scholarly journals Competition between hydrogen bonding and dispersion interactions in the crystal structures of the primary amines

CrystEngComm ◽  
2014 ◽  
Vol 16 (19) ◽  
pp. 3867-3882 ◽  
Author(s):  
Andrew G. P. Maloney ◽  
Peter A. Wood ◽  
Simon Parsons
Keyword(s):  
Hydrogen Bonding ◽  
Crystal Structures ◽  
Crystal Packing ◽  
Short Chain ◽  
Primary Amines ◽  
Dispersion Interactions ◽  
Chain Compounds ◽  
The Cross ◽  
Long Chain

In the short chain amines H-bonding dominates crystal packing, but dispersion wins-out for the long chain compounds. The cross-over point occurs between butyl and pentylamine, where interactions are finely balanced.

Salt formation, hydrogen-bonding patterns and supramolecular architectures of acridine with salicylic and hippuric acid molecules

2021 ◽  
Vol 77 (12) ◽  
Author(s):  
Suresh Suganya ◽  
Kandasamy Saravanan ◽  
Ramakrishnan Jaganathan ◽  
Poomani Kumaradhas
Keyword(s):  
Hydrogen Bonding ◽  
Intermolecular Interactions ◽  
Hippuric Acid ◽  
Crystal Packing ◽  
Noncovalent Interactions ◽  
Salt Formation ◽  
Aminosalicylic Acid ◽  
Dispersion Interactions ◽  
Supramolecular Architectures ◽  
Quantitative Contributions

The intermolecular interactions and salt formation of acridine with 4-aminosalicylic acid, 5-chlorosalicylic acid and hippuric acid were investigated. The salts obtained were acridin-1-ium 4-aminosalicylate (4-amino-2-hydroxybenzoate), C13H10N+·C7H6NO3 − (I), acridin-1-ium 5-chlorosalicylate (5-chloro-2-hydroxybenzoate), C13H10N+·C7H4ClO3 − (II), and acridin-1-ium hippurate (2-benzamidoacetate) monohydrate, C13H10N+·C9H8NO3 −·H2O (III). Acridine is involved in strong intermolecular interactions with the hydroxy group of the three acids, enabling it to form supramolecular assemblies. Hirshfeld surfaces, fingerprint plots and enrichment ratios were generated and investigated, and the intermolecular interactions were analyzed, revealing their quantitative contributions in the crystal packing of salts I, II and III. A quantum theory of atoms in molecules (QTAIM) analysis shows the charge–density distribution of the intermolecular interactions. The isosurfaces of the noncovalent interactions were studied, which allows visualization of where the hydrogen-bonding and dispersion interactions contribute within the crystal.

Salts of aromatic carboxylates: the crystal structures of nickel(II) and cobalt(II) 2,6-naphthalenedicarboxylate tetrahydrate

2001 ◽  
Vol 34 (6) ◽  
pp. 710-714 ◽  
Author(s):  
James A. Kaduk ◽  
Jason A. Hanko
Keyword(s):  
Hydrogen Bonding ◽  
Crystal Structures ◽  
Crystal Packing ◽  
Geometry Optimization ◽  
Metal Cations ◽  
Carboxyl Groups ◽  
Water Molecules ◽  
Triclinic Space Group ◽  
Aromatic Carboxylates ◽  
Monte Carlo Simulated Annealing

The crystal structures of isostructural 2,6-naphthalenedicarboxylate tetrahydrate salts of nickel(II) and cobalt(II) have been determined using Monte Carlo simulated annealing techniques and laboratory X-ray powder diffraction data. These compounds crystallize in the triclinic space groupP\bar{1}, withZ= 2;a= 10.0851 (4),b= 10.9429 (5),c= 6.2639 (3) Å, α = 98.989 (2), β = 87.428 (3), γ = 108.015 (2)°,V= 649.32 (5) Å3for [Ni(C12H6O4)(H2O)4], anda= 10.1855 (6),b= 10.8921 (6),c= 6.2908 (5) Å, α = 98.519 (4), β = 87.563 (4), γ = 108.304 (3)°,V= 655.28 (8) Å3for [Co(C12H6O4)(H2O)4]. The water-molecule H atoms were located by quantum chemical geometry optimization usingCASTEP. The structure consists of alternating hydrocarbon and metal/oxygen layers parallel to theacplane. Each naphthalenedicarboxylate anion bridges two metal cations; each carboxyl group is monodentate. The resulting structure contains infinite chains parallel to [111]. The octahedral coordination sphere of the metal cations containstranscarboxylates and four equatorial water molecules. The carboxyl groups are rotated by 15–20° out of the naphthalene plane. The metal/oxygen layers are characterized by an extensive hydrogen-bonding network. The orientations of the carboxyl groups are determined by the formation of short (O...O = 2.53 Å) hydrogen bonds between the carbonyl O atoms and theciswater molecules. Molecular mechanics energy minimizations suggest that coordination and hydrogen-bonding interactions are most important in determining the crystal packing.

