{Cu(Ⅱ)(Me_6[14]-4,11-二烯N_4)}(ClO_4)_2的晶体结构和从头算研究

Crystal Structure and Quantum Chemistry of {Cu(Ⅱ)(Me_6[14]4,11-dieneN_4)}(ClO_4)_2

Me6[14]4,11 dieneN4与Cu2+配合形成大环配合物,经X射线衍射测定其晶体结构,并用量子化学从 头算方法研究配合物的电子结构及分子轨道组成.该晶体属于单斜晶系,空间群为P21/c,晶胞参数:a= 1.0483(4),b=1.6956(2),c=1.3838(2)nm,β=105.11(2)°,V=2.37479(10)nm3,Z=4,Dc=1.518g/cm3, μ=11.92cm 1,F(000)=1132,R1=0.042.大环配体的N与Cu配合分别形成椅式六员环和半椅式五员环, N-Cu-N键角差异使中心金属原子与配基原子构成畸形四方形,两个甲基位于大环同侧形成大环的“旗杆”碳 的结构特征.

The tetraaza macrocyclic ligand, 5,7,7,12,14-hexamethyl-1,4,8,11-tetraazcyclotetradeca -4, 11-diene(Me 6[14]4,11-dieneN 4) and copper(Ⅱ) result in the formation of macrocyclic complex.The crystal structure of the macrocyclic copper complex {Cu(Ⅱ)(Me 6[14]4,11-dieneN 4)} 2+ has been determined by X-ray diffraction method.A quantum chemistry calculation is used by means of G98W package and taking LanL2DZ basis set.The crystal belongs to monoclinic space group P2 1/c with a=1.0483(4), b=1.6956(2), c= 1.3838(2)nm, β=105.11(2)°, V=2.37479(10)nm 3, Z=4, Dc= 1.518 g/cm 3, μ=11.92 cm -1, F(000)=1132, final R=0.042 for 4292 unique reflection. The title compound, {Cu(Ⅱ)(Me 6[14]4,11- diene N 4)} 2+, is a 14-membered tetraaza macrocyclic mononuclear complex in which the Cu atom is a distorted square-planar coordinated by four N atoms. The distortion of molecule is explicated by the N-Cu-N angle and by the diatance of N atoms. The macrocyclic complex is in stable folded configuration where the six-membered rings are in chair form and five-membered rings are in half-chair form. The macrocyclic complex is similar to boat conformation, while C(6) and C(15) form the structure as flagpole carbon. The non-bond distances between C(6)…C(15) is 0.437 nm.