and Ceruloplasmin

The interaction of binuclear rhodium(II) complexes [Rh(2)(OOCCH(3))(4)(H(2)O)(2)], [Rh(2){OOCCH(OH)Ph}(2)(phen)(2)(H(2)O)(2)] {OOCCH(OH)Ph}(2), [Rh(2)(OOCCH(3))(2)(bpy)(2)(H(2)O)(2)](OOCCH(3))(2) and [Rh(2)Cl(2)(OOCMe)(2)(bpy)(2)](3H(2)O) with ceruloplasmin, cysteine, glutathione and coenzyme A have been investigated using. UV-Vis and CD spectroscopies. The complexes containing phen or bpy at pH = 7.4 and 4.0 are readily reduced with sulfhydryl compounds, while rhodium(II) acetate is relatively stable in these conditions. Complex [Rh(2){OOCCH(OH)Ph}(2)(phen)(2)(H(2)O)(2)] strongly changes structure of ceruloplasmin leading to the decrease of of alpha-helix content and loss of oxidase activity.     

Syntheses and Characterization of Diorganotin Derivatives of 2-Mercapto-5-methyl-1,3,4-thiadiazole: X-ray Crystal Structure of Polymeric (C3H3S2N2) [(n-C4H9)6Sn3O(OH)2](C3H3S2N2)

Diorganotin derivatives of 2-mercapto-5-methyl-1,3,4 -thiadiazole, (R = Me 1, n-Bu 2, Ph 3, PhCH₂ 4), have been synthesized and characterized by IR, ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy. Among them, polymer 2 was also characterized by X-ray crystallography diffraction analysis. This revealed that 2 showed a unique tricyclic structure consisting of a fused five-membered Sn₂ON₂ ring and a four-membered Sn₂O₂ ring. These formed a planar N₂Sn₃O₂ skeleton, with distorted trigonal bipyramidal coordination at the two tin centers and a distorted octahedral coordination at the other tin center. The supramolecular structure of polymer 2 was a 1D zig-zag polymeric chain stabilized by intermolecular O–H...S hydrogen bonds. An erratum to this article can be found at     

二维层状磷酸铝化合物[Al(HPO4)(H2PO4)(C10H8N2)]的合成与表征

利用溶剂热法成功地合成出一个二维层状磷酸铝化合物[Al(HPO4)(H2PO4)(C10H8N2)].通过X-ray粉末衍射、单晶X射线、ICP、元素分析及热重分析等对该化合物进行了表征.该化合物属于单斜晶系,空间群P21/c(No.14),晶胞参数a = 10.932(2) ?,b = 15.7183(3) ?, c = 8.4177(17) ?,α = 90o,β = 108. 95(3)o ,γ = 90o, V=1368.0(5)?3,Z=4.其骨架由AlO4N2八面体通过共顶点与H2PO4和HPO4四面体连接而形成(4,12)网络层状结构.该网层结构按AA方式堆积,同时相邻层的2,2'-联吡啶分子之间具有Pi-Pi键相互作用.该工作进一步丰富了磷酸铝化合物的结构化学,并且为实现定向设计和合成提供了实验和理论依据.     

一种新型铜配合物Cu_2(C_6H_8O_4)_2(C_3H_7NO)_2的合成和晶体结构

本文以苯并咪唑-5-羧酸、己二酸、硫酸铜为原料,以水/DMF(v/v 1:1)为溶剂,采用水热合成法合成了新型铜配合物Cu_2(C_6H_8O_4)_2(C_3H_7NO)_2单晶,并通过单晶衍射仪测定了晶体结构。该配合物属于为单斜晶系,空间群为P21/n,晶胞参数为:a=9.4764(5)?,b=8.2618(5)?,c=15.0990(8)?,β=106.259(1)o,V=1134.85(11)?3,Z=2。     

{CdI4[（C4H6N2）2+C2H4]}n的合成与晶体结构

用溶液挥发法合成了一个新的有机-无机杂化聚合物{Cd I4[(C4H6N2)2+C2H4]}n,并通过X-射线单晶衍射仪对其进行结构表征。化合物1属于单斜晶系,C2/c空间群,a=34.383(7)?,b=8.1299(16)?,c=15.199(3)?,β=112.47(3)°,V=3926.0(13)?3,Z=8。化合物1由有机阳离子[(C4H6N2)2+C2H4]和无机[Cd I4]2-阴离子组成一个零维簇结构,相邻的簇与簇之间通过氢键作用形成三维超分子网状结构。     

