Desynchronization of Pedal Motion: Crystallographic and Theoretical Study of (E)-4

Abstract

The single crystal X-ray diffraction analysis of the title compound, C <inf>15</inf>H<inf>16</inf>N<inf>2</inf>O, reveals that its molecules exhibit whole-molecule disorder at both crystal lattice sites due to pedal motion in solid state. The compound crystallizes in the monoclinic space group P 2 <inf>1</inf>/c with a = 20.5504(14) Å, b = 10.8887(5) Å, c = 12.0191(8) Å and β = 96.927(5)°. While major pedal conformers of the compound in solid state are stabilized by intermolecular O-H⋯N type hydrogen bonds leading to the formation of C(7) chains at Site 1 and C(8) chains at Site 2 along [0 1 0] axis, C-H⋯π type intermolecular interactions between major and minor conformers also serve to stabilize minor pedal conformers. An interesting feature about the crystal structure is that pedal conformers at Site 1 have two different occupancy factors arising from desynchronization of pedal motion along [2 1 0] direction in crystal phase. Quantum chemical calculations at the B3LYP/6-31++G level suggest that the desynchronization of pedal motions make more unstable pedal conformers at Site 1 than those at Site 2. © 2008 Springer Science+Business Media, LLC.