Hydrogen bonding in enantiomeric versus racemic mono-carboxylic acids; a case study of 2-phenoxypropionic acid

2003 ◽  
Vol 59 (1) ◽  
pp. 132-140 ◽  
Author(s):  
Henning Osholm Sørensen ◽  
Sine Larsen
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Crystal Structures ◽  
Carboxylic Acids ◽  
Crystal Packing ◽  
Cyclic Dimer ◽  
Optically Pure ◽  
Pure Enantiomer ◽  
Hydrogen Bonded

The structural and thermodynamic backgrounds for the crystallization behaviour of racemates have been investigated using 2-phenoxypropionic acid (PPA) as an example. The racemate of PPA behaves normally and forms a racemic compound that has a higher melting point and is denser than the enantiomer. Low-temperature crystal structures of the pure enantiomer, the enantiomer cocrystallized with n-alkanes and the racemic acid showed that hydrogen-bonded dimers that form over crystallographic symmetry elements exist in all but the structure of the pure enantiomer. A database search for optically pure chiral mono-carboxylic acids revealed that the hydrogen-bonded cyclic dimer is the most prevalent hydrogen-bond motif in chiral mono-carboxylic acids. The conformation of PPA depends on the hydrogen-bond motif; the antiplanar conformation relative to the ether group is associated with a catemer hydrogen-bonding motif, whereas the more abundant synplanar conformation is found in crystals that contain cyclic dimers. Other intermolecular interactions that involve the substituent of the carboxylic group were identified in the crystals that contain the cyclic dimer. This result shows how important the nature of the substituent is for the crystal packing. The differences in crystal packing have been related to differences in melting enthalpy and entropy between the racemic and enantiomeric acids. In a comparison with the equivalent 2-(4-chlorophenoxy)-propionic acids, the differences between the crystal structures of the chloro and the unsubstituted acid have been identified and related to thermodynamic data.

A Comparison of the Enamino Carbonyl Conjugation Efficiency for Hydrogen Bonding Formation in Pyridone and Dihydropyridone Systems

2000 ◽  
Vol 55 (1) ◽  
pp. 5-11 ◽  
Author(s):  
Teresa Borowiak ◽  
Irena Wolska ◽  
Artur Korzański ◽  
Wolfgang Milius ◽  
Wolfgang Schnick ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Steric Hindrance ◽  
Crystal Packing ◽  
Intermolecular Hydrogen Bond ◽  
Asymmetric Unit ◽  
Intermolecular Hydrogen Bonds

The crystal structures of two compounds containing enaminone heterodiene systems and forming intermolecular hydrogen bonds N-H·O are reported: 1) 3-ethoxycarbonyl-2-methyl-4-pyridone (hereafter ETPY) and 2) 3-ethoxycarbonyl-2-phenyl-6-methoxycarbonyl-5,6-di-hydro-4-pyridone (hereafter EPPY). The crystal packing is controlled by intermolecular hydro­ gen bonds N-H·O = C connecting the heteroconjugated enaminone groups in infinite chains. In ETPY crystals the intermolecular hydrogen bond involves the heterodienic pathway with the highest π-delocalization that is effective for a very short N·O distance of 2.701(9) Å (average from two molecules in the asymmetric unit). Probably due to the steric hindrance, the hydrogen bond in EPPY is formed following the heterodienic pathway that involves the ester C = O group, although π-delocalization along this pathway is less than that along the pyridone-part pathway resulting in a longer N·O distance of 2.886(3) Å

Hydrogen bonding of alcohols with AOT in carbon tetrachloride: an infrared study

1985 ◽  
Vol 63 (12) ◽  
pp. 3367-3370 ◽  
Author(s):  
Pierre Ménassa ◽  
Camille Sandorfy
Keyword(s):  
Hydrogen Bonding ◽  
Infrared Spectroscopy ◽  
Carbon Tetrachloride ◽  
Equilibrium Constants ◽  
Short Chain ◽  
Infrared Study ◽  
Free Band ◽  
Long Chain ◽  
Cyclic Alcohols ◽  
Aliphatic Chains

