Two crown-ether-coordinated caesium halogen salts

Acta Crystallogr C Struct Chem. 2014 May;70(Pt 5):455-9. doi: 10.1107/S2053229614006809. Epub 2014 Apr 18.

Abstract

The crystal structures of two crown-ether-coordinated caesium halogen salt hydrates, namely di-μ-bromido-bis[aqua(1,4,7,10,13,16-hexaoxacyclooctadecane)caesium(I)] dihydrate, [Cs2Br2(C12H24O6)2(H2O)2]·2H2O, (I), and poly[[diaquadi-μ-chlorido-μ-(1,4,7,10,13,16-hexaoxacyclooctadecane)dicaesium(I)] dihydrate], {[Cs2Cl2(C12H24O6)(H2O)2]·2H2O}n, (II), are reported. In (I), all atoms are located on general positions. In (II), the Cs(+) cation is located on a mirror plane perpendicular to the a axis, the chloride anion is located on a mirror plane perpendicular to the c axis and the crown-ether ring is located around a special position with site symmetry 2/m, with two opposite O atoms exactly on the mirror plane perpendicular to the a axis; of one water molecule, only the O atom is located on a mirror plane perpendicular on the a axis, while the other water molecule is completely located on a mirror plane perpendicular to the c axis. Whereas in (I), hydrogen bonds between bromide ligands and water molecules lead to one-dimensional chains running along the b axis, in (II) two-dimensional sheets of water molecules and chloride ligands are formed which combine with the polymeric caesium-crown polymer to give a three-dimensional network. Although both compounds have a similar composition, i.e. a Cs(+) cation with a halogen, an 18-crown-6 ether and a water ligand, the crystal structures are rather different. On the other hand, it is remarkable that (I) is isomorphous with the already published iodide compound.

Keywords: CsBr; CsCl; crown ether; crystal structure; hydrate; hydrogen bonding.