POLYSULFONYLAMINES .65. A NOVEL CENTROSYM METRIC SOLID-STATE CONFORMATION OF 18-CROWN-6 - SYNTHESIS AND CRYSTAL-STRUCTURES OF THE MONOMERICSUPRAMOLECULES (CH2CH2O)(6)CENTER-DOT-2 HN(SO2-2-NAPHTHYL)(2) AND (CH2CH2O)(6)CENTER-DOT-2 (PROH)-PR-I-CENTER-DOT-2 HN(SO(2)PH)(2)

The complexes 18C6 . 2 HN(SO2-2-Naphthyl)(2) (2a) and 18C6 . 2 (PrOH)- Pr-i . 2 HN(SO(2)Ph)(2) (3e) were obtained by co-crystallization of 18 -crown-6 (18C6) with the appropriate di(arenesulfonyl)amine from isopr opanol solutions at temperatures greater than or equal to 20 degrees C (for 2a) or at -20 degrees C (for 3e). Both structures contain isolat ed formula units displaying crystallographic inversion symmetry. The c onformation of the crown rings is characterized by the torsion angle s equence g(+)g(+)aag(-)g(+)ag(+)ag(-)g(-)aag(+)g(-)ag(-)a, unprecedente d in solid-state structures of 18C6 complexes. The six ether oxygen at oms and four out of twelve carbon atoms of the ring are coplanar withi n +/-7 pm. In 2a (triclinic, space group P (1) over bar), the disulfon ylamine molecules are linked to the oxygen atoms of the g(+/-)ag(-/+)g (-/+) units via N-H ... O hydrogen bonds (H ... O 201 pm, N-H O 161 de grees). In 3e (triclinic, space group P (1) over bar), each amine is N -H ... O bonded to an isopropanol molecule (H ... O 193 pm, N-H ... O 175 degrees) that is connected to a crown oxygen atom of the same conf ormational type as indicated above for 2a (H ... O 198 pm, O-H ... O 1 66 degrees).