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Symmetrical Noncovalent Interactions Br···Br Observed in Crystal Structure

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Symmetrical Noncovalent Interactions Br···Br Observed in Crystal Structure S S symmetry Communication SymmetricalCommunication Noncovalent Interactions Br···Br Symmetrical Noncovalent Interactions Br···Br ObservedObserved in Crystal Structure of Exotic Primary PeroxidePrimary Peroxide Dmitrii S. Bolotin 1,*, Mikhail V. Il’in 1, Vitalii V. Suslonov 2 and Alexander S. Novikov 1,* Dmitrii S. Bolotin 1,*, Mikhail V. Il’in 1, Vitalii V. Suslonov 2 and Alexander S. Novikov 1,* 1 Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 7/9, Saint Petersburg 1 Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 7/9, 199034, Russia; Saint [email protected] 199034, Russia; [email protected] 2 2 CenterCenter for for X-ray X-ray Diffraction Diffraction Studies, Studies, Saint Saint Petersburg Petersburg State State University, University, Universitetskii Universitetskii Pr., Pr., 26, 26, Saint PetersburgSaint Petersburg 198504, 198504,Russia; Russia;[email protected] [email protected] * Correspondence:Correspondence: [email protected] [email protected] (D.S.B.), (D.S.B.); [email protected] [email protected] (A.S.N.) (A.S.N.) Received: 31 March 2020; Accepted: 14 April 2020; Published: date Received: 31 March 2020; Accepted: 14 April 2020; Published: 17 April 2020 Abstract: 4-Bromobenzamidrazone reacts with cyclopentanone giving Abstract: 4-Bromobenzamidrazone reacts with cyclopentanone giving 3-(4-bromophenyl)-5-(4- 3-(4-bromophenyl)-5-(4-peroxobutyl)-1,2,4-triazole, which precipitated as pale-yellow crystals peroxobutyl)-1,2,4-triazole, which precipitated as pale-yellow crystals during the reaction. The during the reaction. The intermolecular noncovalent interactions Br···Br in the single-crystal XRD intermolecular noncovalent interactions Br Br in the single-crystal XRD structure of the peroxo structure of the peroxo compound were studied··· theoretically using quantum chemical calculations compound were studied theoretically using quantum chemical calculations (!B97XD/x2c-TZVPPall) (ωB97XD/x2c-TZVPPall) and quantum theory of atoms in molecules (QTAIM) analysis. These and quantum theory of atoms in molecules (QTAIM) analysis. These attractive intermolecular attractive intermolecular noncovalent interactions Br···Br is type I halogen···halogen contacts and noncovalent interactions Br Br is type I halogen halogen contacts and their estimated energy is their estimated energy is 2.2–2.5··· kcal/mol. These weak··· interactions are suggested to be one of the 2.2–2.5 kcal/mol. These weak interactions are suggested to be one of the driving forces (albeit driving forces (albeit surely not the main one) for crystallization of the peroxo compound during surely not the main one) for crystallization of the peroxo compound during the reaction and thus its the reaction and thus its stabilization in the solid state. stabilization in the solid state. Keywords: organic peroxide; triazole; DFT; QTAIM; noncovalent interactions; halogen bonding Keywords: organic peroxide; triazole; DFT; QTAIM; noncovalent interactions; halogen bonding 1.1. Introduction Introduction ShortShort halogen···halogen halogen halogen contacts contacts can can be be classified classified on on two two types types (Figure (Figure 11))[ [1].1]. Type Type I I is is simply ··· duedue to crystal packingpacking eeffects,ffects, whilewhile type type II II (halogen (halogen bonding) bonding) is is directed directed noncovalent noncovalent interactions interactions [2] [2]formed formed between between the theσ-hole σ-hole (electrophilic (electrophilic region) region) on theon the halogen halogen (Hal) (Hal) atom atom and and a nucleophile. a nucleophile. FigureFigure 1. 1. TypesTypes of of Hal···Hal Hal Hal noncovalent noncovalent interactions. interactions. ··· AlthoughAlthough both types ofof HalHal···HalHal contactscontacts havehave similar similar abundance, abundance, today today halogen halogen bond bond (type (type II) ··· II)has has drawn drawn significantly significantly higher higher attention attention and and similarly similarly toto hydrogenhydrogen bonds,bonds, metallophilic contacts, contacts, and stacking interactions, halogen bonding is now widely used in crystal growth and design and in Symmetry 2020, 12, x; doi: FOR PEER REVIEW www.mdpi.com/journal/symmetry Symmetry 2020, 12, 637; doi:10.3390/sym12040637 www.mdpi.com/journal/symmetry Symmetry 2020, 12, x FOR PEER REVIEW 2 of 7 Symmetry 2020, 12, x 637 FOR PEER REVIEW 2 of 7 and stacking interactions, halogen bonding is now widely used in crystal growth and design and in andsupramolecular stacking interactions, engineering halogen [1,3–5]. bonding The isrecently now widely published used inrelevant crystal growthreviews and are design devoted