Sergei A. Kotlyar

The 1 : 1 complexes between benzo-18-crown-6, 18-crown-6 and aminosulfuric acid

The title compounds were prepared by treating a methanol solution of the corresponding crown ether with an aqueous solution of aminosulfuric acid.Crystals of [benzo-18-crown-6·H2NSO2OH] suitable for X-ray crystallography were obtained by recrystallization from methanol. The crystals are orthorhombic, space groupP212121,a = 14.310(7),b = 12.516(4),c = 10.890(4) Å. Refinement led to a final conventionalR value of 0.051 for 909 reflections.Crystals of [18-crown-6·H2NSO2OH] suitable for X-ray crystallography were obtained by recrystallization from acetone. They are orthorhombic, space groupP212121,a = 17.027(6),b = 14.866(5),c = 8.345(4) Å. The structure was solved by a heavy atom method and refined to an agreement value of 0.067.

Crystal structure of inclusion compounds: The complexes of thecis-syn-cis and thecis-anti-cis isomers of dicyclohexano-18-crown-6 with 4-methylbenzenesulfamide

The crystal structure of two complexes of the isomerscis-syn-cis (isomer A) andcis-anti-cis (isomer B) of dicyclohexano-18-crown-6 with 4-methylbenzenesulfamide have been determined by X-ray single crystal diffraction methods. The two structures have been solved by direct methods and refined to agreement values of 0.067 and 0.038 for isomers A and B respectively. The first isomer forms an inclusion compound with a host/guest ratio of 1 : I; the second one of I:2. The amino groups of the guest molecules are connected by N-H...O hydrogen bonds with oxygen atoms of the polyether molecules. The methyl groups of 4-methylbenzenesulfamide do not form hydrogen bonds.[/p]The host-guest interactions in the molecular complexes, the reciprocal influence of the two molecules on their conformation and the intermolecular contacts between the molecules in the crystal are discussed.

A Simple Method for Iodination of Benzo- and Dibenzocrown Ethers

Iodination of benzo-12-crown-4, benzo-15-crown-5 and benzo-18-crown-6 by equimolar amounts of N-iodosuccinimide in ethanol in the presence of sulfuric acid additions proceeds quickly and selectively and results in corresponding 4I-iododerivatives with 78-86% yields. Reactivity of [3.3]dibenzo-18-crown-6 slightly differs from that of benzocrown ethers and diiodide (mixture of cisand trans-isomers) is obtained with 76% yield.

Structure of 1,4,7,10,13-pentaoxa-16-(sulfanil)azacyclooctadecane

The crystal structure of 1,4,7,10,13-pentaoxa-16-(sulfanil)azacyclooctadecane was determined in an x-ray diffraction structural analysis. This structure consists of centrosymmetric hydrogen-bonded dimers of independent 1,4,7,10,13-pentaoxo-16-(sulfanil)azacyclooctadecane molecules and is a host-guest autocomplex, in which the macrocyclic part of the molecule is the host and the sulfanil substituent of another molecule is the guest.