摘要
以异烟酸和1,10-邻菲啰啉为配体通过水热反应合成了化学合物Mn(C6H4O2N)2(H2O)4,首次用X-射线单晶衍射仪测定了其晶体结构,同时使用G03程序对该化合物进行了量子化学计算,探讨了化合物的Wiberg键级、电荷布居及前线分子轨道的能量、原子轨道布居规律。结果表明:该晶体属三斜晶系,空间群P?1,晶胞参数为:a=0.6347(3)nm,b=0.6922(3)nm,c=0.9286(4)nm,α=96.226(7)o,β=104.929(6)o,γ=112.939(6)o,V=0.3529(3)nm3,Dc=1.747g/cm3,Z=1,F(000)=191。最终偏离因子R1=0.0457,wR2=0.1368。在标题化合物中2个异烟酸根的2个氮原子及4个水分子与Mn(Ⅱ)配位,形成了六配位的变形八面体结构。标题化合物的总能量为-688.6472au,最高占据轨道HOMO的能量为-0.29657a.u,最低空轨道LUMO的能量为-0.00904a.u,两前沿轨道的能量间隙为0.30561a.u。其能级间隙值较大,说明标题化合物基态的稳定性较好;同时其Wiberg键级及电荷布居的数据与晶体测试结果相吻合,表明理论化学的方法应用于该化合物结构的研究较令人满意。
The title compound Mn（C6H4O2N）2（H2O）4 with 4-pyridinecarboxylic acid and 1,10-phenanthroline has been synthesized and characterized by hydrothermal synthesis.For the first time,its crystal structure has been determinted by the X-ray diffraction determination.The quantum chemical calculation of the title compound has been performed by G03W program.The wiberg bond order,mulliken atomic charge of the compound and the energy,proportion of its frontier molecular orbital have also been discussed.The result shows that the crystal belongs to triclinic,space group P？1,a =0.634 7（3） nm,b=0.692 2（3） nm,c=0.928 6（4） nm,α=96.226（7）o,β=104.929（6）o,γ=112.939（6）o,V=0.352 9（3） nm3,Dc=1.747 g/cm3,Z=1,F（000）=191,R1=0.045 7,wR2=0.136 8.The crystal structure shows that the manganese（Ⅱ） is coordinated with two nitrogen atoms from two 4-pyridinecarboxylic acid and four oxygen atoms from four water to forming distorted octahedral coordination geometry.The energy of the title compound is-688.647 2 au that of HOMO and LUMO are-0.296 57 a.u and-0.009 04 a.u,respectively,and their energy gap is 0.305 61 a.u,indicating that the ground state of the title compound has good stability.The date of the wiberg bond and mulliken atomic charge are consistent with sturctural determination of the title complex,which shows that it is satisfacted that the theoretical chemistry method was applied to study the structure of the compound.
出处
《计算机与应用化学》
CAS
CSCD
北大核心
2010年第12期1669-1672,共4页
Computers and Applied Chemistry
基金
衡阳阳市科技计划项目(2009KJ26)
湖南省重点建设学科资助项目
关键词
异烟酸
水热合成
晶体结构
量化计算
4-pyridinecarboxylic acid
hydrothermal synthesis
crystal structure
quantum chemical calculation
作者简介
联系人：杨颖群（1970-），女，祁阳人，副教授．E-mail：yyingqun@126．com．
