Electronic and Crystal Packing Effects in Terms of Static and Kinetic Force Field Features: Picolinic Acid N-Oxide and Methimazole,Crystal Growth & Design

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Electronic and Crystal Packing Effects in Terms of Static and Kinetic Force Field Features: Picolinic Acid N-Oxide and Methimazole
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2023-02-02 , DOI: 10.1021/acs.cgd.2c01286
Sergey V. Kartashov ₁ , Sergey A. Shteingolts ₁ , Adam I. Stash ₂ , Vladimir G. Tsirelson _{3,

4} , Robert R. Fayzullin ₁

Affiliation

Herein, we experimentally obtained and studied the inner-crystal scalar potential fields and the associated vector force fields of static and kinetic nature in picolinic acid N-oxide (PANO) and methimazole. The “through-bond” and “through-space” electronic effects were defined and distinguished via the vector fields and concurred with the penetration of the electron contributor’s electrostatic and kinetic force field pseudoatoms (φ_es- and φ_k-basins) into the occupier’s chemical atom (ρ-basin). A special focus was given to the dipolar N⁺–O^– bond as well as to the thioamide N–C═S and carboxylic O═C–OH fragments. An unusual way of interatomic charge transfer was revealed between two nonbonded hydrogen atoms [COO−]H···H[−C] in the PANO crystal. The experimental electric and kinetic force fields in the molecular crystals were compared to the theoretical ones for the free molecules and hydrogen-bonded associates, which helped figure out the natural consequences of the crystal packing effect. As expected, the appearance of neighboring attractors in a dense crystal packing requires zero-flux surfaces (ZFSs) emerging in the vector fields and the compression of the outer force field pseudoatoms of a molecule. We proposed to consider a ZFS in the kinetic force field to be a turning surface for electrons in the sense that an electron passed through the boundary is immediately affected by the redirected force attributed to another attractor. The strengthening and noticeable increase observed in the covalency of the intramolecular hydrogen bond O–H···O in the PANO crystal is a direct consequence of such compression of the hydrogen atom and pseudoatoms by the inner-crystal environment. The Pauli and fermionic scalar and vector fields were applied to locate electron lone pairs and describe their involvement in noncovalent interactions within the donor–acceptor mechanism.

中文翻译：

静态和动态力场特征方面的电子和晶体堆积效应：吡啶甲酸 N-氧化物和甲巯咪唑

在此，我们通过实验获得并研究了吡啶甲酸 N-氧化物 (PANO) 和甲巯咪唑的内部晶体标量势场和相关的静态和动态矢量力场。“穿透键”和“穿透空间”电子效应通过矢量场定义和区分，并与电子贡献者的静电和动能场伪原子（φ es - 和 φ k -basins）渗透_到占据_者的化学原子（ρ-盆地）。特别关注偶极 N ⁺ –O ^–键以及硫代酰胺 N-C=S 和羧基 O=C-OH 片段。在 PANO 晶体中的两个非键合氢原子 [COO−]H···H[−C] 之间揭示了一种不寻常的原子间电荷转移方式。将分子晶体中的实验电场和动能场与自由分子和氢键结合的理论场进行了比较，这有助于找出晶体堆积效应的自然结果。正如预期的那样，密集晶体堆积中相邻吸引子的出现需要矢量场中出现零通量表面 (ZFS) 和分子的外力场假原子的压缩。我们建议将动能场中的 ZFS 视为电子的转向表面，因为通过边界的电子会立即受到归因于另一个吸引子的重定向力的影响。在 PANO 晶体中观察到的分子内氢键 O-H···O 共价键的加强和显着增加是晶体内环境对氢原子和假原子的这种压缩的直接结果。泡利和费米子标量场和矢量场用于定位电子孤对电子并描述它们参与供体-受体机制中的非共价相互作用。在 PANO 晶体中观察到的分子内氢键 O-H···O 共价键的加强和显着增加是晶体内环境对氢原子和假原子的这种压缩的直接结果。泡利和费米子标量场和矢量场用于定位电子孤对电子并描述它们参与供体-受体机制中的非共价相互作用。在 PANO 晶体中观察到的分子内氢键 O-H···O 共价键的加强和显着增加是晶体内环境对氢原子和假原子的这种压缩的直接结果。泡利和费米子标量场和矢量场用于定位电子孤对电子并描述它们参与供体-受体机制中的非共价相互作用。

更新日期：2023-02-02

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