Pseudoacids. III: formation and structures of new cyclic oxocarboxylic acids

Crystal and molecular structures for aryl- and benzyl-substituted 3-hydroxy-3,4-dihydroisobenzopyran-1-one are described. For the 4,4-dimethyl derivative, two monoclinic modifications are produced on sublimation: (1) P2₁/c, a = 23.668(6) Å b = 11.749(4) Å c = 7.215(2) Å = 96.70(2); V = 1992.6(10) ų; (2) P2₁/c, a = 11.509(4) Å, b = 12.429(4) Å, c = 6.933(2) Å, = 91.12(3), V = 991.6(6) Å. In both, hydroxy groups are pseudoaxial, and molecules form dimeric complementary but noncooperative hydrogen bonds. In the 6-methoxy derivative (3), P2₁/c; a = 14.185(7) Å b = 4.105(4) Å c = 15.598(13) Å = 98.59(6); V = 898.1(10) ų, the hydroxy group is pseudoequatorial, and the intermolecular hydrogen bonding forms infinite chains. In the 4,4-dimethyl-7-nitro derivative (4), C2/c, a = 19.365(4), b = 8.425(2), c = 13.464(4), = 92.62(2), V = 2194.2(7) ų, the hydroxy group is pseudoaxial, and the intermolecular hydrogen bonding forms chains. Compared to the unmethylated compounds, the interbond angles within the ring at the dimethylated carbon are contracted.