摘要
采用水热法合成了2种新型超分子配合物[Cu(C6H4O2N)2(H2O)4](1)和[Cd(C6H4O2N)2(H2O)4](2),通过元素分析、红外光谱、热分析、X-射线衍射等技术对其进行了表征.2种配合物均属三斜晶系,空间群P1,配合物1晶胞参数a=0.7769(2)nm,b=0.9186(2)nm,c=1.0725(3)nm,α=92.905(4)°,β=95.024(4)°,γ=111.117(3)°,V=0.7085(3)nm3,Z=2,Mr=379.81,Dc=1.780 g/cm3,F(000)=390,μ=1.589 mm-1,最终偏离因子R1=0.022 4,R2=0.067 5;配合物2晶胞参数a=0.643 94(12)nm,b=0.695 98(13)nm,c=0.941 53(18)nm,α=94.878(3)°,β=104.733(3)°,γ=111.986(2)°,V=0.370 69(12)nm3,Z=1,Mr=428.67,Dc=1.920 g/cm3,F(000)=214,μ=1.518 mm-1,最终偏离因子R1=0.027 3,R2=0.074 6.配合物的中心原子M2+(M2+=Cu2+,Cd2+)与2个吡啶-4-甲酸根及4个H2O配位,形成具有畸变八面体构型的基本结构单元,相邻单元通过O—H…O氢键的相连拓展为三维超分子体系.在实验的基础上,采用密度泛函理论(DFT)的B3LYP/Lanl2dz计算方法对2种配合物进行了几何优化、前线轨道能量、单点能量等后续计算.
Two compounds [Cu（C6H4O2N）2 （H2O）4]（1）,[Cd（C6H4O2N）2 （H2O）4]（2） were synthesized through hydrothermal method. The structure was characterized by elemental analysis, IR spectroscopy, thermal analysis and single-crystal X-ray diffraction. Two complexes crystallize in triclinic system, space group P1. Crystal data of 1：a=0.776 9（2）nm, b=0.9186（2）nm, c=1.072 5（3）nm, α=92.905（4）°, β=95.024（4）°, γ=111. 117（3）°, V=0. 708 5（3）nm^3, Z=2, Mr=379.81, Dc=l. 780 g/cm^3, F（000）= 390, μ=1. 589 mm^-1 , the final RI and R2 are 0. 022 4 and 0. 067 5. Crystal data of 2：a=0. 643 94（12）nm, b= 0. 695 98（13）nm, c=0. 941 53（18）nm, α=94. 878（3）°,β=104. 733（3）°, γ=111. 986（2）°, V=0. 370 69（12）nm3, Z= 1, Mr =428. 67, Dc =1. 920 g/cm^3, F（000）=214,μ=1. 518 mm^-1 , the final R1 and R2 are 0. 027 3 and 0. 074 6. The central Cu^2＋ ,Cd^2＋ ion of two compounds were in slightly distorted octahedron geometry completed by two nitrogen atoms from two 4-Pyridinecarboxylic acid radical and four oxygen atoms from four coordinated water molecules. Through the O-H…O hydrogen bonds, the neighboring units were linked into a two-dimensional planar structure, which were further organized by different intermolecular hydrogen bonds （O-H…O） to afford a 3D supramolecular structure. On the basis of the experimentation, the structure of two complexes were optimized by using DFT（B3LYP/Lanl2dz） methods, and the energies of frontier molecular orbitals and zero-point energies of the molecule were calculated and discussed.
出处
《宁夏大学学报（自然科学版）》
CAS
北大核心
2008年第1期61-65,共5页
Journal of Ningxia University(Natural Science Edition)
基金
陕西省自然科学基金资助项目(2006B26)
陕西省教育厅科研基金资助项目(06JK155
04JS38)
关键词
吡啶-4-甲酸酐
超分子体系
氢键
水热法
晶体结构
密度泛函理论
4-pyridinecarboxylic acid anhydride
supramolecular compound
hydrogen bond
hydrothermal method
crystal structure
density functional theory
