H2O, HDO, and CH3OH Infrared Spectra and Correlation with Solvent Basicity and Hydrogen Bonding

1971 ◽  
Vol 49 (6) ◽  
pp. 837-856 ◽  
Author(s):  
D. N. Glew ◽  
N. S. Rath
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Infrared Spectra ◽  
Dibasic Acid ◽  
Tertiary Amines ◽  
Type Symmetry ◽  
Solvent Basicity ◽  
Organic Amines ◽  
Lower Frequencies ◽  
Hydrogen Bonded

A study has been made of the infrared O—H bands for CH3OH, DOH, and H2O in solution and of their correlation with hydrogen bonding and solvent basicity. Infrared bands for the three fundamentals and the first bending overtone of H2O and for the O—H stretching fundamentals of DOH and CH3OH have been measured between 30 and −40 °C in a solvent range extending from weakly interacting fluorocarbons to strongly hydrogen-bonding organic amines. The O—H stretching bands for the weakly acidic solutes CH3OH, DOH, and H2O are mostly Lorentzian in shape and move to lower frequencies with higher extinctions in the more basic solvents. Many correlations are found between the stretching frequencies and band areas, and between the frequencies and solvent basicity. Monofunctional CH3OH is found to be a stronger acid and forms stronger hydrogen-bonds with a given base than do the doubly bonded DOH and HOH which show equal dibasic acid strengths.The wide, overlapped, fundamental stretching bands for H2O strongly hydrogen-bonded to the tertiary amines and for ice have been partially resolved and unequivocally assigned, showing that there is no cross-over of the ν 3 and ν1 bands despite the strong hydrogen-bonding.At higher temperatures in solvents containing both hydrophobic and strongly basic groups water was found with the lower Cs type symmetry, in which unbonded O—H groups gave sharp bands in the 3680–3650 cm−1 region in addition to the wide hydrogen-bonded bands at lower frequencies.

HYDROGEN BONDING IN THE AMINE HYDROHALIDES: II. THE INFRARED SPECTRUM FROM 4000 TO 2200 CM−1

1960 ◽  
Vol 38 (1) ◽  
pp. 34-44 ◽  
Author(s):  
C. Brissette ◽  
C. Sandorfy
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Infrared Spectrum ◽  
Infrared Spectra ◽  
Primary Amine ◽  
Lithium Fluoride ◽  
Aliphatic Amine ◽  
Combination Bands ◽  
Lower Frequencies ◽  
Amine Salts

The infrared spectra of a number of amine hydrohalides have been measured in the lithium fluoride region.Hydrogen bonding and the torsional oscillations of the [Formula: see text] groups influence these spectra characteristically. The [Formula: see text] stretching frequencies give broad or fairly broadbands. They are near 3000 cm−1 for aliphatic primary amine salts. The corresponding band lies at somewhat lower frequencies for secondary amine salts and much lower for tertiary ones. The aromatic amine hydrohalides exhibit these bands at lower frequencies than do the aliphatic amine salts of the same order. There is a shift to higher frequencies in the series hydrochloride, hydrobromide, hydriodide.All these spectra contain a number of sharper bands which may or may not coincide with the hydrogen-bonded stretching bands. These are combination bands involving mainly deformation vibrations, and they shift to lower frequencies, throughout the series hydrochloride, hydrobromide, hydriodide.The importance of electrical anharmonicity for the appearance of these bands is stressed.The hydrogen bonds in amine hydrohalides appear to be largely electrostatic in character.

The influence of pressure on the infrared spectra of hydrogen-bonded solids. VI. Ammonium salts

1978 ◽  
Vol 31 (1) ◽  
pp. 11 ◽  
Author(s):  
SD Hamann
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Infrared Spectra ◽  
Ammonium Salts ◽  
Bond Strengths ◽  
As If ◽  
Lower Frequencies ◽  
Hydrogen Bonded

The infrared spectra of 33 polycrystalline ammonium salts have been measured at 25°C, at pressures up to 45 kbar. The N-H stretching and bending bands of the hydrogen-bonded NH4+ ions of most of the salts shift anomalously to higher and to lower frequencies, respectively, as the pressure is raised. In this sense, the salts behave as if they had very strong hydrogen bonds, instead of quite weak ones. ��� A fairly good correlation exists between the N-H stretching frequencies of salts with N+-H...O bonds and their hydrogen bond strengths as measured by the minimum N+...O distances in their crystals.

Hydrogen bonding and conformation in cis- and trans-2-alkoxy-3-hydroxytetrahydrofurans

1968 ◽  
Vol 46 (1) ◽  
pp. 21-24 ◽  
Author(s):  
W. W. Zajac Jr. ◽  
F. Sweet ◽  
R. K. Brown
Keyword(s):  
Hydrogen Bonding ◽  
Infrared Spectra ◽  
Hydroxyl Absorption ◽  
Cis And Trans ◽  
In Cis ◽  
Infrared Data ◽  
Hydrogen Bonded

Infrared spectra show both free and hydrogen bonded hydroxyl absorption in several trans-2-alkoxy-3-hydroxytetrahydrofurans. The extent of non-bonded hydroxyl is greater than that of bonded hydroxyl. Suggestions are made of possible conformations which might account for the infrared data.

