物理化学学报 >> 2010, Vol. 26 >> Issue (09): 2410-2416.doi: 10.3866/PKU.WHXB20100919

结构化学 上一篇    下一篇

[Mn(AZT)2(H2O)4] (HTNR)2·4H2O的合成、晶体结构、热行为及感度性质

冯金玲1, 张建国1, 张同来1, 崔燕2   

  1. 1. 北京理工大学爆炸科学与技术国家重点实验室,北京100081;
    2. 防化研究院第六研究所, 北京102205
  • 收稿日期:2010-04-01 修回日期:2010-05-23 发布日期:2010-09-02
  • 通讯作者: 张建国, 张同来 E-mail:zhangjianguobit@yahoo.com.cn; ztlbit@bit.edu.cn
  • 基金资助:

    国家自然科学基金(20471008)和教育部新世纪优秀人才支持计划(NCET-09-0051)资助项目

Synthesis, Crystal Structure, Thermal Behavior and Sensitivity of [Mn(AZT)2(H2O)4] (HTNR)2·4H2O

FENG Jin-Ling1, ZHANG Jian-Guo1, ZHANG Tong-Lai1, CUI Yan2   

  1. 1. State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081, P. R. China;
    2. The 6th Department, Research Institute of Chemical Defense (PLA), Beijing 102205, P. R. China
  • Received:2010-04-01 Revised:2010-05-23 Published:2010-09-02
  • Contact: ZHANG Jian-Guo, ZHANG Tong-Lai E-mail:zhangjianguobit@yahoo.com.cn; ztlbit@bit.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (20471008) and Programfor NewCentury Excellent Talents in Universities of the Ministry of Education of China (NCET-09-0051).

摘要:

通过酸性2,4,6-三硝基间苯二酚(HTNR)的锰盐与3-叠氮-1,2,4-三唑(AZT)在水溶液中反应, 制备得到一种新颖的锰配合物[Mn(AZT)2(H2O)4] (HTNR)2·4H2O. 通过元素分析和红外光谱对配合物进行了表征, 用X 射线单晶衍射分析确定其晶体结构. 该配合物为三斜晶系, 空间群为Pī, 中心锰(II)离子为六配位的畸变的八面体结构, 分子内和分子间强烈的氢键作用构成了有序的三维(3D)网状结构. 采用差示扫描量热(DSC)和热重-微分热重(TG-DTG) 分析技术研究了配合物的热分解特性, 并预测了它的热分解反应机理. 利用Kissinger 方法和Ozawa-Doyle 方法研究了其第一放热分解峰的分解动力学过程. 其分解过程包括一个吸热峰和三个放热峰, 在600 益的分解产物为MnO 和MnO2的混合物. 同时. 对这个配合物进行了感度(撞击感度、火焰感度、摩擦感度)性能分析, 结果表明, 它对外界刺激具有很强的响应性和选择性.

关键词: 晶体结构, 3-叠氮-1,2,4-三唑, 锰(II)配合物, 感度, 热行为

Abstract:

A novel energetic coordination complex of [Mn(AZT)2(H2O)4] (HTNR)2·4H2O (AZT=3-azido-1,2,4- triazole, HTNR=2,4,6-trinitro resorcinol) was prepared by the reaction between the acidic manganese (II) salt of 2,4,6-trinitro resorcinol and AZT in an aqueous solution. The complex was characterized by elemental analysis and FTIR spectroscopy. The molecular structure was determined by X-ray single crystal diffraction. The crystal belongs to the triclinic systemwith a Pī space group. The central manganese(II) cation has a slightly distorted octahedron feature. Three-dimension networks were formed and the layers are linked by extensive hydrogen bonding. The thermal decompositionmechanismof [Mn(AZT)2(H2O)4] (HTNR)2·4H2O was predicted based on differential scanning calorimetry (DSC) and thermogravimetry-derivative thermogravimetry (TG-DTG) analyses. One endothermic peak and three exothermic peaks are present during the thermal decomposition process with the final residue at 600 ℃being MnO and MnO2. The kinetic parameters of the exothermic process for the complex were studied using Kissinger's and Ozawa- Doyle's methods. Furthermore, impact sensitivity, flame sensitivity, and friction sensitivity tests reveal that the title complex is sensitive and selective towards external stimulants.

Key words: Crystal structure, 3-Azido-1,2,4-triazole, Manganese(II) complex, Sensitivity, Thermal behavior

MSC2000: 

  • O641