[(C_(16)H_(32)N_4)~(-4)·2Mn~(2+)·4HCl·[(C_(16)H_(36)N_4)·2H_2O]多元包合物的晶体结构

[(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 A CLATHRATE COMPOUND- (meso-Me_6[14]aneN_4)~(-4) ZMn~(2+)·4HC1(meso-Me_6[14] aneN_4) 2H_2O

The title compound crystalizes in the space group Pi with un(?)t. Cell constants a=9.028(2), b=11.055(2), c=12.202(4)A, =71 .70(2), β88.41(2), γ=75.32(2)0. Itcontains one formula unit of Mn2Cl4O2N8C32H76. 2597 independent intensities are collected on adiffractometer using CuK radiation. The block-diagonal least squares refinement for all atoms gives a final discrepancyR =0.073.The result of structure analysis shows that .this clathrate compound consists of four kinds of structure units, i.e. the negatively charged macrocycle II (meso-Me6[14]aneN4 )4-, two Mn2+ ions, four Hydrochloric acid molecules and a neutral macrocycle I (meso-Me6(14laneN4)-2H2O.Four hydrochloric acid molecules are located around the macro-cycle II, and four N atoms of the macrocycle Ⅱ (the macrocycle Ⅰ also) constitute a plane, and the perpendicular distances of the two manganese ions are -2.448 and 2.558 from this plane, respectively. All of them and macrocycle I are arranged alternativety,along the, direction of c. In addition, the crystal structure has a strong hydrogen-bond network in the XV plane.