Acta Crystallographica Section B

Structural Science

Volume 56, Part 1 (February 2000)

research papers

Acta Cryst. (2000). B56, 68-84 [ doi:10.1107/S0108768199009714 ]

Supramolecular chemistry of amine-phenol adducts; novel three-dimensional framework structures in adducts of bis(2-aminoethyl)amine with 4,4'-sulfonyldiphenol, 1,1,1-tris(4-hydroxyphenyl)ethane and 3,5-dihydroxybenzoic acid, and in the methanol-solvated adduct of tris(2-aminoethyl)amine with 4,4'-biphenol

C. Glidewell, G. Ferguson, R. M. Gregson and C. F. Campana

Abstract: Bis(2-aminoethyl)amine-4,4'-sulfonyldiphenol (1/3) (1) (orthorhombic Pccn with Z' = 0.5) is a salt, [HN(CH₂CH₂NH₃)₂]²⁺.[O₂S(C₆H₄O)₂]^2-.[O₂S(C₆H₄OH)₂]₂, containing both dianionic and neutral bis-phenol units. The neutral and anionic bis-phenol units are linked by strong O-HO^- hydrogen bonds to form ladders built from $R{_4}{^4}(48)$ rings: each ladder is interwoven with its two nearest neighbours to form a continuous two-dimensional sheet. The amine cations play two roles: they link each ladder to its two next-nearest neighbours by means of N-HO hydrogen bonds and they also link each sheet to the two neighbouring sheets, again via N-HO hydrogen bonds, thus generating a three-dimensional framework. Bis(2-aminoethyl)amine-1,1,1-tris(4-hydroxyphenyl)ethane-methanol (1/4/1) (2) (triclinic P1 with Z' = 0.5) consists entirely of neutral fragments. The tris-phenol units are linked by O-HO hydrogen bonds into molecular ladders built from $R{_4}{^4}(48)$ rings: these ladders are linked by the amine units, firstly into sheets and thence into a three-dimensional framework. Bis(2-aminoethyl)amine-3,5-dihydroxybenzoic acid (1/2) (3) (monoclinic P2₁/c with Z' = 1) is a salt [HN(CH₂CH₂NH₃)₂]²⁺.[{(HO)₂C₆H₃COO}^-]₂. The 3,5-dihydroxybenzoate anions are linked by O-HO hydrogen bonds into interwoven and cross-connected (001) sheets linked by further O-HO hydrogen bonds into a three-dimensional framework. The (001) sheets are further linked by ladders formed from both cations and anions. Tris(2-aminoethyl)amine-4,4'-biphenol-methanol (1/3/1), (4) (monoclinic P2₁), is a salt [{(H₂NCH₂CH₂)₂N(CH₂CH₂NH₃)}⁺]₂.[OC₆H₄C₆H₄O]^2-.[HOC₆H₄C₆H₄OH]₅.[MeOH]₂, with Z' = 1. The asymmetric unit, containing ten independent molecular components, can be regarded as a supermolecule held together by a total of 13 independent hydrogen bonds, of O-HO, O-HN and N-HO types. The supermolecules are linked by O-HO and N-HO hydrogen bonds into two-dimensional sheets, generated by translation; further N-HO hydrogen bonds around the 2₁ screw axes link neighbouring sheets together into a three-dimensional framework.

Keywords: Supramolecular chemistry; Amine-phenol adducts; Hydrogen bonding.