3,6,9,16,19,22-Hexaazatricyclo

The adduct (1) formed between the hexaaza macrocycle 3,6,9,16,19,22-hexaazatricyclo[22.2.2.2(11,14]triconta-1(26),11(29),12,14(30),24,27-hexaene, C24H38N6, and 4,4'-sulfonyldiphenol, O2S(C6H4OH)2, is a salt [(C24H40N6)2+].2[(HOC6H4SO2C6H4O)-], and the adduct (2) formed by the same macrocyclic amine with 4,4'-biphenol is an aquated salt which also contains neutral biphenol molecules, [(C24H40N6)2+]. 2[(HOC6H4C6H4O)-].(HOC6H4C6H4OH).2H2O. In both compounds the cations lie across centres of inversion: there are two crystallographically distinct cation sites in (1) and the conformations of the cations occupying them are quite different. In (2) the single type of cation site is occupied by a conformationally disordered cation: the major and minor components represent two further distinct conformers. In (1) the anions are linked by O-H...O hydrogen bonds into chains, and each cation is linked by a total of six N-H...O hydrogen bonds to anions in four different chains, so linking the chains into continuous sheets. In (2) the anions and the water molecules are linked into sheets, which are further linked into a continuous three-dimensional framework by both the cations and the neutral biphenol units.

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-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 N4 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 (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-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-5,5,7,12,12,14-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 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. In meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetrade cane-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-tetraazacyclo tetradecane-4,4'-biphenol (1/3) (8) is a salt containing both neutral and anionic biphenol units, [C16H38N4]2+.2[HOC6H4-C6H4O]-.[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.

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

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-.[O2S(C6H4OH)2]2, containing both dianionic and neutral bis-phenol units. The neutral and anionic bis-phenol units are linked by strong O-H...O- hydrogen bonds to form ladders built from R4(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-H...O hydrogen bonds and they also link each sheet to the two neighbouring sheets, again via N-H...O 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-H...O hydrogen bonds into molecular ladders built from R4(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 P2(1)/c with Z' = 1) is a salt [HN(CH2CH2NH3)2]2+.[[(HO)2C6H3COO]-]2. The 3,5-dihydroxybenzoate anions are linked by O-H...O hydrogen bonds into interwoven and cross-connected (001) sheets linked by further O-H...O 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 P2(1)), is a salt [((H2NCH2CH2)2.N(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-H...O, O-H...N and N-H...O types. The supermolecules are linked by O-H...O and N-H...O hydrogen bonds into two-dimensional sheets, generated by translation; further N-H...O hydrogen bonds around the 2(1) screw axes link neighbouring sheets together into a three-dimensional framework.

Two different three-dimensional hydrogen-bonded framework structures in two hydrated adducts meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane--terephthalic acid--water (1/1/4) and (1/1/6)

Co-crystallization of meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, C16H36N4, with terephthalic acid (1,4-benzenedicarboxylic acid), C8H6O4, from ethanol yields the tetrahydrate (C16H36N4).(C8H6O4).(H2O)4 (1), meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecaneterephthalic acid-water (1/1/4), while similar co-crystallization from methanol yields the hexahydrate (C16H36N4).(C8H6O4).(H2O)6 (2), meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-terephthalic acid-water (1/1/6). Both compounds are salts, [C16H38N4]2+.[C8H4O4]2-. 4H2O (1) and [C16H38N4]2+.[C8H4O4]2-.6H2O (2): in (2) both ionic components lie across centres of inversion and in both salts there are two protons held within the N4 cavity of the cation. In the structure of (1), the cations and anions are linked into chains by means of paired N-H...O hydrogen bonds, and the water molecules are linked into continuous chains by means of O--H...O hydrogen bonds, in which each of the H atoms is independently disordered over two equally populated sites. The water chains link the ionic chains into a continuous three-dimensional framework by means of further O-H...O hydrogen bonds. In (2) the cations and anions are linked by single N--H...O hydrogen bonds, again into chains: at the same time the anions and the water molecules are linked by multiple O-H...O hydrogen bonds into continuous two-dimensional nets, which are linked by the cations, by means of N--H...O hydrogen bonds into a three-dimensional framework, entirely different from that in (1).

