Herein we report the results of preparing metal compounds (where the metal ions are Co2+, Ni2+, Cu2+, Zn2+) with the cyclic ligand 1,4,8,11-tetraazacyclotetradecane [cyclam] under a variety of conditions of metal-ligand ratios and solvent media. In all cases, we used metal Cl2·nH2O salts (except for anhydrous CoCl2), as specified. Outcome: we isolated species with a four-coordinate metal in the N4 cavity of the ligand alone, and also with either one or two additional axial ligands. Those axial ligands can be (a) a single chloride, leading to penta-coordinated moncationic products; (b) two chlorides, leading to octahedral-neutral compounds; (c) two waters, giving rise to hexa-coordinated [(cyclam)metal(H2O)2]2+ species. Finally, in the case of HCl added to the reaction medium, the cyclam can be di-protonated and appears as [(cyclam)H2]2+ in the crystals. With such a variety of products, it is not surprising that since the metal coordination numbers vary, the cyclam ligand stereochemistries are thereby affected. Interestingly, the [(cyclam)metal] species are invariably hydrogen-bonded to one another in infinite strings of two kinds: (1) those for which the crystal’s Z′ = 1 have single strings; (2) when Z′ = 2, there is a pair of homogeneous strings attached to one another by a variety of hydrogen-bonding linkages. Finally, we observed an interesting pair of hydroxonium cations: the first is hydoxonium cations in a pleated 2-D sheet consisting of fused pentagons located between sheets of [(cyclam)metal] moieties; the second one is an infinite string of composition {(H3O+)-(H2O)-(H3O+)-(H2O)-(H3O+)-(H2O)-(H3O+)}∞.

中文翻译：

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1,4,8,11-四氮杂环十四烷（cyclam）在与环状配体环内外的金属离子形成Co2+、Ni2+、Cu2+和Zn2+化合物中的多功能性

在此，我们报告了制备金属化合物的结果（其中金属离子是Co2+， 你2+, 铜2+, 锌2+）与环状配体 1,4,8,11-四氮杂环十四烷 [cyclam] 在各种金属配体比例和溶剂介质条件下。在所有情况下，我们都使用金属 Cl2·nH2O盐（无水CoCl除外2）， 作为指定。结果：我们在配体的 N4 空腔中分离出具有四配位金属的物质，并且还具有一个或两个额外的轴向配体。这些轴向配体可以是（a）单一氯化物，产生五配位单阳离子产物；(b) 两个氯化物，产生八面体中性化合物；(c) 两种水，产生六配位[(cyclam)金属(H2哦）2]2+物种。最后，当反应介质中添加 HCl 时，cyclam 可以被双质子化并显示为 [(cyclam)H2]2+在晶体中。对于如此多种的产品，由于金属配位数不同，因此环己烷配体的立体化学受到影响也就不足为奇了。有趣的是，[(cyclam)metal] 物种总是以两种无限串的形式彼此形成氢键：(1) 晶体 Z′ = 1 具有单串的物质；(1) 晶体 Z′ = 1 具有单串的物质；(2) 当Z′=2时，存在一对通过各种氢键相互连接的均质链。最后，我们观察到一对有趣的氢氧阳离子：第一个是折叠二维片中的氢氧阳离子，该片由位于[(cyclam)金属]片之间的稠合五边形组成；第二个是无限的组合串 {(H3氧+）-（H2哦3氧+）-（H2哦3氧+）-（H2哦3氧+)}无穷大。