2-氨基-3H-吩噁嗪-3-酮的溶剂热法合成、晶体结构及密度泛函理论研究

Solvothermal synthesis,crystal structure and density functional theory research of 2-amino-3H-phenoxazin-3-one

采用溶剂热法合成了2-氨基-3H-吩噁嗪-3-酮,并通过红外光谱、元素分析、x射线单晶衍射进行了结构表征。结构解析表明,该晶体属于单斜晶系,P2_1/c空间群,晶胞参数为a=1.29322(10)nm,b=0.50832(4)nm,c=1.47609(11)nm,β=99.323(1)°,V=957.52(13) A^3,Z=4,Dc=1.472 Mg/m^3,F(000)=440,μ=0.10 mm^(-1),Mr=212.20,最终偏差因子(对I>2σ(I)的衍射点)R_1[F^2>2σ(F^2)]=0.037,wR_2(F^2)=0.097(对全部衍射点),权重方案w^(-1)=1/[σ~2(Fo^2)+(0.0402P)~2+0.2667P],P=(Fo^2+2Fc^2)/3。该化合物分子由3个共轭环形成几乎共平面的结构。应用密度泛函理论DFT方法,结合6-31*基组优化了几何构型,通过同一水平的振荡分析和单点能分析得出热力学参数、净电荷分布和原子轨道对分子轨道的贡献。

Abstract： 2-amino-3H-phenoxazin-3-one was synthesized by solvent-thermal method. The structure was characterized by elemental analysis, IR spectrum and X-ray diffraction. The result indicates that the crystal belongs to monoclinic space group P21/c with the cell parameters： a=1.29322（10） nm, b=0.50832（4） nm, c=1.47609（11） nm, β=99.323（1）°, V=957.52（13） A3, Z=4, Dc=1.472 Mg/m^3, F（000）=440, p=0.10 mm^-1, Mr=-212.20; Final indices[I〉2sigma（I）]R1[F^2〉2a（F2）]=0.037, wR2（F2）=0.097[all data],weighting scheme w^-1=/[σ^2（Fσ2）＋（0.0402p）2＋0.2667P], P=（Fo2＋2Fc2）/3. The compound consists of three nearly coplanar conjugated rings. DFT method and 6-31 ＊ levels were employed to optimize its geometry. Via the single-point energy and vibration analysis at the same level, thermodynamic parameters, mulliken charge distribution and contribution of atomic orbitals to some frontier molecular orbitals were obtained.