摘要
利用X-射线单晶衍射技术测定了香草醛缩氨基硫脲合镍(Ⅱ)配合物甲醇溶剂化物Ni(C9H10N3O2S)2.4CH3OH)的单晶结构。测定结果表明,该晶体属单斜晶系,C2/c空间群,晶胞参数分别为a=2.571 2(6),b=0.730 41(18),c=1.656 3(4)nm,β=104.212(4)°,V=3.015 4(13)nm3,Z=4.在晶体结构中,中心离子Ni(Ⅱ)与2个配体中的N、S原子形成四配位的平面四边形结构,配体在与Ni(Ⅱ)配位时,其结构发生硫酮式与硫醇式互变异构,最终以硫醇阴离子形式与Ni(Ⅱ)配位,因而得到中性配位单元.相邻配位单元通过N3-H3A…S1氢键形成一维链状结构;甲醇分子既作为质子的受体又作为质子的给体,每个配位单元通过多重O-H…O、N-H…O氢键形成溶剂化物,生成沿ab平面的氢键二维结构;计算表明,包结在其中的甲醇客体构成一维孔道结构,占据晶格体积的35.4%.
The title compound,[Ni（C9H10N3O2S）2]·4CH3OH is synthesized and characterized by X-ray diffraction analysis.The crystal is monoclinic space group C2/c with a=2.571 2（6）,b=0.730 41（18）,c=1.656 3（4） nm,β=104.212（4）°,V=3.015 4（13） nm3,Z=4.The results show that the Ni（Ⅱ） is four-coordinated with two N atoms and two S atoms from two vanillin thiosemicarbazone ligands giving a quadrangle coordination structure.With thione-thiol tautomerization taking place,the ligands coordinate to Ni（Ⅱ） center in the anionic form.Having plenty of active hydrogenbonding sites,the ligands act as either proton acceptor or donor encapsulated methanol solvent aggregates within its crystal lattice by hydrogen bonds.Resulting in a porous crystal structure of Ni（Ⅱ） complex,the size of formed channels corresponds to 35.4% of the unit-cell volume,which depends on the type of substituents on phenyl group of ligand and the volume of the solvent.
出处
《天津师范大学学报（自然科学版）》
CAS
北大核心
2010年第3期64-68,80,共6页
Journal of Tianjin Normal University：Natural Science Edition
关键词
镍配合物
互变异构
孔道结构
氢键
nickel complex
tautomerization
porous
hydrogen bond
