DNAZ酰基衍生物的分子结构及量子化学研究

Molecular Structure and Quantum Chemical Investigation of Acyl Derivatives of DNAZ

合成了3,3-二硝基氮杂环丁烷(DNAZ)的酰基衍生物N-乙酰基-3,3-二硝基氮杂环丁烷(ADNAZ)和N-甲酰基-3,3-二硝基氮杂环丁烷(FDNAZ),并得到可用于X射线衍射的单晶.ADNAZ属于正交晶系,P212121空间群,晶胞参数a=0.6844(3)nm,b=0.6994(3)nm,c=1.6948(6)nm,V=0.8112nm3,Z=4.FDNAZ属于单斜晶系,P21/c空间群,晶胞参数a=1.0322(4)nm,b=0.6054(2)nm,c=1.1268(4)nm,β=100.135(5)°,V=0.6932nm3,Z=4.用ADF(Amsterdam density functional)的DFT(Density functional theo-ry)方法对两个化合物进行了几何优化和频率计算,得到了其几何构型参数、原子Hirshfeld电荷、原子间Mayer键级和前线轨道能量及组成.理论分析表明,两个化合物中活性较大的原子均为酰基氧原子.

N-acetyl-3,3-dinitroazetidine （ADNAZ） and N-formyl-3,3-dinitroazetidine （ FDNAZ）, acyl derivatives of 3,3-dinitroazetidine（DNAZ） were prepared. Single crystals suitable for X-ray measurement were obtained. ADNAZ crystallizes in the orthorhombic system, space group P212121 with unit cell parameters α = 0. 6844（3） nm, b =0. 6994（3） nm, c = 1. 6948（6） nm, V=0. 8112 nm^3, Z =4. FDNAZ crystallizes in the monoelinie system, space group P21/c with unit cell parameters α= 1. 0322 （4） rim, b = 0. 6054 （2） nm, c = 1. 1268 （4） nm, β = 100. 135 （ 5 ）°, V = 0. 6932 nm^3, Z = 4. The density functional theory （DFT） method of the Amsterdam density functional （ADF） was used to calculate the geometry and frequency of the two derivatives. The geometry, Hishfeld charges of atoms, Mayer bond orders, frontier orbital energy and the main atomic orbital percentage were calculated. The analytical results indicate that the oxygen atom of acyl group is an active atom for ADNAZ and FDNAZ.