Aniline–phenol recognition: from solution through supramolecular synthons to cocrystals

The Long-Range Synthon Aufbau Module (LSAM) concept is utilized in the crystal engineering of 1:1 cocrystals of trichlorophenols and halogen-substituted anilines. NMR studies show the presence of LSAMs in solution and also the sequence of association of hydrogen bonding and π⋯π stacking interations that constitute the LSAMs.


S1. Crystallization details
: The two compounds were taken together in a mortar in 1:1 ratio and ground with a few drops of MeOH. The grinding process was repeated thrice.
Solutions of resulting powder were kept for crystallizations. Diffraction quality crystals were obtained from a 1:1 solvent mixture of n-hexane and MeOH after 3-4 days by solvent evaporation.
3,4,5-trichlorophenol: 3-chloroaniline (12): The phenol was taken in a mortar and a few drops of 3-chloroaniline were added to it. The mixture was ground and the grinding process was repeated thrice. Solutions of resulting powder were kept for crystallizations. Diffraction quality crystals were obtained from CHCl 3 after 3-4 days by solvent evaporation. 3,4,5-trichlorophenol: 2,5-dichloroaniline (13): The two compounds were taken together in a mortar in 1:1 ratio and ground with a few drops of MeOH. The grinding process was repeated thrice. Solutions of resulting powder were kept for crystallizations. Diffraction quality crystals were obtained from CHCl 3 after 3-4 days by solvent evaporation. 3,4,5-trichlorophenol:3,5 -dichloroaniline (14): The two compounds were taken together in a mortar in 1:1 ratio and ground with a few drops of MeOH. The grinding process was repeated thrice. Solutions of resulting powder were kept for crystallizations. Diffraction quality crystals were obtained from acetone after 3-4 days by solvent evaporation. 3,4,5-trichlorophenol: 3,4-dichloroaniline (15): The two compounds were taken together in a mortar in 1:1 ratio and ground with a few drops of MeOH. The grinding process was repeated thrice. Solutions of resulting powder were kept for crystallizations. Diffraction quality crystals were obtained from CH 2 Cl 2 after 3-4 days by solvent evaporation. 3,4,5-trichlorophenol:4-bromoaniline (16): The two compounds were taken together in a mortar in 1:1 ratio and ground with a few drops of MeOH. The grinding process was repeated thrice.
Solutions of resulting powder were kept for crystallizations. Diffraction quality crystals were obtained from acetone after 3-4 days by solvent evaporation.
3,4,5-trichlorophenol: 4-iodoaniline (17): The two compounds were taken together in a mortar in 1:1 ratio and ground with a few drops of MeOH. The grinding process was repeated for thrice.
Solutions of resulting powder were kept for crystallizations. Diffraction quality crystals were obtained from a 1:1 solvent mixture of n-hexane and MeOH after 3-4 days by solvent evaporation. 3,4,5-trichlorophenol: 3-chloro-4-iodoaniline (18): The two compounds were taken together in a mortar in 1:1 ratio and ground with a few drops of MeOH. The grinding process was repeated thrice. Solutions of resulting powder were kept for crystallizations. Diffraction quality crystals were obtained from MeOH after 3-4 days by solvent evaporation. 3,4-trichlorophenol: 4-chloroaniline (19): The two compounds were taken together in a mortar in 1:1 ratio and ground with a few drops of MeOH. The grinding process was repeated thrice.

2,
The resulting powder was put for sublimation. Needle like crystals were obtained after two days. (20):The phenol was taken in a mortar and a few drops of 3-chloroaniline were added to it. The mixture was ground and the grinding process was repeated thrice. The resulting powder was put for sublimation. Needle like crystals were obtained after two days. (21): The two compounds were taken together in a mortar in 1:1 ratio and ground with a few drops of MeOH. The grinding process was repeated thrice. The resulting powder was dissolved in different solvents. Nice crystals were obtained from EtOH after 3-4 days by solvent evaporation. (22): The two compounds were taken together in a mortar in 1:1 ratio and ground with a few drops of MeOH. The grinding process was repeated thrice. The resulting powder was put for sublimation. Needle like crystals were obtained after one day. (23): The two compounds were taken together in a mortar in 1:1 ratio and ground with a few drops of MeOH. The grinding process was repeated thrice. Solutions of resulting powder were kept for crystallizations. Diffraction quality crystals were obtained from MeOH after 3-4 days by solvent evaporation. (24): The two compounds were taken together in a mortar in 1:1 ratio and ground with a few drops of MeOH. The grinding process was repeated thrice. Solutions of resulting powder were kept for crystallizations. Diffraction quality crystals were obtained from EtOH after 3-4 days by solvent evaporation.