Hydrogen Peroxide Insular Dodecameric and Pentameric Clusters in Peroxosolvate Structures

Abstract

Peroxosolvates of 2-aminonicotinic acid (I) and lidocaine N-oxide (II) including the largest insular hydrogen peroxide clusters were isolated and their crystal structures were determined by single-crystal X-ray diffraction. An unprecedented dodecameric hydrogen peroxide insular cluster was found in I. An unusual cross-like pentameric cluster was observed in the structure of II. The topology of the (H O ) assembly was never observed for small-molecule clusters. In I and II new double and triple cross-orientational disorders of H O were found. Cluster II is the first example of a peroxosolvate crystal structure containing H O molecules with a homoleptic hydrogen peroxide environment. In II, a hydrogen bond between an H O molecule and a peptide group -CONH⋅⋅⋅O H was observed for the first time.

Crystalline Peroxosolvates: Nature of the Coformer, Hydrogen-Bonded Networks and Clusters, Intermolecular Interactions

“…The next group in terms of the number of compounds (42 compounds) are peroxosolvates formed by molecular organic compounds with a lone electron pair(s) on the nitrogen and/or oxygen atom(s). The main representatives of this group of crystalline hydrogen peroxide adducts are organophosphorus compounds containing the P=O functional group [49,[70][71][72][73][74][75][76] and nitrogen-containing heterocyclic compounds [25,26,[77][78][79][80][81][82][83][84], in particular N-oxides [85][86][87][88][89][90][91][92], obtained as a result of the oxidation reaction of the corresponding compounds with hydrogen peroxide. Urea peroxosolvate [2,27] is used as a solid source of hydrogen peroxide, and, along with 1,4-diazabicyclo[2.2.2]octane (DABCO) peroxosolvate [93], is used in organic syntheses to obtain anhydrous hydrogen peroxide solutions.…”

“…Peroxosolvates of a number of proteionogenic L-amino acids (serine, threonine, leucine, isoleucine, tyrosine, glycine, and phenylalanine) [94,95] and non-proteinogenic amino acids (gamma-aminobutyric acid, beta-alanine, and sarcosine) were obtained and structurally characterized at the Kurnakov Institute of General and Inorganic Chemistry RAS [95,96]. The class of zwitterions related to amino acids that form peroxosolvates includes pyridine carboxylic acids: nicotinic, isonicotinic, and picolinic acids [97], as well as 2-aminonicotinic acid [85]. Peroxosolvates of cyclic dipeptides-diglycine, disarcosine, and dialanine-are an example of the nonoxidative interaction of concentrated hydrogen peroxide and a peptide fragment [13].…”

DL-Piperidinium-2-carboxylate bis(hydrogen peroxide): unusual hydrogen-bonded peroxide chains

“…The structures of amino acid peroxosolvates have been studied intensively as simple models of hydrogen peroxide binding with proteins (Prikhodchenko et al, 2011;Kapustin et al, 2014). Peroxide and water-peroxide clusters are now of special interest since they may simulate cooperative hydrogen-bonded switching in the transportation of hydrogen peroxide species through cell membranes (Grishanov et al, 2017;Varadaraj & Kumari, 2020;Wang et al, 2020). Recently, several structures of organic peroxosolvates with peroxide hydrogen-bonded 1D-aggregates have been reported (Chernyshov et al, 2017;Navasardyan et al, 2017Navasardyan et al, , 2018.…”

“…4). The occurrence of interperoxide hydrogen-bonds results in the formation of simple infinite hydrogen-bonded 'hydroperoxo'-linked chains (Grishanov et al, 2017), running along the c-axis direction (Fig. 5).…”

Effect of aluminum vacancies on the H2O2 or H2O interaction with a gamma‐AlOOH surface. A solid‐state DFT study

“…It has been recently demonstrated that H 2 O 2 coordination with zinc and cobalt is facilitated by second‐sphere hydrogen‐bonding interactions with the two hydrogen bonds of the H 2 O 2 molecule as proton donor (DH‐bonds) . Formation of two relatively short (strong) DH‐bonds by H 2 O 2 molecule is always realized in peroxosolvates with organic and inorganic molecules and salts due to the relatively high acidity of the hydrogen peroxide . It was suggested that hydrogen bonding of the metal coordinated hydrogen peroxide is a general phenomenon that plays a key role in the stabilization of the M–(H 2 O 2 ) complex.…”