三环己基锡吡啶-4-甲酸酯聚合物的合成、结构和量子化学研究

摘要

The tricyclohexyltin pyridine-4-carboxylate polymer [Cy3Sn (O2CC5H4N)]n (Cy=cyclohexyl) has been synthesized via the reaction of the tricyclohexyltin hydroxide with the pyridine-4-carboxylic acid, and the structure has been characterized by IR, 'H NMR spectra and elemental analysis. The crystal structure has been determined by X-ray diffraction. Its crystal belongs to monoclinic system, space group Pllc with a= 1.222 4 (4) nm, b=O.98O9(5) nm, c=2.089 9(9) nm,/3=107.238(3)°, Z=4, V =2.393 6(4) nm3, Dc=1.360 g-cnr3,μ(Mo Ka)=l.O85 mm-1, F(000)= 1016, R1=O.O28 2, Wr2=0 068 4. In the complex, tin atoms are five-coordinated trigonal bipyramid configuration with linked to oxygen and nitrogen atom of pyridine-4-carboxylic acid. A "double-chain" structure of the adjacent chains is formed, through the C-H···O hydrogen bonds. Interestingly, there are σ → π effects between the Cy-H of one "double-chain" and the pyridine ring of another "double-chain", which allow the complex to form two-dimensional structure. The stabilities of the complex, the orbital energies and composition characteristics of some frontier molecular orbitals have been investigated with the aid of G98W software. CCDC: 809067.%双齿配体吡啶-4-甲酸与三环己基氢氧化锡反应,合成了三环己基锡吡啶-4-甲酸酯聚合物[Cy3Sn (02CCsH4N)]n(Cy为环己基).经IR、1H NMR、元素分析和X射线衍射表征结构,晶体结构属单斜晶系,空间群P21/c,晶体学参数:a=1.222 4(4) nm,b=0.980 9(5) nm,c=2.089 9(9) nm,β=107.238(3)°,Z＝4,V=2.393 6(4)nm3,Dc=1.360 g·cm-3,μ(Mo Kα)=1.085 mm-1,F(000)=1 016,R1=0.0282,wR2=0.0684.中心锡原子为五配位三角双锥构型,通过吡啶-4-甲酸的1个氧和吡啶氮原子配位成链.两条相邻的链之问经氢键(C-H…O)作用组成“双链”结构,“双链”之间通过环己基H与另链的吡啶环发生σ→r作用形成二维结构.利用量子化学G98W软件,在lan12dz基组对配合物的稳定性、前沿分子轨道组成及能量进行研究.