Unequal torsional rotations driven by normal to modulated phase transition in 4-biphenylcarboxy coupled L-phenylalaninate governed by non-covalent constraints

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 lattice. The distortion is described by disparate rotational property around the chiral centers ( ϕ chiral ’ -129 degrees and 58 degrees) of the two molecules in the asymmetric unit. Each of these molecules comprise of planar biphenyl moieties ( ϕ biphenyl = 0 degrees). 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 wave vector, q = δ (101), δ = 12 . The (3+1) dimensional modulated structure at T = 100 K suggests that the phase transition drives the biphenyl moieties towards non coplanar conformations with significant variation of internal torsion ( ϕ maxbiphenyl ≤ 20 degrees). These intramolecular rotations lead to dimerization of the molecular stacks that are described predominantly by intermolecular tilts and small variations in intermolecular distances. Atypical of modulated structures and superstructures of biphenyl and other polyphenyls, ϕ biphenyl of one independent molecule is two to four times larger than the other. We suggest that while the rotations arise from intramolecular steric factors, competing intermolecular H–C ··· C–H contacts and weak C–H ··· O hydrogen bonds govern the distinctively unequal torsional property of the molecules.

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