Acta Crystallographica Section B

Structural Science

Volume 56, Part 1 (February 2000)

Acta Cryst. (2000). B56, 39-57 [doi:10.1107/S0108768199006072]

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

R. M. Gregson, C. Glidewell, G. Ferguson and A. J. Lough

Abstract: 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 N₄ cavity of the macrocycle by N-HN hydrogen bonds, and the phenolate anions contain intramolecular O-HO^- hydrogen bonds. The ions are linked into a finite centrosymmetric aggregate by means of N-HO hydrogen bonds. meso-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane-4,4'-thiobiphenol-methanol (1/2/2), (C₁₆H₃₆N₄).(C₁₂H₁₀O₂S)₂.(CH₄O)₂ (2), and meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-4,4'-sulfonylbiphenol-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-HO^- 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-5,5,7,12,12,14-hexamethyl-1,4,8,11-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-Hexamethyl-1,4,8,11-tetraazacyclotetradecane-phenylphosphonic acid-water (1/4/2) (6) is a salt, [C₁₆H₄₀N₄]⁴⁺.4[C₆H₅PO₃H]^-.2H₂O, containing the centrosymmetric tetra-protonated 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. In meso-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)₂C₆H₃COO]^- are linked into continuous two-dimensional nets, which are in turn linked by the centrosymmetric cations 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[HOC₆H₄C₆H₄O]^-.[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.

Online 1 February 2000


	Structure factor file (CIF format) (165.5 kbytes) Contains datablock 1

	Structure factor file (CIF format) (186.4 kbytes) Contains datablock 2

	Structure factor file (CIF format) (200.6 kbytes) Contains datablock 3

	Structure factor file (CIF format) (155.5 kbytes) Contains datablock 4

	Structure factor file (CIF format) (322.4 kbytes) Contains datablock 5

	Structure factor file (CIF format) (235.0 kbytes) Contains datablock 6

	Structure factor file (CIF format) (170.2 kbytes) Contains datablock 7

	Structure factor file (CIF format) (207.4 kbytes) Contains datablock 8

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