Clathrate and channel inclusion systems co-exist in the crystal structure of a bis-C-pivot macrocycle (Z? = 2)

15,22-Bis(dimethoxyphosphoryl)-2,5,8-trioxa-16,21-diazatricyclo [21.4.0.09,14] heptacosa-9,11,13,23,25,27(1)-hexaene (1c) crystallises from tetrahydrofuran/methanol (7 : 1) as an inclusion compound with one mole of each of the solvent species. The methanol occupies a clathrate inclusion site within a stacked column of host molecules, while the THF occupies channels which lie between the host columns, which are held rigidly apart by antiparallel N–HO[double bond, length as m-dash]P hydrogen bonds. The marked pseudosymmetry of the crystal structure (Z? = 2) arises because of the twisting of the host columns about their axes to reduce the channel volumes to fit THF. The phosphorylation reaction of imines used here has the potential to provide a supramolecular synthon of a predictable fixed orientation with respect to such a host molecul