Crystal engineering using bisphenols: interwoven ladders, sheet and framework structures in the binary adducts of 4,4'-sulfonyldiphenol with pyrazine (2/1), 4,4'-bipyridyl (1/1), trans-1,2-bis(4-pyridyl)ethene (1/1), 1,2-bis(4-pyridyl)ethane (1/1) and 4,4'-trimethylenedipyridine (1/1), and in 4,4'-sulfonyldiphenol-4,4'-trimethylenedipiperidine-water (2/2/1).

The structures of six hydrogen-bonded adducts of 4,4'-sulfonyldiphenol with heteroaromatic amines have been determined. In 4,4'-sulfonyldiphenol-pyrazine (2/1) the pyrazine molecules lie across centres of inversion. The bisphenol molecules are linked into C(8) chains parallel to [100] by means of O-H.O=S hydrogen bonds, and antiparallel pairs of these chains are cross-linked by the pyrazine molecules, via O-H.N hydrogen bonds, to form molecular ladders containing R(6)(6)(50) rings between the rungs of the ladders. Each ladder is interwoven with two neighbouring ladders, thus producing a continuous two-dimensional sheet. The structure of 4,4'-sulfonyldiphenol-4,4'-bipyridyl (1/1) consists of spiral C(2)(2)(21) chains parallel to [010] containing alternating bisphenol and bipyridyl molecules linked by O-H.N hydrogen bonds: these chains are linked by two types of C-H.O hydrogen bonds which form C(5) chains along [001] and C(2)(2)(10) chains along [101], thus generating two interconnected nets characterized in the one case by a chequerboard pattern of R(6)(6)(44) and R(6)(6)(52) rings, and in the other by a single type of R(6)(6)(46) ring. 4,4'-Sulfonyldiphenol-trans-1,2-bis(4-pyridyl)ethene (1/1) [systematic name: 4,4'-sulfonyldiphenol-trans-4,4'-vinylenedipyridine (1/1)] and 4,4'-sulfonyldiphenol-1,2-bis(4-pyridyl)ethane (1/1) [systematic name: 4,4'-sulfonyldiphenol-trans-4,4'-ethylenedipyridine (1/1)] are isomorphous: the 1,2-bis(4-pyridyl)ethene component exhibits orientational disorder, corresponding approximately to a 180 degrees rotation of ca 23% of the molecules about the N.N vector; in each compound the structure is built from C(2)(2)(23) chains of alternating bisphenol and bis(pyridyl) molecules connected by O-H.N hydrogen bonds, running parallel to [112] and generated by translation. The [112] chains are linked by C-H.O hydrogen bonds which generate C(2)(2)(12) chains parallel to [101], so forming a two-dimensional net built from R(6)(6)(50) rings. The structure of 4,4'-sulfonyldiphenol-4,4'-trimethylenedipyridine (1/1) consists of C(2)(2)(24) chains parallel to [100] generated by translation and consisting of alternating bisphenol and bis(pyridyl) molecules linked by O-H.N hydrogen bonds. Pairs of such chains are coiled together to form double helices, and pairs of such double helices, of opposite hand, are linked together by paired C-H.O hydrogen bonds in R(2)(2)(10) rings to form pairs of interwoven ladders in which the C(2)(2)(24) chains form the uprights and the R(2)(2)(10) rings form the rungs, between which are R(6)(6)(50) rings: an R(2)(2)(10) ring belonging to one ladder lies at the centre of an R(6)(6)(50) ring belonging to the other. 4,4'-Sulfonyldiphenol-4,4'-trimethylenedipiperidine-water (2/2/1) is a salt, 2C(13)H(27)N(2)(+).2C(12)H(9)O(4)S(-).H(2)O, containing two independent singly protonated diamine cations, two independent bisphenolate anions, and neutral water molecules. The two independent diamine cations are linked by N-H.N hydrogen bonds into C(2)(2)(24) chains running parallel to [001] and generated by translation, and each type of bisphenolate anion forms an independent spiral C(12) chain, also parallel to [001]. The three types of chain are linked by the water molecules: the two types of bisphenolate chain are linked by water molecules acting as double donors in O-H.O(-) hydrogen bonds in a C(6)(4)(32) chain parallel to [100], thus generating a two-dimensional net built from R(8)(6)(56) rings; the diamine chains are linked to these nets by means of N-H.O hydrogen bonds in which the water molecules act as acceptors and further hydrogen bonds, of N-H.O(-) and N-H.O=S types, link these two-dimensional nets into a continuous three-dimensional framework.