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

Abstract

The structure of 4,4′-thiodiphenol–1,4,8,11-tetraazacyclotetradecane (2/1), (C12H10O2S)2.C10H24N4 (1), monoclinic, P21/c, a = 11.1602 (12), b = 10.8084 (12), c = 14.001 (2) Å, β = 103.127 (10)°, 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 N4 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 [cyclamH2]2+ cations by means of N—H...O hydrogen bonds. The structure of 4,4′-sulfonyldiphenol–1,4,8,11-tetraazacyclotetradecane (2/1), (C12H10O4S)2.C10H24N4 (2), triclinic, P1¯, a = 10.9345 (10), b = 11.0060 (10), c = 14.350 (2) Å, α = 79.532 (10), β = 86.739 (10), γ = 87.471 (10)°, 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\over2, y, 1\over2), 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, P1¯, a = 8.2208 (11), b = 16.245 (2), c = 17.337 (2) Å, α = 81.694 (13), β = 89.656 (14), γ = 86.468 (12)°, with Z = 2, the structure contains centrosymmetric diprotonated cyclam cations of precisely the same type as found in (1), phenolate anions [(HOC6H4)2C(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 [211¯] directions. The combination of these chain motifs generates two independent three-dimensional networks which are fully interwoven, but not bonded to one another.