This work describes the syntheses and characterizations of double-armed benzo-15-crown-5 containing nitro (1), amine (2), and imine (3-5) groups, and their sodium complexes (1a-5a). Structures of the ligands (1-5) and sodium complexes (1a-5a) were identified via elemental analyses, and infrared, H-1- nuclear magnetic resonance (NMR), C-13-NMR, and mass spectrometry. The metal extractions were examined by using ultravoilet-visible spectrophotometry. Single crystal for 2 was successfully obtained, and its X-ray crystal structure was resolved. The compound 2 crystallizes in triclinic, space group p-1 with a = 9.1420(3), b = 14.9580(4), c = 20.4110(5), and Z = 4. (C) 2013 Wiley Periodicals, Inc.