两个三环己基锡吡啶羧酸酯化合物的合成、结构及量子化学研究

Synthesis,Crystal Structure and Quantum Chemistry of Two Tricyclohexyltin Pyridinecarboxylate Complexes

以2-氯烟酸(ClPyCOOH)、吡啶-3-甲酸(PyCOOH)分别与三环己基氢氧化锡反应,合成了两个三环己基锡杂环羧酸酯[Cy3Sn(ClPyCOO)(H2O)](1),[Cy3Sn(PyCOO)(H2O)](2)(Cy为环己基)。经IR、1H NMR、元素分析和X射线衍射表征结构。配合物均属单斜晶系,空间群C2/c。晶体学参数:化合物1,a=2.018 97(5)nm,b=1.361 16(4)nm,c=1.957 58(5)nm,β=104.815 0(10)°,Z=8,V=5.200 9(2)nm3,Dc=1.386 g.cm-3,μ(Mo Kα)=1.108 mm-1,F(000)=2 240,R1=0.043 7,wR2=0.138 0。化合物2,a=2.005 44(14)nm,b=1.355 58(10)nm,c=1.911 38(14)nm,β=107.260(3)°,Z=8,V=4.962 2(6)nm3,Dc=1.361 g.cm-3,μ(Mo Kα)=1.052 mm-1,F(000)=2 112,R1=0.035 2,wR2=0.112 5。中心锡原子均为五配位三角双锥构型。分子间存在氢键作用,配合物1、2分别形成二维结构。利用量子化学G98W软件,在LANL2DZ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。

Two tricyclohexyltin heteroaromatic carboxylates [Cy3Sn（ClPyCOO）（H2O）]（1）,[Cy3Sn（PyCOO）（H2O）]（2）（Cy=cyclohexyl） were synthesized by the reactions of 2-chloronicotinic acid（ClPyCOOH） and nicotinic acid（PyCOOH） with tricyclohexyltin hydroxide,respectively.The structures have been characterized by IR,1H NMR spectra and elemental analysis.Theirs crystal structures have been determined by X-ray diffraction.The crystals both belong to monoclinic system,space group C2/c.The crystallographic parameters of complex 1： a=2.018 97（5） nm,b=1.361 16（4） nm,c=1.957 58（5） nm,β=104.815 0（10）°,Z=8,V=5.200 9（2） nm3,Dc=1.386 g·cm-3,μ（Mo Kα）=1.108 mm-1,F（000）=2 240,R1=0.043 7,wR2=0.138 0.The complex 2： a=2.005 44（14） nm,b=1.355 58（10） nm,c=1.9113 8（14） nm,β=107.260（3）,Z=8,V=4.962 2（6） nm3,Dc=1.361 g·cm-3,μ（Mo Kα）=1.052 mm-1,F（000）=2 112,R1=0.035 2,wR2=0.112 5.The tin atoms of two complexes are five-coordinated trigonal bipyramid configuration.The 2D network structures of two complexes are formed by the hydrogen bonds.The stabilities,the orbital energies and composition characteristics of some frontier molecular orbitals of the complexes have been investigated with the aid of G98W software.CCDC： 809069,1;832584,2.