Synthesis and structures of three benzoannelated macrobicyclic diamides

• Published in: Acta crystallographica. Section C, Crystal structure communications Crystal structure communications, 2022-03, Vol.78 (3), p.176-180
• Main Authors: Smith, Gary L. N., Taylor, Richard W.
• Format: Article
• Language: English
• Subjects: benzoannelated; cryptand; crystal structure; Crystallography, X-Ray; Diamide; Diketones; high dilution; Hydrogen Bonding; macrobicyclic diamides; Nitrogen tetroxide; Synthesis
• ISSN: 2053-2296; 0108-2701; 2053-2296; 1600-5759
• DOI: 10.1107/S2053229622001449

We report the synthesis and structures of 9,10,20,21‐tetrahydro‐5,14‐(ethanooxyethano)dibenzo[e,q][1,4,10,13,7,16]tetraoxadiazacyclooctadecine‐6,13‐dione [systematic name: 8,11,21,24,29‐pentaoxa‐1,18‐diazatetracyclo[16.8.5.02,7.012,17]hentriaconta‐2,4,6,12(17),13,15‐hexaene‐19,26‐dione C24H28N2O8, I], 6,7,9,10,12,13,20,21‐octahydro‐5,14‐(ethanooxyethano)dibenzo[e,q][1,4,10,13,7,16]tetraoxadiazacyclooctadecine‐23,27‐dione (8,11,21,24,29‐pentaoxa‐1,18‐diazatetracyclo[16.8.5.02,7.012,17]hentriaconta‐2,4,6,12,14,16‐hexaene‐27,31‐dione; C24H28N2O7, II), and 9,10,20,21‐tetrahydro‐5,14‐(ethanooxyethanooxyethano)dibenzo[e,q][1,4,10,13,7,16]tetraoxadiazacyclooctadecine‐6,13‐dione [8,11,21,24,29,32‐hexaoxa‐1,18‐diazatetracyclo[16.8.8.02,7.012,17]tetratriaconta‐2,4,6,12(17),13,15‐hexaene‐19,26‐dione; C26H32N2O7, III]. All three compounds are made up of two tertiary diamides and are composed of two 15‐membered rings with N2O3 donor sets and one 18‐membered ring with an N2O4 donor set (compounds I and II) or three 18‐membered rings with N2O4 donor sets (compound III). The solid‐state structures of compounds I and II show little effects from the movement of the amide groups. However, compound III has a larger cavity and a different orientation of donor atoms in comparison to compounds I and II. Three benzoannelated macrobicyclic diamides were synthesized, characterized, and analyzed by X‐ray crystallography. The compounds show the structural effects of varying the location of the diamides and changing the size of the macrocycles.