18冠6与K_2[M(mnt)_2](M=Cu、Ni)配合物的合成与结构研究

Synthesis and Crystal Structure of 18-Crown-6 Complexeswith K_2[M (mnt)_2] (M = Cu、Ni)

研究了18冠6分别与K2[M(mnt)2][M=Cu、Ni;mnt,1,2－dicyanoethene-l,2－dithiolato,丁二腈烯二硫醇阴离子,C2S2(CN)22-]的反应,得到的配合物[K(18C6)]2 [Cu(mnt)2](1)、[K(18C6)]2[Ni(mnt)2](2)通过元素分析、红外光谱、X射线单晶衍射进行了表征。两个配合物均为三斜晶系,空间群 P－1.l的晶体学结构数据:a=1.226 97(19),b=1.227 80(19),c＝1.566 5(3)nm,α＝95.083(3),β=101.534(3),γ＝91.007(3)0 ,V＝2.301 6(6)nm3,Z=2,Dcalc.=1.350 Mg/m3 ,F(000)=976,R1=0.0726,wR2=0.184 3.2的晶体学结构数据:a=1.116 20(17),b=1.220 54(18),c=1.279 39(18)nm,α=111.647(2),β=92.792(3),γ=103.201(2)0,V=2.546 1(4)nm3,Z=1,Dcalc.=1.304 Mg/m3,F(000)=642,R1=0.045 9,wR2=0.100 3.l中的[Cu(mnt)22-通过mnt的氮原子与[Na(18C6)]+中的钠原子成键,形成了一维链状结构;[Na(18C6)(H2O)]+只起平衡电荷的作用。2中的[Ni(mnt)2]2-也通过配体的mnt氮原子与两个[Na(18C6)(H2O)]+中的钠原子成键,形成稳定的中性配合物。

The reactions of 18-crown-6 with K2M (mnt)2 (M = Cu,Ni;mnt = 1,2-dicyanoethene-l,2-dithiolate, C2S2(CN)22-) are studied and the novel complexes {[Na (18C6)]3[Na(18C6)(H2O)]}[Cu(mnt)2]2(1) and [Na(l8C6)(H2O)]2[Ni (mnt)2]·(18C6) (2) are characterized by elemental ana1ysis,IR and X-ray diffraction analysis.l and 2 belong to triclinic,space group P-1 with cel1 dimensions: l,a =l, 226 97(19),b=1.227 80(19),c= 1.566 5 (3) nm,α= 95.083 (3), β= l01 534(3), γ= 91.007(3)0,V=2.301 6(6) nm3,Z=2, Dcalc.= l.350 Mg/m3, F(000) = 976, Rl = 0.072 6,wR2 = 0.184 3 and 2,a = l.l16 20(17),b= 1.220 54(18),c= l.279 39(18) nm,α= l11.647(2), β= 92.792(3),γ=103.201(2)0,V=2.546 l (4) nm3,Z= l,Dcalc.= l.304 Mg/m3,F(000) = 642,R1=0.045 9,wR2=0.l00 3.and l disp1aysan one-dimensional infinite chain of [Na(18C6)+ comp1ex cations and [Cu (mnt)2]2- complex anionbridged by Na-Ninteractions between adjacent [Na(18C6)+ units. The function of the complex cation[Na(18C6) (H2O)+ is balancing charge in crystal. In 2, two [Na (l8C6) (H2O)]+ complex cations and a[Ni(mnt)2]2-complex anion form a stable neutral complex through Na-N binding.