Polymorphs of phenazine hexacyanoferrate(II) hydrate: supramolecular isomerism in a 2D hydrogen-bonded network

2021 ◽  
Vol 77 (2) ◽  
pp. 211-218
Author(s):  
Ivica Cvrtila ◽  
Vladimir Stilinović
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
The Other ◽  
Two Dimensional ◽  
Structural Motifs ◽  
Supramolecular Isomerism ◽  
Other Hand ◽  
Π Stacking ◽  
Hydrogen Bonded

The crystal structures of two polymorphs of a phenazine hexacyanoferrate(II) salt/cocrystal, with the formula (Hphen)3[H2Fe(CN)6][H3Fe(CN)6]·2(phen)·2H2O, are reported. The polymorphs are comprised of (Hphen)2[H2Fe(CN)6] trimers and (Hphen)[(phen)2(H2O)2][H3Fe(CN)6] hexamers connected into two-dimensional (2D) hydrogen-bonded networks through strong hydrogen bonds between the [H2Fe(CN)6]2− and [H3Fe(CN)6]− anions. The layers are further connected by hydrogen bonds, as well as through π–π stacking of phenazine moieties. Aside from the identical 2D hydrogen-bonded networks, the two polymorphs share phenazine stacks comprising both protonated and neutral phenazine molecules. On the other hand, the polymorphs differ in the conformation, placement and orientation of the hydrogen-bonded trimers and hexamers within the hydrogen-bonded networks, which leads to different packing of the hydrogen-bonded layers, as well as to different hydrogen bonding between the layers. Thus, aside from an exceptional number of symmetry-independent units (nine in total), these two polymorphs show how robust structural motifs, such as charge-assisted hydrogen bonding or π-stacking, allow for different arrangements of the supramolecular units, resulting in polymorphism.

scholarly journals The infrared spectra of protic ionic liquids: performances of different computational models to predict hydrogen bonds and conformer evolution

2020 ◽  
Vol 22 (14) ◽  
pp. 7497-7506 ◽  
Author(s):  
O. Palumbo ◽  
A. Cimini ◽  
F. Trequattrini ◽  
J.-B. Brubach ◽  
P. Roy ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Ionic Liquids ◽  
Hydrogen Bonds ◽  
Dft Calculations ◽  
Infrared Spectra ◽  
Computational Models ◽  
Far Infrared ◽  
Protic Ionic Liquids ◽  
Far Infrared Spectra

DFT calculations with the ωB97-D functional reproduce hydrogen bonding features of the far-infrared spectra of diethylmethylammonium methanesulfonate and diethylmethylammonium trifluoromethanesulfonate.

Cinnamic acid hydrogen bonds to isoniazid andN′-(propan-2-ylidene)isonicotinohydrazide, anin situreaction product of isoniazid and acetone

2014 ◽  
Vol 70 (4) ◽  
pp. 392-395 ◽  
Author(s):  
Inese Sarcevica ◽  
Liana Orola ◽  
Mikelis V. Veidis ◽  
Sergey Belyakov
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Carboxylic Acid ◽  
Hydrogen Bonds ◽  
Cinnamic Acid ◽  
Slow Evaporation ◽  
Hydrogen Bonded

A new polymorph of the cinnamic acid–isoniazid cocrystal has been prepared by slow evaporation, namely cinnamic acid–pyridine-4-carbohydrazide (1/1), C9H8O2·C6H7N3O. The crystal structure is characterized by a hydrogen-bonded tetrameric arrangement of two molecules of isoniazid and two of cinnamic acid. Possible modification of the hydrogen bonding was investigated by changing the hydrazide group of isoniazidviaanin situreaction with acetone and cocrystallization with cinnamic acid. In the structure of cinnamic acid–N′-(propan-2-ylidene)isonicotinohydrazide (1/1), C9H8O2·C9H11N3O, carboxylic acid–pyridine O—H...N and hydrazide–hydrazide N—H...O hydrogen bonds are formed.

scholarly journals Hydrogen-bonding patterns in 2-amino-4,6-dimethoxypyrimidine–4-aminobenzoic acid (1/1)

2006 ◽  
Vol 62 (7) ◽  
pp. o2976-o2978 ◽  
Author(s):  
Kaliyaperumal Thanigaimani ◽  
Packianathan Thomas Muthiah ◽  
Daniel E. Lynch
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Carboxyl Group ◽  
Acid Molecule ◽  
Aminobenzoic Acid ◽  
Graph Set ◽  
Supramolecular Chain ◽  
Bonding Patterns ◽  
Hydrogen Bonded

In the title cocrystal, C6H9N3O2·C7H7NO2, the 2-amino-4,6-dimethoxypyrimidine molecule interacts with the carboxyl group of the 4-aminobenzoic acid molecule through N—H...O and O—H...N hydrogen bonds, forming a cyclic hydrogen-bonded motif [R 2 2(8)]. This motif further self-organizes through N—H...O hydrogen bonds to generate an array of six hydrogen bonds with the rings having the graph-set notation R 2 3(6), R 2 2(8), R 4 2(8), R 2 2(8) and R 2 3(6). The 4-aminobenzoic acid molecules self-assemble via N—H...O hydrogen bonds to form a supramolecular chain along the c axis.

