LAUSR

Abstract Four solvates of the imide-based macrocycle (IO)4 are reported herein as the acetone, ethanol, dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) crystal structures (where I and O represent the isophthaloyl group and imide linker, respectively). The acetone solvate (1) or (IO)4•0.375(CH3COCH3) contains an acetone molecule residing on a 2-fold axis with 0.75 site occupancy in the monoclinic space group C2/c. Acetone is encapsulated in lattice pockets between six (IO)4 macrocycles, four of which are at hydrogen bonding distances. The isomorphous hemi-ethanol solvate structure (2) or (IO)4•0.5(C2H5OH) has ethanol molecules disordered about 2-fold axes and each is effectively surrounded by six (IO)4 macrocycles. The DMF solvate structure (3) in the monoclinic space group P21/n contains two DMF molecules, one of which is disordered and present with a minor component of H2O. In contrast to solvent behaviour in (1) and (2), DMF molecules aggregate in 1D channels parallel with the (-101) plane in the (IO)4•2(DMF)•0.1(H2O) structure with DMF occupying ~20% of the unit cell volume. The DMSO crystal structure (4) was obtained from poorly formed, striated and cracked crystals in the monoclinic space group C2. It contains DMSO molecules with extensive disorder and with partial occupancy solvent molecules of indeterminate composition aligned in channels between (IO)4 macrocycles. Analysis of the development of imide-based macrocycles with different substituents is commented on as well as the solvatomorphic behaviour in tennimides, together with comparisons with ab initio calculations.