N-Confused strapped calix[4]pyrrole: the missing member of calix[4]pyrrole chemistry.

The first example of N-confused strapped calix[4]pyrrole 5 is presented. The structural integrity of 5 and its regular isomer 4 was unambiguously confirmed by single crystal X-ray diffraction analysis. Anion binding studies using 1 H NMR titration carried out in CDCl 3 revealed a small but detectable tendency of 5 to interact with an anion. Conversely, the isomeric regular strapped calix[4]pyrrole 4 displayed high selectivity for fluoride anions under similar experimental conditions. The high fluoride selectivity of 4 and unexpectedly low anion affinity of 5 were ascribed to the presence of intramolecular hydrogen bonds within strapping subunits.