Crystal engineering using bis- and tris-phenols.: Adducts with 1,4,8,11-tetraazacyclotetradecane (cyclam):: Isolated ladders in the adduct with 4,4′-thiodiphenol, tethered ladders in the adduct with 4,4′-sulfonyldiphenol and two interwoven three-dimensional networks in the adduct with 1,1,1-tris(4-hydroxyphenyl)ethane

The structure of 4,4'-thiodiphenol-1,4,8,11-tetraazacyclotetradecane (2/1), (C12H10O2S)(2). C10H24N4 (1), monoclinic, P2(1)/c, a=11.1602(12), b=10.8084(12), c = 14.001(2) Angstrom, beta = 103.127(10)degrees, with Z = 2, contains phenolate anions [HOC6H4SC6H4O](-) and diprotonated cyclam cations [C10H26N4](2+): these cations have the centrosymmetric trans-III conformation and the two additional protons are contained within the N-4 cavity of the macrocycle, held by three-centre hydrogen bonds. The phenolate anions form chains, held together by O-H ... O hydrogen bonds, and pairs of these chains are cross-linked into ladders by the [cyclamH(2)](2+) cations by means of N-H ... O hydrogen bonds. The structure of 4,4'-sulfonyldipheno1-1,4,8,11-tetraazacyclotetradecane (2/1), (C12H10O4S)(2 .)C10H24N4 (2), triclinic, P (1) over bar, a = 10.9345(10), b=11.0060(10), c= 14.350 (2)Angstrom, alpha = 79.532(10), beta = 86.739(10), gamma = 87.471 (10)degrees, with Z = 2, contains phenolate anions [HOC6H4SO2C6H4O](-) and cyclam dications [C10H26N4](2+): the phenolate anions are linked into antiparallel chains, cross-linked by the cyclam cations. There are two distinct types of ladder in the structure running along (0, y, 0) and (1/2, y, 4), respectively, and these bundled ladders are tied together by C-H ... O hydrogen bonds to form a continuous three-dimensional array. In 1,1, 1 -tris(4-hydroxyphenyl)ethane-1,4,8,11-tetraazacyclotetradecane-methanol (2/1/1), (C20H18O3)(2 .)C10H24N4 CH4O (3), triclinic, P (1) over bar, a= 8.2208(11), b=16.245(2), c=17.337(2)Angstrom, alpha=81.694 (13), beta = 89.656 (14), gamma = 86.468 (12)degrees, with Z = 2, the structure contains centrosymmetric diprotonated cyclam cations of precisely the same type as found in (1), phenolate anions [(HOC6H4)(2)C(CH3)C6H4O](-) and neutral methanol molecules. The molecular components are linked together by nine different types of hydrogen bond, five of O-H ... O type and four of N-H ... O type, to form chains running in the [001], [010] (two sets), [211] and [21 (1) over bar] directions. The combination of these chain motifs generates two independent three-dimensional networks which are fully interwoven, but not bonded to one another.