Cubanecarboxylic Acids. Crystal Engineering Considerations and the Role of C−H···O Hydrogen Bonds in Determining O−H···O Networks

Abstract

A family of 4-substituted-1-cubanecarboxylic acids have been synthesized and their X-ray crystal structures analyzed. The rare syn-anti O−H···O catemer 6 is a recurring pattern in this series of compounds. Catemer 6 is observed in the crystal structures of 4-chloro-1-cubanecarboxylic acid ( 10 ), 4-bromo-1-cubanecarboxylic acid ( 11 ), 4-iodo-1-cubanecarboxylic acid ( 12 ), and 4-(methoxycarbonyl)-1-cubanecarboxylic acid ( 13 ). The ready occurrence of catemer 6 in this family is ascribed to its stabilization by auxiliary C−H···O hydrogen bonds formed by the relatively acidic cubyl C−H groups. The frequency of occurrence of 6 also facilitates its definition as a useful supramolecular synthon. As is true in many catemers, the formation of 6 is sensitive to steric factors. Therefore, the robustness of this synthon may be assessed by analyzing the crystal structures of molecules wherein the 4-substituent is too small (R = H, 14 ), too large (R = Ph, 15 ), or has a specific hydrogen bonding preference of its own (R = CONH 2, 16 ). In these structures, either dimer 3 (in 14 and 15 ) or heterodimer 22 (in 16 ) is observed. Powder diffraction shows that the previously noted structure of 1,4-cubanedicarboxylic acid ( 7 ) that contains catemer 6 is characteristic of the bulk material. In summary, the syn-anti catemer is the dominant supramolecular synthon in this family of cubanecarboxylic acids.