and into supramolecular engineeringengineering [1 ,[1,3–5].3–5]. The The recently recently published published relevant relevant reviews reviews are devoted are todevoted theoretical to theoretical approaches to Hal···Hal contacts [6,7] and also application of Hal···Hal contacts in theoreticalapproaches approaches to Hal Hal to contacts Hal···Hal [6,7 ]contacts and also [6,7] application and also of HalapplicationHal contacts of Hal···Hal in supramolecular contacts in supramolecular engineering··· [8–12], catalytic reactions [13], organometallic··· and coordination supramolecularengineering [8–12 engineering], catalytic reactions [8–12], [ 13catalytic], organometallic reactions and [13], coordination organometallic chemistry and [14 –coordination18], polymer chemistry [14–18], polymer science [19], medical chemistry and drug discovery [20–23], and to the chemistryscience [19 ],[14–18], medical polymer chemistry science and drug [19], discovery medical [chemistry20–23], and and to thedrug involvement discovery of[20–23], Hal Hal and contacts to the involvement of Hal···Hal contacts in human function [24]. ··· involvementin human function of Hal···Hal [24]. contacts in human function [24]. In this communication, we describe symmetrical type I noncovalent interactions observed In this communication, we describe symmetrical type I noncovalent interactions observed between betweenIn this two communication, bromine atoms, wewhich describe allow symmetricalisolation of primarytype I noncovalentperoxide formed interactions in the reaction observed of betweentwoamidrazone bromine two and atoms,bromine cyclopentanone which atoms, allow which isolation(along allow with of isolation primary different of peroxide primaryhydrogen formed peroxide bonds in theandformed reaction other in crystalthe of amidrazonereaction packing of amidrazoneand cyclopentanone and cyclopentanone (along with di (alongerent hydrogenwith different bonds hydrogen and other bonds crystal and packing other e ectscrystal dominating packing effects dominating in this respect).ff ff effectsin this respect).dominating in this respect). 2. Results and Discussion 2. Results Results and and Discussion Discussion Reaction of 4-bromobenzamidrazone 1 with cyclopentanone 2 (1.2 equiv.) in methanol at 60 °C Reaction of 4-bromobenzamidrazone 1 with cyclopentanone 2 (1.2 equiv.) in methanol at 60 C for 96Reaction h in air of results4-bromobenzamidrazone in unpredictable formation 1 with cyclopentanone of 1,2,4-triazole 2 (1.2 3 featuringequiv.) in aliphaticmethanol peroxide at 60 ◦°C for 9696 hh in in air air results results in unpredictablein unpredictable formation formation of 1,2,4-triazole of 1,2,4-triazole3 featuring 3 featuring aliphatic aliphatic peroxide peroxide chain as chain as several pale-yellow crystals, which were studied by single-crystal XRD (Scheme 1a and chainseveral as pale-yellow several pale-yellow crystals, which crystals, were which studied were by single-crystal studied by XRDsingle-crystal (Scheme1 aXRD and Figure(Scheme2), among1a and Figure 2), among the formation of 1,4-di(4-bromophenyl)tetrazine as a major product of the reaction Figurethe formation 2), among of 1,4-di(4-bromophenyl)tetrazinethe formation of 1,4-di(4-bromophenyl)tetrazine as a major product as ofa major the reaction product [25 of]. the Reaction reaction of [25]. Reaction of other para-substituted aromatic amidrazones, i.e., 4-RC6H4C(NH2)=NNH2 (R = CF3, [25].other Reactionpara-substituted of other aromaticpara-substituted amidrazones, aromatic i.e., amidrazones, 4-RC6H4C(NH i.e.,2)= 4-RCNNH6H2 4(RC(NH= CF2)=NNH3, H, MeO)2 (R = under CF3, H, MeO) under the same conditions resulted in formation of only the corresponding tetrazines [25], the same conditions resulted in formation of only the corresponding tetrazines [25], whereas generation H, MeO) under the same conditions resulted in formation of only the corresponding+ tetrazines [25], whereas generation of the peroxide substrates was not observed+ even by HRESI -MS. whereasof the peroxide generation substrates of the wasperoxide not observed substrates even was by not HRESI observed-MS. even by HRESI+-MS. HO a HO O O 5mol%a TsOH, O MeOH, in air, N NH2 5mol% TsOH, N NH g O MeOH,60 °C, in96 air h, N NH N NH2 N NH g Ar 60 °C, 96 h OH N NH Ar –H2O Ar O OH NH N Ar 2 –H2O Ar O N 1 2 Ar = 4-BrC6H4 3 Ar NH2 N NH 1 2 Ar = 4-BrC6H4 3 H b H2O –H2O f b H2O –H2O f H O HO H O HO O N N N NH O2 N N O (from air) N NH O N N N NH O2 N N O Ar Ar (from air) Ar N NH Ar c Ar dAr e Ar NH2 NH2 NH2 N c d e Ar NH2 NH2 NH2 NH H Scheme 1. Reaction scheme of the formation of primary aliphatic peroxide (a) and the plausible Scheme 1. Reaction scheme of the formation of primary aliphatic peroxide (a) and the plausible Scheme 1. Reaction scheme of themechanism formation of ofits primary generation aliphatic (b–g).
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