[Cu(en)_2][Cu(en)_2H_2O]_2[Cd(H_2O)PW_(11)O_(39)]·2H_2O的合成与晶体结构

Synthesis and Crystal Structure of [Cu(en)_2] [Cu(en)_2H_2O]_2 [Cd(H_2O)PW_(11)O_(39)]·2H_2O

在水热条件下,利用三缺位Keggin杂多磷钨酸盐前躯体Na9[α-PW9O34].7H2O与CuCl2、CdSO4、乙二胺反应,合成了一种新的无机-有机复合磷钨酸盐[Cu(en)2][Cu(en)2H2O]2[Cd(H2O)PW11O39].2H2O,并经红外光谱、热重分析、循环伏安、电催化等测试手段进行了表征.结果表明,标题化合物属于单斜晶系,空间群P21/c,晶胞参数:a=1.2872(2)nm,b=1.4781(2)nm,c=3.1965(5)nm,α=90.00°,β=93.270(2)°,γ=90.00°,V=6.0718(16)nm3,Z=4,Dc=3.753g/cm3,GOOF=1.015,R1=0.0653,wR2=0.1384.标题化合物分子由1个[Cu(en)2]2+、2个[Cu(en)2H2O]42+、1个镉取代的杂多阴离子[Cd(H2O)PW11O39]6-及2个H2O组成,并通过铜氧弱作用及氢键形成超分子网络.

An inorganic-organic composite new mono-nuclearcluster [Cu（en）2H2O]3 [Cd（H2O）PW11O39]is synthesized by reaction of trivacant Keggin polyoxotungstate precursor Na9[α-PW9O34]·7H2O,CuCl2,CdSO4 and ethylenediamine（en） under hydrothermal conditions and characterized by IR spectrum,thermogravimetric analysis and cyclic voltammetry.The result of X-ray single-crystal diffraction indicates that the title compound crystallizes in the monoclinc space group with a=1..2872（2） nm,b=1.4781（2） nm,c=3.1965（5）nm,α=90.00°, β= 93.791（2）°,γ=90.00°,V =6.0718（16） nm3,Z = 4,Dc=3.753 g/cm3,GOOF=1.015,R1=0.0653,wR2=0.1384.X-ray single-crystal structural analysis displays that the title compound consists of one [Cu（en）2]2＋ cation,two [Cu（en）2H2O]4＋2 cations,one Cd2＋ substituted polyoxoanion [Cd（H2O）PW11O39]6-and two water,and these fragments are linked into supramolecular network through metal-oxygen weak interactions and hydrogen bonds.