Formation of One-Dimensional Chains, Two-Dimensional Bilayers and a Three-Dimensional Diamondoid Architecture in Hydrogen-Bonded Adducts of 4,4'-Biphenol with 1,4-Diazabicyclo[2.2.2]octane and 1,2-Diaminoethane

Abstract

In 4,4′-biphenol–1,4-diazabicyclo[2.2.2]octane (1/1), C12H10O2.C6H12N2 (1), monoclinic, C2/c, a = 12.1510 (9), b = 6.3202 (4), c = 21.051 (2) Å, β = 98.875 (10)° with Z = 4, the biphenol units lie across twofold rotation axes and the diamine units are disordered across centres of inversion. The molecular components are linked by means of O—H...N hydrogen bonds into zigzag chains with graph set C^{2}_{2}(16) running parallel to the [201] direction; the chains are not coiled and there are no interactions between neighbouring chains. In 4,4′-biphenol–1,2-diaminoethane–methanol (2/1/1), (C12H10O2)2.C2H8N2.CH4O (2), triclinic, P1¯, a = 9.4592 (7), b = 10.6311 (10), c = 12.2085 (14) Å, α = 91.812 (9), β = 93.091 (6), γ = 90.652 (6)° with Z = 2, there are seven independent hydrogen bonds of O—H...O, O—H...N and N—H...O types and each oxygen and each nitrogen acts as a single donor and single acceptor of hydrogen bonds. The four independent components are linked by means of O—H...O and O—H...N hydrogen bonds into a linear aggregate, and further O—H...N and O—H...O hydrogen bonds generate chains in the [011] direction containing alternating biphenol and diamine units, and in the [021] direction containing methanol and pairs of biphenol molecules. These two types of chain intersect to form a continuous two-dimensional net, graph set R^{10}_{10}(62), with biphenol molecules at the nodes: pairs of these nets are linked into bilayers by N—H...O hydrogen bonds, but the nets are not interwoven. In 4,4′-biphenol–1,2-diaminoethane (1/1), C12H10O2.C2H8N2 (3), monoclinic, P21/a, a = 8.2121 (5), b = 5.3401 (3), c = 14.6014 (9) Å, β = 99.962 (7)° with Z = 2, each of the components lies across a centre of inversion. The O atoms act as single donors and double acceptors of hydrogen bonds and the N atoms as double donors and single acceptors, so that both oxygen and nitrogen are effectively four-coordinate; all the hydrogen bonds are of O—H...N or N—H...O type. Chains built from N—H...O and O—H...N hydrogen bonds run parallel to [100] and [010] and the intersection of these gives two-dimensional nets built from R^{6}_{6}(12) rings: these nets are linked by the —C6H4C6H4— and —CH2CH2— spacer units into a continuous three-dimensional diamondoid structure.