一氯桥双核铜配合物:Cu_2(phen)_2Cl_4的合成、晶体结构及性质研究

Study on the Crystal Synthesis,Structure and Properties of a Chloro-bridged Dinuclear Copper (Ⅱ) Complex-Cu_2(phen)_2Cl_4

本文报导了Cu2 (phen) 2 Cl4配合物的合成方法。X射线衍射分析表明标题配合物属单斜晶系 ,空间群Cc(no .9) ,晶胞参数 :a =0 .986 4 (2 )nm ,b =1.786 0 (4)nm ,c=1.3398(3)nm ,β =10 6 .6 0 (3)° ,V =2 .2 6 2 (8)nm3 ,Dc=1.84 8g/cm3 ,F(0 0 0 ) =12 5 6 ,Z =4。 30 6 4个独立衍射点中 2 812个满足F2o 2σ(F2o) ,R1和wR2 分别为 0 .0 4 82和 0 .10 6 6。标题配合物由双核 [Cu2 (phen) 2 Cl4]络分子组成 ,每个铜原子与邻菲啉配体的 2个N原子和 3个Cl原子配位形成畸变CuN2 Cl3 四方锥。配位多面体通过两氯原子形成共棱的Cu2 N4Cl6双四方锥。通过氢键和芳环堆积作用 ,络分子形成三维网络结构。标题配合物为顺磁物质 ,在 5～ 30 0K区间内遵循Curie Weiss定律 ,χm(T +0 .6 4 9) =0 .4 0 5cm3 ·K·mol-1(χm 为每摩尔Cu2 + 离子磁化率 ) ,其Cu2 + 离子的室温有效磁矩为 1.8B .M .,与Cu2 + 自由离子的磁矩基本相同 ,表明铜离子之间不存在磁交换作用。热分析显示该配合物在 2

The title complex was synthesized in a high yield.Single crystal X ray diffraction analyses indicated that the complex crystallizes in the monoclinic space group Cc (no.9) with the cell dimensions: a =0.9864(2)nm, b =1.7860(4)nm, c =1.3398(3)nm, β =106.60(3)°, V =2.262(8)nm 3, D c=1.848g/cm 3, F (000)=1256, Z =4, R 1=0.048 and wR 2=0.1066 for 2812 observed reflections with F 2 o2 σ(F 2 o) out of 3064 unique reflections.The crystal structure consists of the [Cu 2(phen) 2Cl 4] complex molecules,in which the Cu atoms are each coordinated by two N atoms and three Cl atoms from one phen ligand to form distorted CuN 2Cl 3 squre pyramids.Two adjacent CuN 2Cl 3 polyhedra are condensed via two bridging Cl atoms to result in an edge shared bi square pyramid.Through the intermolecular π π stacking interactions and hydrogen bondings,the complex molecules are assembled into 3D network.Cu 2(phen) 2Cl 4 is paramagnetic and obeys Curie Weiss law with χ m ( T +0.649)=0.405 cm 3·K ·mol -1 between 5 300K( χ m being magnetic susceptibility per mole Cu 2+ ions).The effective magnetic moment of 1.8 B.M.at room temperature is close to the spin only value for free Cu 2+ ion,suggesting no magnetic ordering between Cu 2+ ions.Thermogravimetric analyses showed that the title complex is stable below 290℃.