配合物Pd(C4H2O4)(C4H8N2)0.5的合成及对苯酚的氧化羰基化的催化活性

A novel complex Pd(C4H2O4)(C4H8N2)0.5 has been synthesized by solvent thermal synthesis and used as a heterogeneous catalyst for direct synthesis of diphenyl carbonate (DPC) by oxidative carbonylation of phenol. In the reaction system of Pd(C4H2O4)(C4H8N2)0.5/Cu(OAc)2/ tetrabutylammonium bromide/ hydroquinone/ 4A molecular sieves, the effect of reaction temperature, time and CO pressure on catalytic activity were investigated, and the results revealed that the catalyst could catalyze oxidative carbonylation of phenol effectively. Under suitable reaction conditions of T=90℃, t=4h, p(O2)=0.3 MPa, p(CO)=3.9 MPa and CH2Cl2 as solvent, the turnover number (TON) of diphenyl carbonate can reach about 13.50 (mol-DPC/mol-Pd), which is higher than the TON for pure PdCl2 under the same reaction conditions.     

Crystal Structure, Thermal and Magnetic Behavior of Inorganic–Organic Hybrid [VIV 4O10 VV 2O4] (C6H14N2)·H2O Polymeric Framework

Summary The inorganic–organic hybrid [V^IV ₄O₁₀V^V ₂O₄] (C₆H₁₄N₂)·H₂O polymeric framework was prepared under mild hydrothermal conditions from a mixture of DABCO and V₂O₅ in deionized water with a 1:1:450 mole ratio, at neutral pH. The reaction was carried out at 180 °C for 3 days under autogenous pressure yielding phase pure crystals product. The crystal structure was studied using both powder and single crystal X-ray crystallography, revealing the structure to be of the ({UuDd}:T*)α′ type in the SP+T class and Z-T subclass. The presence of the organic cation was confirmed by FT-IR spectrum and chemical composition analysis. The structure was thermally stable up to over 400 °C, and showed ferromagnetic character at room temperature with the maximum molar susceptibility of 8.26 × 10⁻³ emu/mol⁻¹ at zero applied field.     

稀土配合物[Ln(C3H7NO2)-x-(C3H4N2)(H2O)](ClO4)3(Ln=La,-x-=3;Ln=Pr,Nd,Sm,-x-=2)的合成、表征与热分析

合成了稀土高氯酸盐与咪唑、DL α 丙氨酸的4种配合物晶体。经傅里叶变换红外光谱(FTIR)、元素分析和化学分析测定后确定其组成为[Ln(C3H7NO2)x(C3H4N2)(H2O)](ClO4)3(Ln=La,x=3;Ln=Pr,Nd,Sm,x=2)。用差示扫描量热法(DSC)测定了4种配合物的热分解数据,4个配合物开始熔化分解的温度分别为502 5K,532 4K,495 7K,516 7K,配合物有较高的热稳定性。     

新型配位聚合物[Co(C_5H_5N)_2(H_2O)_2(O_2CC_2H_4CO_2)]_n的水热合成和晶体结构

以CoCl2.6 H2O和丁二酸(CH2COOH)2、三乙胺为原料,在中温水热反应条件下,合成了一种新型配位聚合物[Co(C5H5N)2(H2O)2(O2CC2H4CO2)]n,并对其进行了X射线单晶衍射和红外光谱测定。晶体数据如下:正交晶系,Pbca空间群,a=11.91940(12)nm;b=8.91440(10)nm;c=15.1025(2)nm;α=90.00;β=90.00;γ=90.00;V=1604.71(3)nm3;Z=4;Dc=1.528 g/cm3;μ=1.101 mm-1;F(000)=764;R1=0.0492,wR2=0.0831。该晶体通过分子间氢键和相互作用的π-π键形成一维的链状结构。     

