ABSTRACT
The trigonally trisubstituted acid 3,5-dihydroxybenzoic acid forms hydrated salt-type adducts with organic diamines. In 1,4-diazabicyclo[2.2.2]octane-3,5-dihydroxybenzoic acid-water (1/1/1) (1), where Z' = 2 in P2(1)/c, the constitution is [HN(CH(2)CH(2))(3)N](+).[(HO)(2)C(6)H(3)COO](-).H(2)O: the anions and the water molecules are linked by six O-H.O hydrogen bonds to form two-dimensional sheets and each cation is linked to a single sheet by one O-H.N and one N-H.O hydrogen bond. Piperazine-3,5-dihydroxybenzoic acid-water (1/2/4) (2) and 1,2-diaminoethane-3,5-dihydroxybenzoic acid-water (1/2/2) (3) are also both salts with constitutions [H(2)N(CH(2)CH(2))(2)NH(2)](2+).2[(HO)(2)C(6)H(3)COO](-).4H(2)O and [H(3)NCH(2)CH(2)NH(3)](2+).2[(HO)(2)C(6)H(3)COO](-).2H(2)O, respectively. Both (2) and (3) have supramolecular structures which are three-dimensional: in (2) the anions and the water molecules are linked by six O-H.O hydrogen bonds to form a three-dimensional framework enclosing large centrosymmetric voids, which contain the cations that are linked to the framework by two N-H.O hydrogen bonds; in (3) the construction of the three-dimensional framework requires the participation of cations, anions and water molecules, which are linked together by four O-H.O and three N-H.O hydrogen bonds.
ABSTRACT
Tet-b (racemic 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, C(16)H(36)N(4)) and trimesic acid (1,3,5-benzenetricarboxylic acid, C(9)H(6)O(6)) form a salt partially solvated by both water and methanol, i.e. 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-1,3,5-benzenetricarboxylic acid--methanol--water (1/1/0.78/1.12), C(16)H(38)N(4)(2+) x C(9)H(4)O(6)(2-) x 0.78CH(4)O x 1.12H(2)O. The anions are linked by O--H...O hydrogen bonds [O...O 2.442 (4) and 2.458 (4) A; O--H...O 170 and 171 degrees ] into zigzag chains; orientationally disordered cations are linked to the anion chains by means of N--H...O hydrogen bonds [major orientation: N...O 2.695 (3)--3.071 (4) A, N--H...O 148--179 degrees; minor orientation: N...O 2.75 (2)--3.34 (2) A, N--H...O 147--170 degrees ] and link the chains into sheets. The solvent molecules are all disordered, but appear to play no significant structural role apart from space filling.
ABSTRACT
The trigonally trisubstituted carboxylic acid 3,5-dinitrobenzoic acid, (O(2)N)(2)C(6)H(3)COOH, forms 2:1 salts with a range of organic diamines L, with the general composition [LH(2)](2+) x [[(O(2)N)(2)C(6)H(3)COO](-)](2). When L is a bis-tertiary amine the hard N-H...O hydrogen bonds generate finite three-component aggregates, anion...cation...anion, and these aggregates are further linked by soft C-H...O hydrogen bonds to form one-dimensional molecular ladders when L is N,N,N',N"-tetramethyl-1,2-diaminoethane and chains of rings when L is 4,4'-dipyridylethane or 4,4'-dipyridylethene; two-dimensional sheets are formed when L is 1,4-diazabicyclo[2.2.2]octane and a three-dimensional framework is formed when L is N,N'-dimethylpiperazine. When L is the bis-secondary amine piperazine, the hard N-H...O and soft C-H...O hydrogen bonds each generate continuous motifs in the form of distinct chains of rings, the combination of which generates sheets, while when L is the bis-primary amine 1,2-diaminoethane the hard N-H...O hydrogen bonds alone generate a three-dimensional framework.
