CRYSTAL ENGINEERING USING TRISPHENOLS - 3-DIMENSIONAL HYDROGEN-BONDING NETWORKS IN 1,1,1-TRIS(4-HYDROXYPHENYL)ETHANE, ITS HYDRATED ADDUCT WITH 1,4-DIAZABICYCLO[2.2.2]OCTANE(1 1/1) AND ITS ADDUCT WITH PIPERAZINE(4/3)/

In 1,1,1-tris(4-hydroxyphenyl)ethane, C20H18O3 (1), monoclinic Ia, a = 7.9781(10), b = 18.558(3), c = 11.1995(13)Angstrom, beta = 101.668(9) degrees, with Z = 4, each of the hydroxyl groups acts as both a donor and an acceptor of hydrogen bonds of the type O-H ... O. The molecules are thus connected into square nets, graph set R-4(4)(38), pairs of w hich are then interwoven; the nets are themselves interconnected by fu rther hydrogen bonds to give a continuous three-dimensional network. I n yphenyl)ethane-1,4-diazabicyclo[2.2.2]octane-water (1/1/1), C20H18O3 .-C6H12N2.H2O (2), triclinic <P(1)over bar>, a = 10.421(2), b = 10.734 (2), c = 10.9756(13)Angstrom, alpha = 76.645(12), beta = 74.513(11), g amma = 89.305(13)degrees, with Z = 2, the water molecules are linked t o the trisphenol and the diamine units by O-H ... O and O-H ... N hydr ogen bonds, respectively, to form a linear aggregate. These aggregates are linked into chains by the formation of O-H ... N hydrogen bonds b etween the trisphenol and the neighbouring diamine; however, alongside hydrogen-bond formation between the trisphenol and the diamine, there is also partial transfer of a proton, so that the intra-chain links b etween trisphenol and diamine units are in fact a mixture of O-H ... N and N-H ... O hydrogen bonds. These chains in the [101] direction are cross-linked by further O-H ... O hydrogen bonds, involving only tris phenol O atoms, which form chains in both the [010] and [001] directio ns, thus generating a continuous three-dimensional network. Adduct (3) , 1,1,1-tris(4-hydroxyphenyl)ethane-piperazine (4/3), (C20H18O3)(4).(C 4H10N2)(3), triclinic <P(1)over bar>, a = 12.5049(11), b = 12.7046(10) , c = 14.6226(9)Angstrom, alpha = 113.738(6), beta = 100.839(6), gamma = 102.438(7)degrees, with Z = 1, has two independent trisphenol molec ules in general positions and three independent piperazine molecules l ying about centres of inversion. The five independent components of th e asymmetric unit are linked together by means of three O-H ... N and one O-H ... O hydrogen bonds to form an open aggregate containing no h ydrogen-bonded rings. These aggregates are connected into three sets o f interlinked chains in the [010], [001] and <[(1)over bar 10]> direct ions: the [010] and <[(1)over bar 10]> chains employ only O-H ... O hy drogen bonds, while the [001] chains employ both O-H ... N and N-H ... O hydrogen bonds. Additionally, the inversion symmetry at each pipera zine unit gives rise to further interlinks.