配合物{[Cu(hmtade)][Ni(dmit)_2]}_2·4DMSO的合成、表征及晶体结构

Synthesis,Characterization and Crystal Structure of Complex {[Cu(hmtade)][Ni(dmit)_2]}_2·4DMSO

合成了配合物{[Cu(hmtade)][Ni(dmit)2]}2.4DMSO(1)(hmtade为5,7,7,12,14,14-六甲基-1,4,8,11-四氮杂环十四-4,11-二烯;dmit为1,3-二硫杂环戊二烯-2-硫酮-4,5-二硫醇;DMSO为二甲亚砜),采用元素分析、红外光谱和紫外-可见光谱进行了表征,并用X射线衍射法测定了晶体结构.该晶体属于单斜晶系,P21/n空间群;晶胞参数:a=1.49952(6)nm,b=1.77229(7)nm,c=3.1275(1)nm,β=102.442(1)°,V=8.1163(5)nm3,Dc=1.558Mg/m3,Z=8,F(000)=3944,μ(MoKα)=1.637mm-1,S=1.016,(Δ/σ)max=0.001,R1=0.0673,wR2=0.1672[I>2σ(I)].晶体结构研究表明,配合物{[Cu(hmtade)].[Ni(dmit)2]}2.4DMSO包含2个[Cu(hmtade)][Ni(dmit)2]子单元.每个子单元中,1个dmit中的1个S原子与Cu及Ni配位,形成异双核Cu—Ni配合物.其中Cu(Ⅱ)为五配位的四方锥构形,Cu—N键长在0.1949(5)～0.2007(4)nm范围内,Cu—S键长分别为0.28913(18)和0.28952(18)nm;配阴离子[Ni(dmit)2]2-为畸变四方形,Ni—S键长在0.21729(16)～0.21905(17)nm范围内.溶剂分子DMSO与配体hmtade形成了N—H…O氢键.通过分子内S…S和S…H短接触形成了二聚体,二聚体之间通过S…S短接触形成一维链状结构,并通过S…S,S…H和C…H短接触进一步形成二维和三维结构.

A new complex { [ Cu（hmtade） ] [ Ni（dmit） 2 ]} 2 · 4DMSO（ 1 ） （ hmtade = 5,7,7,12,14,14-hexa- methyl- 1,4,8,11-tetraazacyclotetradeca-4,11-diene, dmit = 4,5-dimercapto-1,3-dithiole-2-thione, DMSO = dimethyl sulfoxide） was synthesized and characterized by means of elemental analysis, Infrared, Ultraviolet- visible spectroscopy, and X-ray structure analysis. Complex 1 belongs to monoclinic system, space group P21/nwitha=l.49952（6） nm, b =1.77229（7） nm, c=3.1275（1） nm, β=102.442（1）°, V= 8. 1163（5） nm3, Dc = 1.558 Mg/m3, Z =8, F（000） =3944, /z（Mo Ka） = 1. 637 mm-1, S = 1. 016, （△/σ）max =0. 001, and final R1 =0. 0673, wR2 =0. 1672[I 〉2σ（I） ]. Two independent structural units of [Cu（hmtade） ] [Ni（dmit）2] are found in an asymmetric unit along with four DMSO solvent molecules. Sul- fur-bridged heterometal Cu--Ni complex is formed by one dmit ligand of [ Cu （hmtade）] [ Ni （dmit）2 ]- The copper（ Ⅱ ） ion is a five coordinated square pyramidal environment, with Cu--N distances in the region of 0. 1949（5）--0. 2007（4） nm and Cu--S distances of 0. 28913（ 18）-0. 28952（18） nm. The nickel（ Ⅱ ） ion which is coordinated by four sulfur atoms of two dmit ligands is in the distorted square geometry, and the Ni--S distances fall in the range of 0. 21729 （ 16 ）--43. 21905 （ 17 ） nm. The N--H＇＂O hydrogen bonds are formed between the nitrogen atom of hmtade ligand and DMSO solvent molecule, and the dimmer is formed through intramolecular S...S and S...H short contacts. Finally, one-dimensional zigzag chain, two-dimensional and three-dimensional networks are formed v/a S...S, S...C or C...H short contacts. ＂