Simplified calculation approaches designed to reproduce the geometry of hydrogen bonds in molecular complexes in aprotic solvents

2018 ◽  
Vol 148 (12) ◽  
pp. 124313 ◽  
Author(s):  
Ilya G. Shenderovich
Keyword(s):  
Hydrogen Bonds ◽  
Molecular Complexes ◽  
Aprotic Solvents ◽  
Simplified Calculation

scholarly journals Well-defined molecular uranium(iii) chloride complexes

2014 ◽  
Vol 50 (30) ◽  
pp. 3962-3964 ◽  
Author(s):  
Henry S. La Pierre ◽  
Frank W. Heinemann ◽  
Karsten Meyer
Keyword(s):  
Molecular Complexes ◽  
Aprotic Solvents ◽  
Chloride Complexes

The first anhydrous molecular complexes of uranium(iii) chloride, soluble in polar aprotic solvents, are reported, including the structures of the dimeric [UCl3(py)4]2 and the trimetallic [UCl(py)4(μ-Cl)3U(py)2(μ-Cl)3UCl2(py)3].

scholarly journals Engineering short, strong hydrogen bonds in urea di-carboxylic acid complexes

CrystEngComm ◽  
2014 ◽  
Vol 16 (35) ◽  
pp. 8177-8184 ◽  
Author(s):  
Andrew O. F. Jones ◽  
Charlotte K. Leech ◽  
Garry J. McIntyre ◽  
Chick C. Wilson ◽  
Lynne H. Thomas
Keyword(s):  
Hydrogen Bond ◽  
Carboxylic Acid ◽  
Hydrogen Bonds ◽  
Neutron Diffraction ◽  
Structural Changes ◽  
Acid Amide ◽  
Molecular Complexes ◽  
Temperature Dependent ◽  
X Ray ◽  
Methyl Substitution

The persistence of the acid⋯amide heterodimer and the effect of methyl substitution on the short strong O–H⋯O hydrogen bond is investigated in urea and methylurea di-carboxylic acid molecular complexes. Temperature dependent structural changes are also reported utilising X-ray and neutron diffraction in tandem.

Aminkomplexe des Goldes, Teil 7: Pseudosymmetrie bei Aminkomplexen des Gold(I)-cyanids [1] / Amine Complexes of Gold, Part 7: Pseudosymmetry in Amine Complexes of Gold(I) Cyanide

2013 ◽  
Vol 68 (5-6) ◽  
pp. 474-492 ◽  
Author(s):  
Cindy Döring ◽  
Peter G. Jones
Keyword(s):  
Hydrogen Bonds ◽  
Molecular Complexes ◽  
Ionic Form ◽  
Amine Complexes

The reaction between (tht)AuCl (tht = tetrahydrothiophene) and KCN leads to gold(I) cyanide. This can be treated with liquid amines or azaaromatics L to give crystalline molecular complexes LAuCN, the first complexes of the type (amine)cyanogold(I): L = cyclohexylamine, isobutylamine, isopropylamine, diethylamine, morpholine, piperidine, pyrrolidine, 2,4-lutidine, 3,5-lutidine, and 4- picoline. The cyclohexylamine complex was also obtained as the adduct LauCN L and the pyrrolidine complex in the ionic form [L2Au]+ [Au(CN)2]-. Two polymorphs of the 3,5-lutidine complex were obtained. Ethylenediamine gave the 2:1 complex L(AuCN)2. Several of the structures were difficult to refine because of pseudosymmetry (e. g. polar axes). The packing diagrams were analyzed in terms of Au-Au contacts and NH....N hydrogen bonds. As proof of the principle that the method is also suitable for other ligands, the complex with t-butyldiisopropylphosphane was synthesized and structurally characterized

scholarly journals Deprotonation of resorcinarenes and novel ammonium salt complexes

2014 ◽  
Vol 70 (a1) ◽  
pp. C678-C678
Author(s):  
Ngong Beyeh ◽  
Arto Valkonen ◽  
Fanfang Pan ◽  
Kari Rissanen
Keyword(s):  
Hydrogen Bonds ◽  
Binding Sites ◽  
Molecular Complexes ◽  
Ammonium Salts ◽  
Hydroxyl Groups ◽  
Binding Modes ◽  
Intermolecular Hydrogen Bonds ◽  
Guest Molecules ◽  
Cone Conformation ◽  
Intramolecular Hydrogen

The bowl shape cavity of resorcinarenes usually stabilized by four intramolecular hydrogen bonds offers an interesting array of binding modes such as C–H...π and cation...π interactions to recognize a variety of guests. The multiple hydroxyl groups can participate in a series of intermolecular hydrogen bonds with guest molecules. This unique cone conformation of resorcinarenes has led to the synthesis of many receptors with convergent arrangement of binding sites suitable for molecular recognition in many applications. Unfunctionalized resorcinarenes are known to easily form molecular complexes with guests of varying shapes and sizes. Amines are very common bases used in many catalytic processes. A good example is the use of amines as bases in the alkylation and acylation of resorcinarenes leading to cavitands, carcerands, hemicarcerands and velcrands. The use of amines in such reactions is to deprotonate the resorcinarene hydroxyl groups, hence facilitating the alkylation and acylation processes. The subsequently protonated ammonium cation then forms interesting supramolecular complexes with the anionic and dianionic resorcinarenes. Furthermore, secondary and tertiary ammonium salts possess hydrogen bond donating -NH2 and -NH respectively and these can further enhance their complexation through intermolecular hydrogen bonds. Here we present our recent examples of supramolecular assemblies resulting from the deprotonation of resorcinarenes by mono- and dibasic amines. Also, our latest supramolecular co-crystals between resorcinarenes as the receptors and a series of secondary and tertiary mono- and diammonium cations are illustrated.

