Unique inclusion behaviour of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetraaminothiacalix[4]-arene towards small organic molecules

Abstract

Tetraaminothiacalixarene 3, bearing four amino groups instead of the hydroxy groups of p-tert-butylthiacalix[4]arene 2, exhibits inclusion properties different from those of compound 2 towards small organic molecules upon crystallisation from neat solvents or guest solutions. X-ray crystallographic analyses reveal that nitromethane and acetonitrile are included into the cone-shaped cavity of compound 3, as is often seen in inclusion crystals of compound 2, whereas dichloromethane occupies a space between two distal benzene rings of compound 3, adopting a 1,3-alternate conformation. Acetic acid, which forms a dimer, fills a pore surrounded by four host molecules with a pinched cone conformation. Furthermore, guest-free crystals of compound 3 with a 1,3-alternate conformation absorb acetonitrile to give inclusion crystals with the same crystal structure as that obtained by the crystallisation. Thus, compound 3 flexibly changes its conformation according to the structures of guest compounds.

Keywords::

• calixarene
• amino group
• crystallisation
• inclusion
• molecular recognition

Acknowledgements

The authors wish to thank Prof. K. Itaya and Prof. T. Yoshioka (Tohoku University) for courteous permission to use their instruments.

Notes

^1. The main structural difference between the two partial cones is the direction of the lone pairs of the amino groups.