铜(Ⅱ)与咪唑及2-羰基丙酸水杨酰腙混配体配合物的合成、晶体结构及热分解研究

Synthesis, Crystal Structure and Thermal Decomposition of Copper(Ⅱ) Complex with Imidazole and 2-Oxo-propionic Acid Salicyloyl Hydrazone

以 2 羰基丙酸水杨酰腙、咪唑与五水硫酸铜在水中反应 ,首次制得混配体配合物Cu(C10 H8N2 O4) (C3 H4N2 ) (H2 O)[C10 H8N2 O42 -为 2 羰基丙酸水杨酰腙负离子 ;C3 H4N2 为咪唑 ] ,并在甲醇溶剂中培养出单晶 .该单晶为深绿色 ,属单斜晶系 ,空间群为P2 ( 1) /c ,晶胞参数a =1.5 0 5 83 ( 5 )nm ,b =1.0 8411( 3 )nm ,c =0 .943 66( 2 )nm ,α =90° ,β =10 1.5 5 83 ( 11)° ,γ =90° ,V =1.5 0 92 7( 7)nm3 ,Z =4,μ =1.479mm-1,Dc=1.62 8Mg/m3 ,F( 0 0 0 ) =75 6.0 0 ,R =0 .0 3 40 ,ωR =0 .0 777,GOF =1.0 2 5 .晶体测试结果表明 ,配合物中Cu(Ⅱ )的配位数为 5 ,处于四方锥配位环境 ,其中配体 2 羰基丙酸水杨酰腙的羧基以单齿配位 ,腙基上CN的N配位以及羰基 (CO)的O配位 ,咪唑的 3位N参与了配位 ,这四个配位原子处于四方锥的锥底 ,另一个配位原子来自H2 O中的O ,它处于四方锥的锥顶 .在晶胞中 ,除分子内存在氢键外 ,分子间也存在氢键 .根据TG DTG曲线研究了配合物的热分解过程 。

In water, a copper(Ⅱ) complex with 2 oxo propionic acid salicyloyl hydrazone and imidazole Cu(C 10 H 8N 2O 4)(C 3H 4N 2)(H 2O) [C 10 H 8N 2O 4 2- is the dinegative ion of 2 oxo propionic acid salicyloyl hydrazone, C 3H 4N 2 is imidazole] has been synthesized. The dark green crystals of the complex were obtained in methanol, and the crystal structure was determined by single crystal X ray diffraction analysis. The results show that the complex is monoclinic of space group P 2(1)/ c , the cell parameters are as follows: a =1.50583(5) nm, b =1.08411(3) nm, c = 0.94366(2) nm, α =90°, β =101.5583(11)°, γ =90°, V =1.50927(7) nm 3, Z =4, μ =1.479 mm -1 , D c= 1.628 Mg/m 3 , F (000)=756.00, R =0.0340, ωR =0.0777, GOF =1.025. In the complex, Cu atom is square pyramidally coordinated by carboxyl monodentate ligand, one N atom of hydrazone CN and one O atom of carbonyl of 2 oxo propionic acid salicyloyl hydrazone, one N atom of imidazole, these four atoms are located at the bottom of the square pyramid, the other coordinating atom is O atom of H 2O locating at the apical position. In the crystal, there are hydrogen bonds either in or between the molecules. The thermal decomposition for the complex was studied and the apparent activation energy was obtained by the Kissinger formulae.