2,2’,4,4’,6,6’-六硝基二联苯的合成、晶体结构与量化计算  

Synthesis, crystal structure and theoretical calculation of 2, 2’, 4, 4’, 6, 6’-hexanitrobiphenyl

作　　者：杨峰 党鑫 李永祥 郭恒杰 柴笑笑 YANG Feng, DANG Xin, LI Yongxiang, GUO Hengjie and CHAI Xiaoxiao(School of Chemical Engineering and Technology, North University of China, Taiyuan 030051, Shanxi, Chin)

机构地区：[1]中北大学化学工程与技术学院

出　　处：《计算机与应用化学》2018年第1期72-79,共8页Computers and Applied Chemistry

摘　　要：本文以2,4,6-三硝基氯苯为原料在惰性溶剂硝基苯中经Ullmann缩合反应制备出了标题化合物2,2’,4,4’,6,6’-六硝基二联苯（HNB）,通过FT-IR、氢核磁共振谱、质谱、元素分析、X-射线单晶衍射等手段对其进行了表征,根据晶体结构数据使用G09程序对化合物的能量、分子前沿轨道、净电荷、分子静电势及Wiberg键级进行计算。结果表明,该晶体属于三斜晶系,空间群为P-1（2）,晶胞参数为：a=8.2552（8）？,b=12.2204（12）？,c=16.3239（15）？,α=98.413（3）°,β=92.635（3）°,γ=104.424（3）°,V=1571.87（30）？~3,μ=0.16 mm^（-1）,ρ=1.793 g·cm^（-3）,Z=4,F（000）=856.0。标题化合物的两个苯环接近垂直,同时每个苯环上的硝基官能团与苯环不在同一平面。标题化合物的总能量为-1690.06539 a.u.,最高占据轨道能量为-0.31512 a.u.,最低未被占据轨道能量为-0.14872a.u.,前沿轨道能量差为0.1664 a.u.,化合物具有较高的化学稳定性;标题化合物分子键级最小的键为C（5）-N（3）（0.9185）和C（11）-N（6）（0.9185）,为分子中易分解点,化合物的量化计算结果与其晶体结构数据相符。The title compound has been synthesized by the Ullmann condensation reaction with picryl chloride as raw material and characterized by FT-IR, H NMR, mass spectrometry and X-ray diffraction. The quantum chemistry calculation of the tittle compound has been performed by G09W package at the B3LYP/6- 31g （d, p） basis set. The energy, molecular frontier orbital, mulliken atomic charge, molecular electrostatic potential and bond index of the complex has also been discussed. The result shows that the crystal belongs to triclinic system with space group P-1（2） with a= 8.2552 （8） A, b= 12.2204 （12） A, c= 16.3239 （15） A, α= 98.413 （3）°, β= 92.635 （3）°, γ= 104.424 （3）°, V= 1571.87 （30） A3, μ= 0.16 mm-1, ρ= 1.793 g.cm-3, Z= 4, F（000）= 856.0. The crystal structure shows that the two benzene rings are nearly vertical with each other and the nitro groups are not coplanar with the benzene ring. The total energy of the title compound is -1690.06539 a.u. that of HOMO and LUMO is -0.31512 a.u. and -0.14872a.u. respectively, and the energy gap of MOs is 0.1664 a.u., indicating that the compound has good chemical stability. The minimum bond index of the compound is C（5）-N（3） （0.9185） and C（11）-N（6）（0.9185）, which represents the easily decomposed part of the compound. The calculated results are in good agreement with the crystal structure data.

关 键 词：六硝基二联苯 晶体结构 量化计算 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O641[理学—物理化学]