摘要
顺式二（乙二胺）二硝基合钴（Ⅲ）酒石酸锑盐，Δ－ｃｉｓ－［Ｃｏ（ｅｎ）２（ＮＯ２）２］２－ｄ－［Ｓｂ２（Ｃ４Ｈ２Ｏ６）２］·２Ｈ２Ｏ，是由酒石酸锑钾对外消旋混合物ｃｉｓ－［Ｃｏ（ｅｎ）２（ＮＯ２）２］Ｃｌ进行拆分的产物。标题化合物（Ｓｂ２Ｃｏ２Ｃ１６Ｎ１２Ｏ２２Ｈ４０）的晶体结构由衍射方法确定。晶体学参数为：正交晶系，空间群Ｐ２１２１２１，ａ＝１０．０３３（５），ｂ＝１３．２０３（２），ｃ＝２５．９２８（７）（），Ｖ＝３４３４（２）３，Ｚ＝４，Ｍｒ＝１１１４．０６，Ｄｃ＝２．１５６Ｍｇｍ－３，μ＝２１．０７ｍｍ－１，Ｆ（０００）＝２２０８，Ｒ＝０．０７２，ＲＷ＝０．０８４。结构表明，分子由２个Ｃｏ（Ⅲ）配离子和一个酒石酸锑阴离子及两个水分子组成，阴离子为一双核螯合离子。Ｓｂ原子一对孤对电子与其周围四个配位氧原子形成变形三角双锥结构。通过Ｃｏ和Ｓｂ原子对ＣｕＫα射线的反常散射效应确定了分子的绝对构型。二个Ｃｏ（Ⅲ）离子均为Δ构型，酒石酸锑阴离子为Ｒ构型。结构分析表明，标题化合物中三点接触离子对在手性识别中起重要作用。
A new complex, Δ cis bis(ethylenediamine)dinitro cobalt(Ⅲ) di μ [(R,R) tartrato(4 ) diantimonate dihydrate, Δ cis [Co(en) 2(NO 2) 2] 2 d [Sb 2(C 4H 2O 6) 2]·2H 2O, was obtained when racemic mixture cis [Co(en) 2(NO 2) 2]Cl was resolved with di μ [(R,R) tartrato(4 )] diantimonate(Ⅲ). The structure of the title compound has been determined by X ray diffraction methods with the cell parameters as follows: orthorhombic, space group P 2 12 12 1, a=10.033(5), b=13 203(2), c=25.928(7) , V =3434(2) 3, Z=4. The structure was solved by Patterson Fourier syntheses methods and refined by full matrix least squares with anisotropic thermal parameters for Co and Sb atoms, isotropic thermal parameters for remaining non hydrogen atoms and all hydrogen atoms to converge to R= 0 072. The structure shows that the molecule consists of two[Co(en) 2(NO 2) 2] + cations, one [Sb 2(tart) 2] 2- anion and two water molecules. The CoN 6 core differs significantly from octahedral geometry due to the strain of compression of the ethylenediamine bite. Sb atom coordinated to four oxygen atoms forms a distorted trigonal bipyramidconfiguration together with the lone electron pairs on the Sb atom. Bases on the anomalous scattering effects fo Co and Sb atoms to Cu Kα radiation, the absolute configuration of the title complex was assigned. The special arrangement of the cations and anions in the crystal structure shows that “three point contacts” between cations and anions plays an important role in chiral recognition.
出处
《无机化学学报》
SCIE
CAS
CSCD
北大核心
1997年第3期270-275,共6页
Chinese Journal of Inorganic Chemistry
基金
天津市教委重点学科资助
关键词
拆分
酒石酸锑
钴
锑
晶体结构
绝对构型
Co\ \ \ Sb\ \ \ crystal structure\ \ \ absolute configuration
