配合物{[Cu(hmtade)][Ni(dmit)2]}2·4DMSO的合成、表征及晶体结构

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=1.558 Mg/m3, Z=8, F(000)=3944, μ(Mo Kα)=1.637 mm-1, S=1.016, (Δ/σ)max=0.001, R1=0.0673, wR2 =0.1672I>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.

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

A new complex { Cu (hmtade)] Ni (dmit) _2] } _2 · 4DMSO ( 1 ) ( hmtade = 5,7,7,12,14,14-hexamethyl- 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, Ultravioletvisible spectroscopy, and X-ray structure analysis. Complex 1 belongs to monoclinic system, space group P2_1/n with a=1.49952(6) nm, b=1.77229(7) nm, c=3.1275(1) nm, β=102.442(1)°, V=8.1163(5) nm~3, D =1.558 Mg/m~3, Z=8, F(000) =3944, /μ(Mo Kα) =1.637 mm-1, S=1. 016,(△/σ)_(max) =0. 001, and final R1 =0. 0673, wR2 =0. 1672I>2_σ(I)]. Two independent structural units of Cu(hmtade)] Ni(dmit)_2] are found in an asymmetric unit along with four DMSO solvent molecules. Sulfur-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)-0. 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 intramoleeular S…S and S…H short contacts. Finally, one-dimensional zigzag chain, two-dimensional and three-dimensional networks are formed via S…S, S…C or C…H short contacts.