Abstract: | 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, 1H‐ nuclear magnetic resonance (NMR), 13C‐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. |