[Ni(NH_2NHCO_2CH_3)_3](NO_3)_2·H_2O的制备、晶体结构和热分解机理  

Preparation,Crystal Structure and Thermal Decomposition Mechanisms of [Ni(NH_2NHCO_2CH_3)_3](NO_3)_2·H_2O

作　　者：宋江闯[1] 张同来[1] 张建国[1] 马桂霞[1] 李玉锋[1] 郁开北[2] 

机构地区：[1]北京理工大学爆炸灾害预防控制中心国家重点实验室,北京100081 [2]中国科学院成都分院分析测试中心,成都610041

出　　处：《化学学报》2003年第9期1444-1448,共5页Acta Chimica Sinica

摘　　要：由硝酸镍水溶液和肼基甲酸甲酯 (NH2 NHCOOCH3 ,MCZ)的水溶液反应 ,制备出未见文献报道的配合物 [Ni(MCZ) 3 ] (NO3 ) 2 ·H2 O .晶体结构测定结果表明 ,该晶体属单斜晶系 ,P2 1/n空间群 ,晶体学参数为 :a =1.3 681(2 )nm ,b =0 .8188(1)nm ,c =1.60 2 9(4 )nm ,β =92 .16(2 )° ,V =1.7943 (6)nm3 ,Dc=1.744g·cm-3 ,Z =4,F(0 0 0 ) =976,μ(MoKα) =1.166mm-1.结构采用全矩阵最小二乘法优化 ,除氢原子采用各向同性热参数外 ,其它非氢原子均采用各向异性热参数修正 ,最终偏离因子R1=0 .0 3 3 7,wR2 =0 .0 85 7.在该配合物分子中 ,肼基甲酸甲酯作为双齿配体 ,由羰基氧原子和端基氮原子与Ni2 + 配位 ,形成五元平面螯合环 ,配合物分子中共有三个这样的螯合环 ,中心离子为六配位八面体构型 .配合物的外界是两个硝酸根离子和一个水分子 ,通过库仑力和氢键与内界结合在一起 .采用TG DTG ,DSC ,IR等表征了标题化合物的热稳定性 .在程序升温条件下 ,该配合物的热分解过程是由一个弱的吸热过程和三个较强的连续的放热过程组成的 ,由TG DTG和IR分析结果证明 ,在 3 2 5℃时的最终分解产物为NiO ,得到了化合物的热分解机理 .The title compound (NO_3)_2·H_2O was prepared by reaction of the aqueous solutions of nickel nitrate and methylcarbazate (MCZ). The crystal structure of (NO_3)_2·H_2O was determined by using single crystal diffraction techniques and crystalline was in monoclinic system with space group P 2_1/ n . The unit cell parameters are as follows: a =1.3681(2) nm, b =0.8188(1) nm, c =1.6029(4) nm, β =92.16(2)°, V =1.7943(6) nm 3, Z =4, F (000)=976, D _c=1.744 g·cm -3 , μ (Mo Kα)=1.166 mm -1 . Positional and thermal parameters were refined by the full-matrix least-squares method. All the non-hydrogen atoms were refined anisotropically but the hydrogen atoms were refined isotropically with the final factor values of R _1=0.0337 and wR _2=0.0857. In the title compound, methylcarbazate serves as a bidentate ligand coordinating to the nickel cation with oxygen atom from carbonyl and the nitrogen atom from hydrazine group so that a five-membered chelating ring is formed. There are three rings in the molecular structure. The coordination number is six and the configuration is octahedral. In the environment of the molecule there are two NO -_3 and one crystal water molecule, which are linked with the inside by electrostatic force and hydrogen bonds. Thermal decomposition mechanisms of the compound were characterized by using TG-DTG, DSC and IR techniques. It was confirmed that decomposing processes of the compound include one endothermal and three continuous exothermic stages, residue is NiO at 325 ℃, finally.

关 键 词：[Ni(NH2NHCO2CH3)3](NO3)2·H2O 制备 晶体结构 热分解机理 肼基甲酸甲酯 硝酸镍 配合物 

分 类 号：O627[理学—有机化学]