meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane as a building block in supramolecular chemistry;: salts formed with 2,2′-biphenol, 4,4′-biphenol, 4,4′-thiodiphenol, 4,4′-sulfonyldiphenol, 3- and 4-hydroxybenzoic acids, 3,5-dihydroxybenzoic acid and phenylphosphonic acid;: supramolecular structures in zero, one, two and three dimensions

The structure of meso-5,5,7,12,12,14-hexamethyl-1,4,8,11 tetraazacyclotetradecane-2,2'-biphenol (1/2), (C16H36N4).-(C12H10O2)(2) (1). is a salt [C16H38N4](2+).2[HOC6H4C6H4O](-): the cations are centrosymmetric with two protons held within the N-4 cavity of the macrocycle by N--H ... N hydrogen bonds, and the phenolate anions contain intramolecular O--H ... O(-)hydrogen bonds. The ions are linked into a finite centrosymmetric aggregate by means of N--H O hydrogen bonds. meso-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane-4,4'-thiobiphenol-methanol (C16H36N4) (C12H10O2S)(2).(CH4O)(2) (2), and meso-5,5,7,12,12,14-hexamethyl-1,4,8,1 l-tetraazacyclotetradecane-4,4'-sulfonyl nol-methanol (1/2/2), (C16H36N4).(C12H10O4S)(2).(CH4O)(2) (3), are isomorphous: each is a salt, [C16H38N4](2+).- 2[HOC6H4SC6H4O](-).2MeOH (2) and [C16H38N4](2+).- 2[HOC6H4SO2C6H4O](-).2MeOH (3), and in each the phenolate anions are linked by O--H O- hydrogen bonds into chains; antiparallel pairs of chains are cross-linked by the cations to form molecular ladders, with neutral methanol molecules acting as spacer units. In meso-5,5,7.12,12,14hexamethyl-1,4,8,1 1-tetraazacyclotetradecane-3-hydroxybenzoic acid-methanol (1/2/2) (4), 3-hydroxybenzoate anions form chains, again cross-linked in pairs by the [C16H38N4](2+) cations to form molecular ladders, different from those in (2) and (3) in that the neutral methanol units are pendent from the ladders, rather than forming a part of it, meso-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane-4-hydroxybenzoic acid-methanol (1/2/1) (5) is again a salt, [C16H38N4](2+).2[HOC6H4COO](-). MeOH: chains of 4-hydroxybenzoate anions are continuously cross-linked by two different types of [C16H38N4](2+) cation into a two-dimensional net. Only one of the two types of cation is linked to the chains via neutral methanol spacer units. meso-5,5,7,12,12,14-Hexane thyl-1,4,8,11-tetraazacyclotetradecane-phenylphosphonic acid-water (1/4/2) (6) is a salt, [C16H40N4](4+).- 4[C6H5PO3H](-).2H(2)O, containing the centrosymmetric tetraprotonated amine units, which have a conformation quite different from the trans-III conformation uniformly found in the [C16H38N4](2+) cations. The phenylphosphonate anions and the water molecules are linked into chains of fused rings, which are linked by the cations into two-dimensional nets. Inmeso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-3,5-dihydroxybenzoic acid (1/2) (7), the 3,5-dihydroxybenzoate anions in the unsolvated salt [C16H38N4](2+).2[(HO)(2)C6H3COO](-) are linked into continuous two-dimensional nets, which are in turn linked by the centrosymmetric cat ions to form a three-dimensional framework. meso-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane-4,4'-biphenol (1/3) (8) is a salt: containing both neutral and anionic biphenol units, [C16H38N4](2+).2[HOC(6)H(4)C(6)H4O](-).[HOC6H4C6H4OH]. The two types of biphenol unit form two-dimensional nets and these nets are linked by the cations to form three independent, three-dimensional frameworks which are fully interwoven, but not bonded to one another.