Extensive hydrogen and halogen bonding,and absence of intramolecular hydrogen bonding between alcohol and nitro groups in a series of endo‐nitronorbornanol compounds

The influence of the substituent at the C2 position on the hydrogen‐bonding patterns is compared for a series of five related compounds, namely (±)‐3‐exo,6‐exo‐dibromo‐5‐endo‐hydroxy‐3‐endo‐nitrobicyclo2.2.1]heptane‐2‐exo‐carbonitrile, C₈H₈Br₂N₂O₃, (II), (±)‐3‐exo,6‐exo‐dibromo‐6‐endo‐nitro‐5‐exo‐phenylbicyclo2.2.1]heptan‐2‐endo‐ol, C₁₃H₁₃Br₂NO₃, (III), (±)‐methyl 3‐exo,6‐exo‐dibromo‐5‐endo‐hydroxy‐3‐endo‐nitrobicyclo2.2.1]heptane‐2‐exo‐carboxylate, C₉H₁₁Br₂NO₅, (IV), (±)‐methyl 3‐exo,6‐exo‐dibromo‐7‐diphenylmethylidene‐5‐endo‐hydroxy‐3‐endo‐nitrobicyclo2.2.1]heptane‐2‐exo‐carboxylate, C₂₂H₁₉Br₂NO₅, (V), and (±)‐methyl 3‐exo,6‐exo‐dibromo‐5‐endo‐hydroxy‐3‐endo‐nitro‐7‐oxabicyclo2.2.1]heptane‐2‐exo‐carboxylate, C₈H₉Br₂NO₆, (VI). The hydrogen‐bonding motif in all five compounds is a chain, formed by O—H...O hydrogen bonds in (III), (IV), (V) and (VI), and by O—H...N hydrogen bonds in (II). All compounds except (III) contain a number of Br...Br and Br...O halogen bonds that connect the chains to each other to form two‐dimensional sheets or three‐dimensional networks. None of the compounds features intramolecular hydrogen bonding between the alcohol and nitro functional groups, as was found in the related compound (±)‐methyl 3‐exo,6‐exo‐dichloro‐5‐endo‐hydroxy‐3‐endo‐nitrobicyclo2.2.1]heptane‐2‐exo‐carboxylate, (I) Boeyens, Denner & Michael (1984b). J. Chem. Soc. Perkin Trans. 2, pp. 767–770]. The crystal structure of (V) exhibits whole‐molecule disorder.