含能化合物(AIM)NO_3与(AIM)(HTNR)·H_2O的合成、晶体结构及性质研究

Synthesis, Crystal Structure and Thermal Analysis of Two New Energetic Compounds (AIM)NO_3 and (AIM)(HTNR)·H_2O

利用2-叠氮咪唑(AIM)与硝酸(HNO3)和斯蒂芬酸(TNR),采用直接法合成了新型含能化合物2-叠氮咪唑硝酸盐和2-叠氮咪唑斯蒂芬酸合水,利用缓慢蒸发溶剂法培养出了可用于X射线衍射的单晶.利用X射线单晶衍射测定了标题化合物的结构,并利用元素分析和红外光谱的方法对其组成进行了表征.实验研究表明2-叠氮咪唑硝酸盐晶体属于单斜晶系,空间群为P21/c,晶胞参数为a=17.034(3),b=6.5214(13),c=13.095(3),β=111.78(3)°,V=1350.8(5)3;Dc=1.693g/cm3;分子式为C3N6O3H4,是由AIM+和NO-3结合成的离子化合物,分子中含有大量的氢键,结构较为稳定.2-叠氮咪唑斯蒂芬酸合水晶体属于三斜晶系,空间群为P1,晶胞参数为a=6.4900(13),b=7.4286(15),c=15.401(3),α=101.57(3)°,β=98.56(3)°,γ=99.89(3)°,V=703.6(2)3;Dc=1.757g/cm3;分子式为C9H8N8O9,是由AIM+和HTNR-结合成的离子合水化合物.利用差示扫描量热法(DSC)和热重-微分热重法(TG-DTG)对其热分解进行分析,结果表明,在10℃/min的升温速率下,两个化合物的热分解均出现1个放热峰,分解产物主要为气体物质.最后对标题化合物进行感度性能测试,结果表明(AIM)NO3具有一定的火焰感度,有望作为含能材料应用于相关领域.

Two new energetic compounds （AIM）NO3 and （AIM）（HTNR）·H2O have been prepared directly by reacting 2-azidoimidazolium with HNO3 and 2,4,6-trinitroresorcinol （TNR）. Single crystals suitable for X-ray measurement were obtained. The compounds were characterized by elemental analysis, fourier trans-form infrared （FTIR） spectra, single crystal X-ray diffraction, differential scanning calorimetry （DSC）, and thermogravimetry-differential thermogravimetry （TG-DTG） analysis. （AIM）NO3 belongs to a monoclinic system with P21/c space group and cell parameters of a=17.034（3）, b=6.5214（13）, c=13.095（3）, β=111.78（3）°, V=1350.8（5） nm3; Dc=1.693 g/cm3. The compound is formed by AIM＋ and NO-3, and belongs to an ionic compound. There are a lot of intramolecular and intermolecular hydrogen bonds existing in the compound, which makes the compound more stable. （AIM）（HTNR）·H2O belongs to a triclinic system with P1 space group and cell parameters of a=6.4900（13）, b=7.4286（15）, c=15.401（3）, α=101.57（3）°, β=98.56（3）°, γ=99.89（3）°, V=703.6（2）3; Dc=1.757 g/cm3. The compound is formed by AIM＋ and HTNR-, and belongs to an ionic compound. Under nitrogen atmosphere with a heating rate of 10 ℃/min, the thermal decomposition of the title compounds show that there is only one exothermic proc-ess with released gas, respectively. Sensitivities of the title compounds have been studied and the result show that （AIM）NO3 has good flame sensitivity.