二维网状结构双核配合物[Ca_2(C_(10)H_8N_2O_4)_2(DMSO)_2(H_2O)_4]·2DMSO的合成、热分解及晶体结构

Synthesis, Thermal Decomposition and Crystal Structure of Two-Dimensional Net work Binuclear Complex [Ca_2(C_(10)H_8N_2O_4)_2(DMSO)_2(H_2O)_4]·2DMSO

以 2 羰基丙酸水杨酰腙 (C10 H10 N2 O4)作为配体与碳酸钙在水中反应 ,在DMF (N ,N 二甲基甲酰胺 )和DMSO (二甲基亚砜 )的混合溶剂中培养了单晶 ,其组成为 [Ca2 (C10 H8N2 O4) 2 (DMSO) 2 (H2 O) 4 ]·2DMSO [C10 H8N2 O2 -4为 2 羰基丙酸水杨酰腙负离子 ] .测定了单晶的结构 ,该单晶为黄色 ,属单斜晶系 ,空间群为P2 (1) /c,晶胞参数a =1 0 63 4 (3 )nm ,b =1 70 3 5(5)nm ,c =1 2 183 (3 )nm ,β=10 6 180 (5)° ,V =2 1192 (10 )nm3,Dc=1 412Mg·m- 3 ,Z =2 ,F(0 0 0 ) =944,μ =0 53 4mm- 1,GOF =0 867.所测单晶是以 2 羰基丙酸水杨酰腙羧基上的一个氧原子作为桥联的双核钙 (II)配合物 ,两个Ca2 + 均处于五角双锥的七配位环境中 ,锥底为配体 2 羰基丙酸水杨酰腙中的三个配位原子 ,以及另一 2 羰基丙酸水杨酰腙羧基上的桥联氧原子和一个水分子的配位氧原子 ,锥顶为一配位水和一配位的DMSO分子 ,即溶剂DMSO也参与了配位 ,从晶胞结构看 ,晶体中除配位的DMSO分子外 ,还有自由的DMSO溶剂分子 ,它们与配位水以氢键连接存在于晶格之中 ,在空间形成了二维网状结构 .通过TG

In water, a calcium(Ⅱ) complex with 2-oxo-propionic acid salicyloyl h ydrazon (C 10 H 10 N 2O 4) has been synthesized. The yellow crystals o f the calcium(Ⅱ ) complex was obtained in a mixed solvent of DMF and DMSO. The formula of the co mplex is [Ca 2(C 10 H 8N 2O 4) 2(DMSO) 2(H 2O) 4]·2DMSO (C 10 H 8N 2O 2- 4 is the dinegative io n of 2-oxo-propionic acid salicyloyl hydrazone). The crystal structure was det er mined by X-ray single crystal diffraction analysis. The results show that the c o mplex is monoclinic of space group P 2(1)/c, the cell parameters are as follows: a= 1 0634(3) nm, b=1 7035(5) nm, c=1 2183(3) nm, β=106 180(5)°, V=2 119 2(10) nm 3, D c=1 412 Mg· m -3 , Z=2, F(000)=944, μ= 0 534 mm -1 , GOF=0 8 67. The complex is a binuclear Ca complex, with one O atom of the carboxyl of 2 -o xo-propionic acid salicyloyl hydrazone bridging two Ca. Each Ca atom is pentago n al bipyramid coordinated by two O atoms and one N atom of tridentates C 10 H 8N 2O 2- 4 ligand, one O atom of DMSO molecule and the O atoms of two H 2O. One H 2O an d on e DMSO locate at the apical position. In the crystal cell, there are free DMSO w hich are connected with H 2O by hydrogen bonds. Because of the hydrogen bonds t he complex formed a two -dimensional network structure in space. The thermal stability of the complex was studied by TG-DTG analysis.