Synthesis and crystal structures of (2.2.2-cryptand)rubidium chloride and bromide hydrates

Two complexes, (2.2.2-cryptand)rubidium chloride and bromide hydrates [Rb(Crypt-222]Hal · 3.5H2O (Hal = Cl (I) and Br (II)), are synthesized. The structures of isomorphic crystals of compounds I and II are studied by X-ray diffraction analysis. The crystals are trigonal: space group P $$\overline 3 $$ , Z = 2; I: a = 11.810 Å, c = 11.302 Å; II: a = 11.890 Å, c = 11.402 Å. The structures are solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.060 (I) and 0.077 (II) for 2650 (I) and 2700 (II) independent reflections (CAD-4 automated diffractometer, λMoK α radiation). In crystals of complexes I and II, the [Rb(Crypt-222)]+ cation of the host-guest type lies on the crystallographic axis 3 and has the approximate symmetry D 3. In complexes I and II, the coordination polyhedron of the Rb+ cation is a two-base-centered trigonal prism somewhat distorted to an antiprism. The crystals of compounds I and II contain H-bonded disordered cubes of the water molecules and Cl− or Br− anions.