Asymmetric rotations and dimerization driven by normal to modulated phase transition in 4-biphenylcarboxy coupled L-phenylalaninate.

Abstract

Amongst the derivatives of 4-biphenylcarboxylic acid and amino acid esters, the crystal structure of 4-biphenylcarboxy-(L)-phenylalaninate is unusual owing to its monoclinic symmetry within a pseudo-orthorhombic crystal system. The distortion is described by a disparate rotational property around the chiral centers (ϕ_chiral ≃ -129° and 58°) of the two molecules in the asymmetric unit. Each of these molecules comprises planar biphenyl moieties (ϕ_biphenyl = 0°). Using temperature-dependent single-crystal X-ray diffraction experiments we show that the compound undergoes a phase transition below T ∼ 124 K that is characterized by a commensurate modulation wavevector, q = δ(101), δ = ½. The (3+1)-dimensional modulated structure at T = 100 K suggests that the phase transition drives the biphenyl moieties towards noncoplanar conformations with significant variation of internal torsion angle (ϕ^max_biphenyl ≤ 20°). These intramolecular rotations lead to dimerization of the molecular stacks that are described predominantly by distortions in intermolecular tilts (θ_max ≤ 20°) and small variations in intermolecular distances (Δd_max ≃ 0.05 Å) between biphenyl molecules. Atypical of modulated structures and superstructures of biphenyl and other polyphenyls, the rotations of individual molecules are asymmetric (Δϕ_biphenyl ≈ 5°) while ϕ_biphenyl of one independent molecule is two to four times larger than the other. Crystal-chemical analysis and phase relations in superspace suggest multiple competing factors involving intramolecular steric factors, intermolecular H-C...C-H contacts and weak C-H...O hydrogen bonds that govern the distinctively unequal torsional properties of the molecules.