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

TL;DR

This study reveals a temperature-induced phase transition in 4-biphenylcarboxy-(L)-phenylalaninate, leading to asymmetric molecular rotations, dimerization, and conformational changes driven by modulated structures and intermolecular interactions.

Contribution

It provides detailed structural insights into the asymmetric rotations and dimerization caused by a phase transition in a biphenyl derivative, highlighting the role of intramolecular and intermolecular factors.

Findings

Phase transition occurs below 124 K with a modulation wave vector.

Biphenyl moieties adopt non-coplanar conformations with significant torsion.

Asymmetric molecular rotations lead to dimerization and structural modulation.

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 lattice. The distortion is described by disparate rotational property around the chiral centers ($\varphi_{\mathrm{chiral}}$ $\simeq$ -129 degrees and 58 degrees) of the two molecules in the asymmetric unit. Each of these molecules comprise of planar biphenyl moieties ($\varphi_{\mathrm{biphenyl}}$ = 0 degrees). Using temperature dependent single crystal X-ray diffraction experiments we show that the compound undergoes a phase transition below $T$ $\sim$ 124 K that is characterized by a commensurate modulation wave vector, $\mathbf{q}$ = $\delta(101)$, $\delta$ = $\frac{1}{2}$. 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 ($\varphi^{\mathrm{max}}_{\mathrm{biphenyl}}$ $\leq$ $20$ 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, the rotations of individual molecules are asymmetric ($\Delta$$\varphi_{\mathrm{biphenyl}}$ $\approx$ 5 degrees) while $\varphi_{\mathrm{biphenyl}}$ 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${\cdot}{\cdot}{\cdot}$C--H contacts and weak C--H${\cdot}{\cdot}{\cdot}$O hydrogen bonds that govern the distinctively unequal torsional property of the molecules.