[Ni(CHZ)_3]SO_4·3H_2O的合成、晶体结构及热分解特性(英文)  

Preparation, Crystal Structure and Thermal Decomposition Character of [Ni(CHZ)_3]SO_4·3H_2O

作　　者：张进[1] 张同来[1] 杨利[1] 张建国[1] 崔燕[1] 

机构地区：[1]北京理工大学爆炸科学与技术国家重点实验室,北京100081

出　　处：《物理化学学报》2008年第5期760-766,共7页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金(20471008)资助项目

摘　　要：用硫酸镍与碳酰肼(CHZ)反应,制备得到一种新型含能配合物[Ni(CHZ)3]SO4·3H2O,通过X射线单晶衍射,元素分析和傅立叶变换红外(FTIR)光谱对其进行了表征.晶体结构测试表明,该化合物晶体属于三斜晶系,P1空间群,a=0.85237(1)nm,b=0.90964(1)nm,c=1.22559(2)nm,β=96.731(2)°,V=0.8849(2)nm3,Z=2,Dc=1.798g·cm-3.在该配合物分子中,碳酰肼作为双齿配体,以羰基O原子和端基N原子与Ni2+离子发生配位,形成3个相互垂直的五元平面螯合环.在氢键、静电引力和范德华力的作用下,该配合物形成了复杂的三维网状结构.对碳酰肼分子进行了DFT-B3LYP/6-311+G**量化计算研究,得到其NBO电荷,从理论上说明碳酰肼的配位点是羰基O原子和端基N原子.采用DSC、TG-DTG和FTIR光谱技术对目标化合物的热分解机理进行了研究,并用Kissinger法和Ozawa-Doyle法对其热分解过程中两个放热峰的非等温反应动力学参数进行了计算.结果表明,该配合物具有较高的能量和良好的热稳定性.A new coordination compound [Ni（CHZ）3]SO4·3H2O （CHZ = carbohydrazide） was synthesized and characterized by elemental analysis and fourier transform infrared （FTIR） spectra, and its crystal structure was determined by X-ray single crystal diffraction. The crystal belonged to the triclinic system, space group P1 with a=0.85237（1） nm, b=0.90964（1） nm, c=1.22559（2） nm, β=96.731（2）°, V=0.8849（2） nm3, Z=2, Dc=1.798 g·cm-3. In the asymmetric unit, three carbohydrazide （CHZ） bidentate ligands were coordinated with a Ni（II） cation by carbonyl O atoms and terminal N atoms of the hydrazine groups to form three planar chelate rings which were vertical to one another. Ni（II） cations, CHZ ligand molecules, sulfate anions, and lattice water molecules were jointed to a complicated three-dimensional network structure through coordination bonds, electrostatic forces and extensive hydrogen bonds. Natural bond orbital （NBO） atomic charges of CHZ were obtained from the density functional theory （DFT） method at the B3LYP/6-311＋G＊＊ level to interpret the reason why the coordination sites in carbohydrazide molecule were the oxygen atom of the carbonyl group and terminal N atoms of the hydrazine group. The thermal decomposition mechanism was tested through differential scanning calorimetry （DSC）, thermogravimetric analyses, and Fourier transform infrared spectra. The kinetic parameters of the two exothermic processes of the title compound were studied applying the Kissinger′s and Ozawa-Doyle′s methods. The results indicated that the title complex possessed high energy and good thermal stability.

关 键 词：镍(Ⅱ)配合物 碳酰肼 晶体结构 热分解 

分 类 号：O641.1[理学—物理化学]