超分子化合物(C12N2H9)2(C12N2H8)[SW12O40]的合成与结构表征

利用水热法合成了超分子化合物（C12N2H9）2（C12N2H8）[SW12O40],通过元素分析和X射线单晶衍射确定了其晶体结构,该晶体为正交晶系,P2（1）2（1）2（1）空间群,晶胞参数为a=12．0168（3）A^。,b=21．0534（6）A^。,c=22．5820（6）A^。,V=5713．1（3）A^。^3,α=β=γ=90°,Z=4,Dc=3．977mg·m^-3,并通过IR和XRD进行了结构表征,采用热重分析研究了晶体的热稳定性。该化合物由邻菲罗林和Keggin结构[SW12O40]^2-阴离子组成,以氢键自组装成超分子结构化合物。     

Study on Crystal Structure and Thermal Decomposition Mechanism of a Novel Coordination Compound [Zn(DAT)2(H2O)4](PA)2⋅2H2O

A novel coordination compound [Zn(DAT)₂(H₂O)₄](PA)₂⋅2H₂O has been synthesized using 1,5‐diaminotetrazole (DAT) as ligands. It crystallizes in the monoclinic space group C2/c, with a=1.51973(19) nm, b=0.67904(9) nm, c=3.0712(4) nm, β=90.507(2)°, V=3.1692(7) nm³, Z=4, and μ=0.888 mm⁻¹. With the intermolecular hydrogen bonds, molecules are linked together to form a three‐dimensional net structure. Thermal decomposition mechanism of the title compound was predicted based on DSC, TG‐DTG, and FT‐IR analyses. The kinetic parameters of the first exothermic process of the title compound were studied applying the Kissinger's and Ozawa–Doyle's methods.     

[(C_2H_5)_4N]_2｛Fe_4S_4[S_2CN(C_2H_5)_2]_4｝的晶体和分子结构

本文报导含类立方烷型簇核Ｆｅ４ｓ４的金硫配位化合物［（Ｃ２Ｈ５）４Ｎ］２｛Ｆｅ４Ｓ４［Ｓ２ＣＮ（Ｃ２Ｈ５）２］４｝的合成、晶体和分子结构测定的结果。     

Complexes Containing N-(2-hydroxyethyl)-ethylenediamine with Tetracyanometallate (II): Synthesis, IR Spectra, Thermal Behavior, Crystal Structure, Magnetic Properties and Catalysis

Two novel cyano-bridged Ni²⁺ and Cu²⁺ compounds, {[M²⁺(hydeten)₂(μ-CN)₂Ni(CN)₂] _n , M²⁺ = Ni²⁺ (c1) and Cu²⁺ (c2), N-(2-hydroxyethyl)-ethylenediamine (hydeten), were prepared and characterized by elemental analysis, IR spectroscopy and thermoanalytical measurements. The one-dimensional polymeric structure of c2, which was determined by X-ray diffraction techniques, was formed with a 2,2-TT-type chain, –Cu(hydeten)₂-NC-Ni(CN)₂-CN-Cu(hydeten)₂-, linkages. Also, while the EPR spectra and magnetic properties of complexes c1 and c2 with [Ni(hydeten)₂Pd(CN)₄] (c3) and [Cu(hydeten)₂Pd(CN)₄] (c4) [Karadağ, Z Kristallogr 222:39, 2007] were investigated, the catalytic activity of c3 and c4 was studied. The EPR spectra of c2 and c4 showed that Cu²⁺ was located in tetragonal distorted octahedral sites (D _4h ) and the ground state of the paramagnetic electron was d _{x² - y²} d_{{ x^{2} - y^{2} }} . The magnetic behavior exhibited weak antiferromagnetic interactions in all the complexes. Also, the catalytic properties of c3 and c4, which were assigned with Suzuki and Heck coupling reactions, showed that they did not have catalytic effects.     

三苯基锡(Ⅳ)四氢吡咯荒酸酯的合成、表征、性质及晶体结构

用三苯基氯化锡和四氢吡咯荒酸钠反应 ,合成了三苯基锡 ( )四氢吡咯荒酸酯。通过元素分析、红外光谱和氢核磁共振谱对其结构进行了表征。用 X-射线单晶衍射测定了该化合物的晶体结构。结果表明 ,化合物中锡原子呈五配位畸变三角双锥构型