Bridging cobalt–calixarene subunits into a Co8 entity or a chain with 4,4′-bipyridyl

• Two metal-calixarene aggregates obtained by solvothermal method.
• Isolated Z-shaped Co8 entities with two Co4-TC4A SBUs bridged by two parallel 4,4′-bpy.
• A zigzag chain with [Co3-SC4A-SO2]2 dimers bridged by single 4,4’-bpy.

Two novel calixarene-based compounds, {[Co4Cl(TC4A)(HCOO)3]2(4,4′-bpy)2} (CIAC-206) and {[Co3(H2O)(SC4A-SO2)(HCOO)2]2(4,4′-bpy)}n (CIAC-207) (H4TC4A = p-tert-butylthiacalix[4]arene, SC4A-SO2 = p-tert-butylsulfonylcalix[4]arene, 4,4′-bpy = 4,4′-bipyridyl) were synthesized under solvothermal conditions, and characterized by single crystal X-ray diffraction analysis, TG–DSC analysis, elemental analysis and IR spectroscopy. These two structures are featured with isolated Z-shaped Co8 entities containing two Co4-TC4A subunits bridged by two parallel 4,4′-bpy (CIAC-206) and some zigzag chains with [Co3-SC4A-SO2]2 dimers bridged by single 4,4′-bpy (CIAC-207), respectively. In order to evaluate their properties, the N2 sorption behavior and magnetic property were examined.