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[(4氮间杂六甲基十四烷环)~(-4)·2Mn~(2+)]·4HCl·[4氮间杂六甲基十四烷环)·2H_2O]的晶体结构已用单晶X线衍射技术测定完成。它属于三斜晶系,P_1空间群,晶胞参数a=9.028(2),b=11.055(2),c=12.202(4),α=71.70(2),B=88.41(2),γ=75.32(2)~°,Z=1。对于2597个可观察独立反射计算R=0.073。结构分析证实,该晶体存在有四类物种,由负4价的四氮间杂六甲基十四烷环(简称电负性大环Ⅱ),2个Mn~(2+)正离子,4个HCl分子和一个携带2个结晶水的4氮间杂六甲基十四烷环(简称电中性大环Ⅰ)组成。 4个HCl分子处于电负性大环Ⅱ的周围,大环Ⅱ和Mn~(2+)离子间按离子键特点取空间最稳定构型与电中性大环Ⅰ沿c方向周期性交替排布,构成四元包合物O~-、N~-、Cl~-等电负性强的离子之间形成很强的H键网。 六十年代以来,以四氨间杂六甲基十四烷环作配体,以Co~(2+)、Co~(3+)、Ni~(2+)等金属离子为络合中心的大环络合物,国外已有许多报导。这些结构的共同特点是大环配体的4个氮原子围绕金属离子以构成四配位或六配位结构,研究表明,络合以后金属的电子组态发生了变化。 近来,我们将Mn~(2+)与上述的配体反应,结果得到与上述结构绝然不同的化合物。NMR谱证实,该化合物中包含电中性和电负性两种大环。环伏安法测其锰离子是2价正离子(详见
The crystal structure of [4-mesohexamethyltetradecane] ~ (-4) · 2Mn ~ (2 +)] · 4HCl · [4-mesohexamethyltetradecane) · 2H_2O] Crystal X-ray diffraction measurements were completed. It belongs to the triclinic system with P_1 space group. The unit cell parameters a = 9.028 (2), b = 11.055 (2), c = 12.202 (4), α = 71.70 (2), B = 88.41 = 75.32 (2) ~ °, Z = 1. R = 0.073 for 2597 observable independent reflections. Structural analysis confirmed that there are four species of the crystal, including four tetra-n-hexamethyltetradecyl tetrazolium (referred to as electronegativation macrocycle Ⅱ), two Mn 2+ positive ions, four HCl molecule and a 4-nitrogen hexagonal tetradecane ring (referred to as electroneutral macrocycle I) carrying two crystal water. Four HCl molecules are located around the electronegative macrocycle Ⅱ. The most stable configuration of the macrocycle Ⅱ and Mn 2+ ions is obtained by the ionic bond and the cyclical alternation along the c direction Cloth, the composition of quaternary clathrates O ~ -, N ~ -, Cl ~ - and other strong negative ion between the formation of a strong H bond network. Since the 1960s, tetramethylammonium tetra-n-octadecane rings have been used as ligands and the metal ions such as Co ~ (2 +), Co ~ (3 +) and Ni ~ Cyclic complexes, there have been many reports abroad. The common feature of these structures is that the four nitrogen atoms of the macrocyclic ligand surround the metal ion to form a tetracoordinate or a hexacoordinate structure. Studies have shown that the electronic configuration of the metal changes after the complexation. Recently, we have Mn ~ (2 +) with the ligands described above, resulting in a completely different from the above structure of the compound. NMR spectroscopy confirmed that this compound contains both electroneutral and electronegativity macrocycles. Cyclic voltammetry to measure its manganese ion is a divalent cation (see