THERMODYNAMICS OF THE MOLECULAR COMPLEXES WITH CHAINS OF HYDROGEN BONDS

1992 ◽  
Vol 06 (02) ◽  
pp. 85-91 ◽  
Author(s):  
I.V. STASYUK ◽  
A.L. IVANKIV
Keyword(s):  
Hydrogen Bonds ◽  
Molecular Complexes ◽  
High Energy ◽  
Spin Model ◽  
Strong Correlations ◽  
Reduced Basis ◽  
Molecular Systems ◽  
Ionic Groups ◽  
Energy Proton ◽  
Initial Basis

A pseudo-spin reduced basis model for the description of the linear hydrogen-bonds molecular systems with strong correlations between protons on the neighbouring bonds is proposed. The proton states corresponding to the high-energy proton configurations near the heavy ionic groups are excluded from the initial basis. Some aspects of thermodynamics and energy spectrum for the proton subsystem of the molecular complexes are considered in the framework of reduced basis model. It is shown that for the complexes with large but finite number of hydrogen bonds N, the polarizability is proportional to N2, the specific heat is proportional to N−1 and the spectrum includes both zone and localized proton states. At the same time it is shown that correct thermodynamic limit is obtained as N→∞ on the base of pseudo-spin model with initial basis. As a result the limits of application of reduced basis model are determined.

Polysulfonylamine, CLXXXVI [1]. Strukturvielfalt in sechs Cokristallen von Tetramethylharnstoff mit Di(4-X-benzolsulfonyl)aminen (X = F, Cl, Br, I, CH3, NO2) / Polysulfonylamines, CLXXXVI [1]. Structural Diversity in Six Tetramethylurea Di(4-X-benzenesulfonyl) amine Cocrystals (X = F, Cl, Br, I, CH3, NO2)

2008 ◽  
Vol 63 (11) ◽  
pp. 1276-1290 ◽  
Author(s):  
Eva-Maria Zerbe ◽  
Silvia Roca Piñol ◽  
Thomas Hamann ◽  
Matthias Freytag ◽  
Peter G. Jones ◽  
...  
Keyword(s):  
Hydrogen Bonds ◽  
Ion Pairs ◽  
Molecular Complexes ◽  
Structural Diversity ◽  
Halogen Bonds ◽  
Aromatic Rings ◽  
Competing Interactions ◽  
X Ray Crystallography ◽  
Isomorphic Series ◽  
Carbonyl Function

Abstract Cocrystallization of tetramethylurea (TMU) with one equivalent of either di(4-fluorobenzenesulfo- nyl)amine (FAH), di(4-chlorobenzenesulfonyl)amine (CAH), di(4-bromobenzenesulfonyl)amine (BAH). di(4-iodobenzenesulfonyl)amine (IAH), di(4-methylbenzenesulfonyl)aniine (MAH>, ordi(4- nitrobenzenesulfonyDamine (NAH), using dichloromethane/petroleum ether as the solvent, afforded the molecular complexes (FAH)2 · TMU (1. monoclinic. P21/c,Z' = 1. structure previously reported), CAHTMU, BAH-TMU and IAH-TMU (2-4, isomorphic series, triclinic, P1̅,Z' = 1), MAH · TMU (5, monoclinic. P21, Z' = 1). and the uranium salt TMUH+NA- (6, monoclinic. P21/c,Z' = 2). The structural results obtained by X-ray crystallography at low temperatures indicate that the varying p- substituents of the di(arenesulfonyl)amines exert a decisive influence on (i) the stoichiometry of the cocrystallization reaction (2:1 for 1 vs. 1:1 for 2-6), (ii) the degree of proton transfer between the strongly acidic (SO2)2NH moieties and the basic carbonyl function of TMU (molecular complexes assembled via N-H···O=C hydrogen bonds in 1 -5 vs. two independent ion pairs based upon charge- assisted C-O-H+ ···N- interactions in 6). and (Hi) the conformation of the disulfonylamineZ-amide units as defined by rotations about the S-N bonds (extended forms displaying anticlinal C-S ··· S'- C' torsions for the two molecules in 1 and the two anions in 6 vs. folded forms featuring synperi- planar C-S ···S'-C torsions for the molecules in 2-5). The packing modes of 1-4 underline the well-known correlation between the atomic number of halogen atoms and their propensity to form halogen bonds. Thus, the structure of 1 is devoid of short F···O contacts, whereas the isomorphic co- crystals 2-4 consist of lamellar layers in which the inner lamellae include the TMU molecules and the peripheral regions are built up from CAH, BAH or IAH molecules associated into catemers via C-Hal ··· O=S bonds. The lamellar layers of the non-isomorphic methyl congener 5. although topological^' similar to those of 2-4, are stacked according to a herringbone pattern that does not arise in the structures of 2-4. The most prominent packing feature of the uranium salt 6 are intimate dimers of two independent NA- ions, stabilized by dipolar nitro-nitro interactions and C-H ··· O=S contacts and further connected into monolayers through C-H ··· Onitro contacts. The uranium ions are inserted between these layers and bonded to the anion dimers by the strong hydrogen bonds mentioned above and numerous C-H ··· Onitro contacts. The presence of two independent formula units appears to arise from frustration between several competing interactions, e. g. dipolar nitro attractions, weak hydrogen bonding to sulfonyl and nitro acceptors and π/π stacking of aromatic rings.

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