Preparation and X-Ray Structures of Complexes of 18-Membered Crown Ethers with Polyfunctional Guests - Urea and (O-Alkyliso) Uronium Salts

The preparation and x-ray structure determinations of six complexes of urea and (o-n-butyliso)uronium salts with crown ethers are presented. Urea forms isostructural 5:1 adducts with 18-crown-6 (1) and aza-18-crown-6 (2), in which two urea molecules are each hydrogen bonded to two neighbouring hetero atoms of the macroring. The remaining urea molecules form two-dimensional layers alternating with crown ether layers. In both complexes the macroring has theg + g + a ag - a ag - a g - g - a ag + a ag + a conformation withci symmetry. In the solid 1:1 complex of o-n-butylisouronium picrate with 18-crown-6 (3) two types of conformations of the macroring were observed: theg + g + a ag - a ag + a ag - g - ag - a ag + a conformation with approximatecm symmetry and to a lesser extent theg + g + a ag - a ag + a g + g + a ag - a ag + a conformation with approximatec2 symmetry. Both conformations allow the guest to form three hydrogen bonds to the macrocyclic host. Three complexes of 18-crown-6 and uronium salts have been prepared and characterized by x-ray crystallography. The 1:1 complexes with uronium nitrate (4) and uronium picrate (5) both exhibit the samec2 conformation and the same hydrogen bonding scheme as in the least occupied form of the previous complex. A 1:2 complex with uroniump-toluenesulphonate (6) has a different hydrogen bonding scheme (two hydrogen bonds per cation to neighbouring oxygen atoms of the macroring) and a different conformation of the host molecule (theag + a ag - a ag + a ag - a ag + a ag - a conformation with almostd3d symmetry). An attempt to prepare a solid uronium nitrate complex with diaza-18-crown-6 in the same way as the 18-crown-6·uronium nitrate (1:1) complex did not yield the expected result. Instead x-ray analysis revealed that the uronium ion is dissociated, resulting in the nitrate salt of the diprotonated diaza crown ether (7).