论文标题

在4-二苯基羧基偶联的L-苯基丙酰氨酸偶联中,不对称旋转和二聚化驱动的二聚化驱动

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

论文作者

Dey, Somnath, Sasmal, Supriya, Mondal, Saikat, Kumar, Santosh, Chowdhury, Rituparno, Sarkar, Debashrita, Reddy, C. Malla, Peters, Lars, Roth, Georg, Haldar, Debasish

论文摘要

在4-二苯基羧酸和氨基酸酯的衍生物中,4-二苯基羧基(L) - 苯基丙酰氨酸的晶体结构由于其在伪 - 正常的晶格中的单斜形对称性而异常。失真是通过手性中心周围的不同旋转特性($φ_ {\ mathrm {Mathrm {Mathrm {Mathrm {Mathrm {Mathrm {Mathrm {Mathrm {Mathrm {Mathrm {Mathrm {$ \ simeq $ -129度和58度)中的两个分子中的两个分子。这些分子中的每一个都包含平面双苯基部分($φ_ {\ mathrm {biphenyl}} $ = 0度)。使用依赖温度的单晶X射线衍射实验,我们表明,该化合物的相变低于$ t $ $ \ sim $ 124 k,其特征在于相应调制波向量,$ \ mathbf {q} $ = $ = $Δ(101)$,$δ$δ$ = $ = $ \ freac = $ \ freac {frac {frac {1} $} $} $} $。 $ t $ = 100 k时的(3+1)维度调制结构表明,相过渡将双苯基部分驱动到具有内部扭转的显着变化的非共面构构($φ^{\ mathrm {max}} _ {这些分子内旋转导致分子堆栈的二聚化,这些堆栈主要通过分子间倾斜和分子间距离的较小变化来描述。双苯基和其他聚苯基的调制结构和上层建筑的非典型,单个分子的旋转是不对称的($δ$δ$Δ$φ另一个。超空间中的晶体化学分析和相位关系表明了涉及分子内空间因子的多个竞争因素,分子间H-c $ {\ cdot} {\ cdot} {\ cdot} {\ cdot} $ c-h接触和弱c- h $ c-h $ {\ cdot} {\ cdot} {\ cdot}分子。

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 ($φ_{\mathrm{chiral}}$ $\simeq$ -129 degrees and 58 degrees) of the two molecules in the asymmetric unit. Each of these molecules comprise of planar biphenyl moieties ($φ_{\mathrm{biphenyl}}$ = 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, $\mathbf{q}$ = $δ(101)$, $δ$ = $\frac{1}{2}$. 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 ($φ^{\mathrm{max}}_{\mathrm{biphenyl}}$ $\leq$ $20$ 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 ($Δ$$φ_{\mathrm{biphenyl}}$ $\approx$ 5 degrees) while $φ_{\mathrm{biphenyl}}$ 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.

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