The interaction of the inverted micelles of AOT (sodium di(2-ethylhexyl)sulfosuccinate) with different alcohols due to hydrogen bonding has been studied by means of infrared spectroscopy. Spectra of solutions of the alcohols with increasing concentrations of AOT showed a decrease in the intensity of the free OH stretching band. At the same time a new OH band due to a H-bonded alcohol-inverted micelle complex appears and its intensity increases as the intensity of the free band decreases. Calculated values of the equilibrium constants for the formation of the complexes n-alcohol–AOT, showed a decrease in alcohol–AOT association with the increase of the length of the aliphatic chains in the n-alcohols. Surprisingly, cholesterol behaved like a short chain while other cyclic alcohols like long chain alcohols.

scholarly journals Hydrogen-bonding network in the organic salts of 4-nitrobenzoic acid

2006 ◽  
Vol 4 (3) ◽  
pp. 458-475 ◽  
Author(s):  
Yurii Chumakov ◽  
Yurii Simonov ◽  
Mata Grozav ◽  
Manuela Crisan ◽  
Gabriele Bocelli ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Crystal Packing ◽  
Building Blocks ◽  
Supramolecular Architecture ◽  
Two Dimensional ◽  
Organic Salts ◽  
Nitrobenzoic Acid ◽  
Ionic Forms

AbstractThe crystal structures of six novel salts of 4-nitrobenzoic acid — namely, 2-hydroxyethylammonium 4-nitrobenzoate (I), 2-hydroxypropylammonium 4-nitrobenzoate (II), 1-(hydroxymethyl)propylammonium 4-nitrobenzoate (III), 3-hydroxypropylammonium 4-nitrobenzoate (IV), bis-(2-hydroxyethylammonium) 4-nitrobenzoate (V), morpholinium 4-nitrobenzoate (VI) — containing the same anion but different cations have been studied. The ionic forms of I-VI serve as building blocks of the supramolecular architecture, and in crystals they are held together via ionic N-H···O and O-H···O hydrogen bonds. In the crystal packing the building blocks of I-III are self-assembled via N-H...O, O-H···O and C-H...O hydrogen bonds to form the chains which are further consolidated into two-dimensional layers by the same type of interactions. In IV-VI the chain-like structures have been generated by building blocks.

Excess heats of tri-n-alkylamines and tetraalkyl tin compounds in linear and branched alkanes: correlations of molecular orientations and steric hindrance effect

1979 ◽  
Vol 57 (5) ◽  
pp. 517-525 ◽  
Author(s):  
R. Philippe ◽  
G. Delmas ◽  
Phuong Nguyen Hong
Keyword(s):  
Steric Hindrance ◽  
Solution Structure ◽  
The Other ◽  
Short Chain ◽  
Flory Theory ◽  
Tin Compounds ◽  
Branched Alkanes ◽  
Linear Alkanes ◽  
Chain Compounds ◽  
Long Chain

Excess heats of the following mixtures of trialkylamines and tetraalkyl tin compounds with branched and linear alkanes have been measured at 25 °C: five trialkylamines NR3 (R = C2H5, C3H7, C4H9, C10H21, C12H25) with six linear alkanes, n-C5, n-C6, n-C8, n-C10, n-C12, n-C16, and three highly branched alkanes, 2,2,4-trimethylpentane, 2,2,4,6,6-pentamethylheptane, and 2,2,4,4,6,8,8-heptamethylnonane (br-C16). Further measurements were carried out on tetrapropyl tin (SnPr4) with n-C8, n-C16, and br-C16.Measurements were made to obtain more information on the heats of disordering of long chain compounds and on an exothermic contribution to the heats coming possibly from the sterically hindered character of one of the components of the mixture. The three short-chain trialkylamines have large heats with the linear long alkanes and small heats with the branched alkanes. On the other hand, the two long-chain trialkylamines have very small heats with linear alkanes and large heats with the branched alkanes. These results are interpreted as indicating no change of liquid or solution 'structure' when two ordered compounds (long alkanes and long-chain amines) are mixed but a change of 'structure' when an ordered compound (long alkane or long-chain amine) is mixed with a non-ordered one (branched alkane or short-chain amine). The heat of disordering of n-hexadecane is obtained with many order breakers and found to depend to some extent on the expansion coefficient of the order breaker. HE values for the series of the shorter NR3 do not vary regularly with molecular weight but are smaller for the propyl (and possibly the ethyl) derivative. Similarly, HE of SnPr4 in n-C16, br-C16, and n-C8 are much lower than the corresponding heats with SnEt4 and SnBut4. This is attributed to the presence of the exothermic contribution to the heats, HE(steric hindrance). The X12 parameter of the Flory theory has been calculated and is interpreted in terms of the disorder and steric hindrance contributions to the heats.

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