chemicallytechFine Chemical TechnologiesТонкие химические технологии2410-65932686-7575MIREA – Russian Technological University (RTU MIREA).10.32362/2410-6593-2021-16-2-113-124chemicallytech-1696Research ArticleTHEORETICAL BASIS OF CHEMICAL TECHNOLOGYТЕОРЕТИЧЕСКИЕ ОСНОВЫ ХИМИЧЕСКОЙ ТЕХНОЛОГИИStructural characterization of hydrogen bonding for antipyrine derivatives: Single-crystal X-ray diffraction and theoretical studiesСтруктурное описание водородной связи в производных антипирина: рентгеноструктурные и теоретические исследованияhttps://orcid.org/0000-0001-7989-8009РуккН. С.RukkN. S.

 к.х.н., доцент кафедры неорганической химии им. А.Н. Реформатского,

119571, Москва, пр-т Вернадского, 86

Cand. Sci. (Chem.), Associate Professor, A.N. Reformatskii Department of Inorganic Chemistry,

86, Vernadskogo pr., Moscow, 119571

roukkn@inbox.ruhttps://orcid.org/0000-0002-0473-770XШамсиевР. С.ShamsievR. S.

д.х.н., профессор кафедры физической химии им. Я.К. Сыркина, 

119571, Москва, пр-т Вернадского, 86

Dr. Sci. (Chem.), Professor, Ya.K. Syrkin Department of Physical Chemistry, 

86, Vernadskogo pr., Moscow, 119571

shamsiev.r@gmail.comАльбовД. В.AlbovD. V.

к.х.н., научный сотрудник, химический факультет,

119992, Москва, Ленинские Горы, 1

Cand. Sci. (Chem.), Senior Scientific Researcher, Faculty of Chemistry, 

1, Leninskie Gory, Moscow, 119992

dmitryalbov@mail.ruМудрецоваС. Н.MudretsovaS. N.

старший научный сотрудник, химический факультет,

119992, Москва, Ленинские Горы, 1

Senior Scientific Researcher, Faculty of Chemistry,

1, Leninskie Gory, Moscow, 119992

МИРЭА – Российский технологический университет (Институт тонких химических технологий им. М.В. Ломоносова)РоссияMIREA – Russian Technological University (M.V. Lomonosov Institute of Fine Chemical Technologies)Russian FederationМосковский государственный университет им. М.В. ЛомоносоваРоссияLomonosov Moscow State UniversityRussian Federation202121052021162113137Copyright © Rukk N.S., Shamsiev R.S., Albov D.V., Mudretsova S.N., 20212021Рукк Н.С., Шамсиев Р.С., Альбов Д.В., Мудрецова С.Н.Rukk N.S., Shamsiev R.S., Albov D.V., Mudretsova S.N.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://www.finechem-mirea.ru/jour/article/view/1696Objectives

Objectives. The paper is devoted to the crystal structure characterization of 5-methyl-2-phenyl4H-pyrazol-3-one (compound I) and 2-(4-chlorophenyl)-5-methyl-4H-pyrazol-3-one (compound II).

Methods

Methods. Single-crystal X-ray diffraction studies and theoretical calculations: Density functional theory and quantum theory of atoms in molecules.

Results

Results. In the solid state, the crystal structure of compound I is characterized by the alternation of OH and NH tautomers connected via O–H---O and N–H---N hydrogen bonds. For compound II, the existence of chains built from the NH monomers via hydrogen bonding can be explained by the peculiarities of cooperative effects. In the framework of quantum theory of atoms in molecules, the following topological characteristics are calculated for all dimers: electron density, Laplacian of electron density, density of kinetic, potential, and total energy in the critical point of the intermolecular hydrogen bond. It is concluded that the hydrogen bond in dimers 1–4, 7 (compound I), and 8–11 (compound II) can be assigned to the intermediate (between covalent and dispersion types) interaction owing to hydrogen bond formation with the participation of electronegative oxygen- (and/or nitrogen-) atoms, whereas H-bond in dimers 5 and 6 (compound I) can be attributed to the dispersion one (no hydrogen bond formation or weak H-bond formation), and it represents the weak interaction, being in agreement with length for intermolecular hydrogen bond in dimers. The electron density and total energy density values demonstrate that the strongest intermolecular H-bonds take place in dimers 1 (OH---O), 4 (OH---O), 7 (OH---N), 8 (OH---O), 9 (NH---N), and 11 (OH---N). The results obtained for compounds I and II are compared with data for antipyrine (1,2-dihydro-1,5-dimethyl-2-phenyl-3H-pyrazol-3-one; compound III)

Conclusions

Conclusions. An important role of intermolecular hydrogen bonding in the crystal packing, molecule association and self-organization via dimer- or more extended species formation has been demonstrated. 

Цели

Цели. Работа посвящена рассмотрению особенностей кристаллического строения для 5-метил-2-фенил-4Н-пиразол-3-она, I, и 2-(4-хлорфенил)-5-метил-4Н-пиразол-3-она, II, в сравнении с результатами теоретических расчетов.

Методы

Методы. Рентгеноструктурный анализ и расчеты в рамках теории функционала плотности и квантовой теории атомов в молекулах.

Результаты

Результаты. Показано, что кристаллическая структура I в твердом агрегатном состоянии характеризуется альтернацией OH и NH таутомеров, связанных посредством водородных связей O–H---O и N–H---N. Для соединения II существование цепочек из связанных водородной связью мономеров NH объясняется особенностями кооперативных эффектов и с теоретической точки зрения. В рамках квантовой теории атомов в молекулах (QTAIM) для всех димеров в критической точке межмолекулярной водородной связи были рассчитаны топологические параметры: электронная плотность, лапласиан электронной плотности, плотность кинетической, потенциальной и полной энергии. Показано, что водородная связь в димерах 1–4, 7 (соединение I) и 8–11 (соединение II) относится к взаимодействию промежуточного типа (между ковалентным и дисперсионным взаимодействием) за счет образования водородных связей с участием электроотрицательных атомов кислорода (и/или атомов азота), а водородная связь в димерах 5 и 6 (соединение I) – к дисперсионному типу (отсутствие водородной связи или образование слабой Н-связи) и представляет собой слабое взаимодействие, что коррелирует с длиной межмолекулярной водородной связи в димерах. На основании анализа значений электронной плотности и плотности полной энергии показано, что наиболее сильные межмолекулярные Н-связи реализуются в димерах 1 (OH---O), 4 (OH---O), 7 (OH---N), 8 (OH---O), 9 (NH---N) and 11 (OH---N). Результаты, полученные для I и II, сопоставлены с данными для 1,2-дигидро-1,5-диметил-2-фенил-3Н-пиразол-3-она, III.

Выводы

Выводы. Показана важная роль межмолекулярной водородной связи в кристаллической упаковке, ассоциации и самоорганизации молекул.

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The authors declare that there are no conflicts of interest present.