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出 处:《无机化学学报》2014年第7期1712-1718,共7页Chinese Journal of Inorganic Chemistry
基 金:国家自然科学基金(No.21301064);河南省基础与前沿技术研究(No.132300410413)资助项目
摘 要:在水热条件下,利用2,5-二甲基苯-1,4-二亚甲基二膦酸(H4L)与CoCl2·6H2O或NiSO4·6H2O反应得到2个同构的过渡金属有机膦酸化合物,[Co(H2O)4(H2L)]n(1),[Ni(H2O)4(H2L)]n(2),并用元素分析、红外光谱、粉末及单晶X-射线等方法对其进行了表征。晶体结构分析表明:化合物1和2都属于三斜晶系,空间群为P1,化合物1的晶胞参数为a=0.497 0(2)nm,b=0.711 3(3)nm,c=1.177 8(5)nm,α=97.779(7)°,β=92.103(7)°,γ=107.217(6)°,V=0.3927(3)nm3,Z=2;化合物2的晶胞参数为a=0.494 35(19)nm,b=0.708 9(3)nm,c=1.172 6(5)nm,α=97.919(6)°,β=92.130(6)°,γ=107.441(5)°,V=0.387 0(3)nm3,Z=2。金属离子采取了八面体构型,6个配位氧原子分别来自2个反式构型的H2L配体和4个配位水分子。每1个金属离子与2个反式构型的H2L配体配位形成了一维线型链状结构。这2个化合物最终通过O-H…O氢键作用形成了三维结构。此外,对2个化合物的热稳定性也进行了研究。Two new isostructural cobalt and nickel phosphonates [M(H2O)4(H2L)]n, M=Co (compound 1) , M--Ni (compound 2) have been hydrothermally synthesized from 2,5-dimethylbenzene-1,4-diylbis (methylene) diphosphonic acid (H4L) and the corresponding metal salts. And the compounds 1 and 2 have been characterized by routine elemental analyses, 1R, powder and single-crystal X-ray diffraction methods. Both compounds crystallize in triclinic space group P1^- with a=0.497 0(2) nm, b=0.711 3(3) nm, c=1.177 8(5) nm, α=97.779(7)°, β=92.103(7)°, γ=107.217(6)°, V=0.3927(3) nm^3 and Z=2 for 1, a=0.494 35(19) nm, b=0.708 9(3) nm, c=1.172 6(5) nm, α=97.919(6)°, β=92.130(6)°, γ=107.441(5)°, V=0.387 0(3) nm3 and Z=2 for 2. Metal ion have all octahedral geometry coordinated to six oxygen atom from two trans-H2L ligands and four coordinated water molecules. Each metal ion is coordinated to two trans-H2L ligands thereby generating an infinite one-dimensional (1D) linear chain. Finally, all the compounds show three-dimensional (3D) network through O-H … O hydrogen bonds. Thermal stability of compounds 1 and 2 have also been investigated.
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