CALIXARENES AS 2ND-SPHERE LIGANDS FOR TRANSITION-METAL IONS - SYNTHESIS AND CRYSTAL-STRUCTURE OF [(H2O)5NI(NC5H5)]2(NA)[CALIX[4]ARENE SULFONATE].3.5H2O AND [(H2O)4CU(NC5H5)2]-(H3O)3 [CALIX[4]ARENE SULFONATE].10 H2O

The title compounds crystallize such that bilayers of calixarenes are separated by hydrophilic layers. In each case the transition metal has, in addition to a primary sphere of ligands, a second-sphere coordination by a calixarene. [(H2O)5Ni(NC5H5)]2(Na)[calix[4]arene sulfonate].3.5 H2O, 1, crystallizes in the triclinic space group P1BAR with a = 12.487(4), b = 14.281(2), c = 15.055(5) angstrom, alpha = 85.66(2), beta = 80.07(2), gamma = 80.48(2)-degrees, and D(c) = 1.64 g cm-3 for Z = 2. Refinement based on 2441 observed reflections led to a final R value of 0.066. There are two different environments for the nickel-containing cations: one is positioned within the hydrophilic layer with the pyridine ligand intercalated into the hydrophobic calixarene bilayer and the other is also positioned within the hydrophilic layer, but the pyridine ligand is inserted into the hydrophobic cavity of the calix[4]arene. [(H2O)4Cu(NC5H5)2](H3O)3[calix[4]arene sulfonate].10 H2O, 2, crystallizes in the triclinic space group P1BAR with a = 15.438(4), b = 15.727(6), c = 12.121(9) angstrom, alpha = 112.74(4), beta = 102.02(4), gamma = 85.34(4)-degrees, and D(c) = 1.57 g cm-3 for Z = 2. Refinement based on 3925 observed reflections led to a final R value of 0.107. The structure is similar to that of 1 except that the one copper-containing cation spans the hydrophilic layer and is intercalated into the bilayer of calixarenes on one side and positioned into the calixarene cavity on the other.