More examples of the 15-crown-5...H2O—M—OH2...15-crown-5 motif, M = Al3+, Cr3+ and Pd2+

2010 ◽  
Vol 66 (2) ◽  
pp. 213-221 ◽  
Author(s):  
Maxime A. Siegler ◽  
Jacob H. Prewitt ◽  
Steven P. Kelley ◽  
Sean Parkin ◽  
John P. Selegue ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Water Molecule ◽  
Lattice Water Molecule ◽  
Literature Survey ◽  
The Other ◽  
Water Molecules ◽  
Lattice Water ◽  
Hydrogen Bonding Pattern ◽  
Hydrogen Bonded

Five structures of co-crystals grown from aqueous solutions equimolar in 15-crown-5 (or 15C5) and [M(H2O)6](NO3) n , M = Al3+, Cr3+ and Pd2+, are reported. The hydrogen-bonding patterns in all are similar: metal complexes including the fragment trans-H2O—M—OH2 alternate with 15C5 molecules, to which they are hydrogen bonded, to form stacks. A literature survey shows that this hydrogen-bonding pattern is very common. In each of the two polymorphs of the compound [Al(H2O)6](NO3)3·15C5·4H2O there are two independent cations; one forms hydrogen bonds directly to the 15C5 molecules adjacent in the stack, while the other cation is hydrogen-bonded to two water molecules that act as spacers in the stack. These stacks are then crosslinked by hydrogen bonds formed by the three nitrate counterions and the three lattice water molecules. The hydrogen-bonded stacks in [Cr(H2O)5(NO3)](NO3)2·1.5(15C5)·H2O are discrete rather than infinite; each unit contains two Cr3+ complex cations and three 15C5 molecules. These units are again crosslinked by the uncoordinated nitrate ions and a lattice water molecule. In [Pd(H2O)2(NO3)2]·15C5 the infinite stacks are electrically neutral and are not crosslinked. In [Pd(H2O)2(NO3)2]·2(15C5)·2H2O·2HNO3 a discrete, uncharged unit containing one Pd complex and two 15C5 molecules is `capped off' at either end by a lattice water molecule and an included nitric acid molecule. In all five structures the infinite stacks or discrete units form an array that is at least approximately hexagonal.

Infrared Spectra of Crystalline Acetic Acid, a Hydrogen-Bonded Polymer

1977 ◽  
Vol 31 (2) ◽  
pp. 110-115 ◽  
Author(s):  
P. F. Krause ◽  
J. E. Katon ◽  
J. M. Rogers ◽  
D. B. Phillips
Keyword(s):  
Hydrogen Bonding ◽  
Acetic Acid ◽  
Infrared Spectra ◽  
Group Analysis ◽  
Structural Models ◽  
Factor Group ◽  
Vibrational Modes ◽  
Cryogenic Temperatures ◽  
Polymeric Chains ◽  
Hydrogen Bonded

The polarized infrared spectra of crystalline acetic acid and two of its deuterated derivatives, CH3COOD and CD3COOD, have been recorded from 400 to 4000 cm−1 at cryogenic temperatures. The spectroscopic results have been interpreted on the basis of a factor group analysis based on two structural models: a crystallographic cell composed of four interacting monomer units some of whose vibrational modes are highly perturbed by hydrogen bonding and a unit cell composed of two noninteracting acetic acid chains. The results are discussed in terms of possible interactions between the hydrogen-bonded acetic acid polymeric chains.

scholarly journals Hydrogen bonding in the crystal structure of the molecular salt of pyrazole–pyrazolium picrate

2016 ◽  
Vol 72 (6) ◽  
pp. 861-863 ◽  
Author(s):  
Ping Su ◽  
Xue-gang Song ◽  
Ren-qiang Sun ◽  
Xing-man Xu
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Organic Salt ◽  
Asymmetric Unit ◽  
Molecular Salt ◽  
Hydrogen Bonded

The asymmetric unit of the title organic salt [systematic name: 1H-pyrazol-2-ium 2,4,6-trinitrophenolate–1H-pyrazole (1/1)], H(C3H4N2)2+·C6H2N3O7−, consists of one picrate anion and one hydrogen-bonded dimer of a pyrazolium monocation. The H atom involved in the dimer N—H...N hydrogen bond is disordered over both symmetry-unique pyrazole molecules with occupancies of 0.52 (5) and 0.48 (5). In the crystal, the component ions are linked into chains along [100] by two different bifurcated N—H...(O,O) hydrogen bonds. In addition, weak C—H...O hydrogen bonds link inversion-related chains, forming columns along [100].

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