scholarly journals Exploration and exploitation of homologous series of bis(acrylamido)alkanes containing pyridyl and phenyl groups: β-sheetversustwo-dimensional layers in solid-state photochemical [2 + 2] reactions

IUCrJ ◽  
2015 ◽  
Vol 2 (5) ◽  
pp. 523-533 ◽  
Author(s):  
Mousumi Garai ◽  
Kumar Biradha
Keyword(s):  
Hydrogen Bonding ◽  
Solid State ◽  
Hydrogen Bonds ◽  
Single Crystal ◽  
Crystal Structures ◽  
Homologous Series ◽  
Bonding Layer ◽  
Two Dimensional ◽  
Systematic Analysis ◽  
Small Change

The homologous series of phenyl and pyridyl substituted bis(acrylamido)alkanes have been synthesized with the aim of systematic analysis of their crystal structures and their solid-state [2 + 2] reactivities. The changes in the crystal structures with respect to a small change in the molecular structure, that is by varying alkyl spacers between acrylamides and/or by varying the end groups (phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl) on the C-terminal of the amide, were analyzed in terms of hydrogen-bonding interference (N—H...NpyversusN—H...O=C) and network geometries. In this series, a greater tendency towards the formation of N—H...O hydrogen bonds (β-sheets and two-dimensional networks) over N—H...N hydrogen bonds was observed. Among all the structures seven structures were found to have the required alignments of double bonds for the [2 + 2] reaction such that the formations of single dimer, double dimer and polymer are facilitated. However, only four structures were found to exhibit such a solid-state [2 + 2] reaction to form a single dimer and polymers. The two-dimensional hydrogen-bonding layerviaN—H...O hydrogen bonds was found to promote solid-state [2 + 2] photo-polymerization in a single-crystal-to-single-crystal manner. Such two-dimensional layers were encountered only when the spacer between acryl amide moieties is butyl. Only four out of the 16 derivatives were found to form hydrates, two each from 2-pyridyl and 4-pyridyl derivatives. The water molecules in these structures govern the hydrogen-bonding networks by the formation of an octameric water cluster and one-dimensional zigzag water chains. The trends in the melting points and densities were also analyzed.

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 Polymorphism of 2-(5-benzyl-6-oxo-3-phenyl-1,6-dihydropyridazin-1-yl)acetic acid with two monoclinic modifications: crystal structures and Hirshfeld surface analyses

2020 ◽  
Vol 76 (3) ◽  
pp. 432-437
Author(s):  
Said Daoui ◽  
Cemile Baydere ◽  
Tarik Chelfi ◽  
Fouad El Kalai ◽  
Necmi Dege ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Acetic Acid ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Hirshfeld Surface ◽  
Two Dimensional ◽  
Asymmetric Unit ◽  
Monoclinic System ◽  
Compound C ◽  
Ring Motif

Two polymorphs of the title compound, C19H16N2O3, were obtained from ethanolic (polymorph I) and methanolic solutions (polymorph II), respectively. Both polymorphs crystallize in the monoclinic system with four formula units per cell and a complete molecule in the asymmetric unit. The main difference between the molecules of (I) and (II) is the reversed position of the hydroxy group of the carboxylic function. All other conformational features are found to be similar in the two molecules. The different orientation of the OH group results in different hydrogen-bonding schemes in the crystal structures of (I) and (II). Whereas in (I) intermolecular O—H...O hydrogen bonds with the pyridazinone carbonyl O atom as acceptor generate chains with a C(7) motif extending parallel to the b-axis direction, in the crystal of (II) pairs of inversion-related O—H...O hydrogen bonds with an R 2 2(8) ring motif between two carboxylic functions are found. The intermolecular interactions in both crystal structures were analysed using Hirshfeld surface analysis and two-dimensional fingerprint plots.

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.

Hydrogen Bonding of two l-(φ-Ammonioalkyl)-2-acyl-cyclopentadienides in the Solid State

2000 ◽  
Vol 55 (6) ◽  
pp. 541-545 ◽  
Author(s):  
Andreas Müller ◽  
Gerhard Maas
Keyword(s):  
Hydrogen Bonding ◽  
Solid State ◽  
Hydrogen Bonds ◽  
Two Dimensional ◽  
Intermolecular Hydrogen Bonds ◽  
Dimensional Network ◽  
Solid State Structures ◽  
Centrosymmetric Dimers

The solid-state structures of a l-(φ-ammoniopropyl)-2-(2-thienylcarbonyl)-cyclopentadienide (2) and a l-(φ-ammoniopentyl)-2-(4-methoxybenzoyl)-cyclopentadienide (3) have been determined. Both betaines self-assemble by NH ··· O hydrogen bonds, but the motifs are different. In the ammoniopropyl case, both intramolecular and intermolecular hydrogen bonds of this type exist, the latter bond being responsible for the formation of infinite chains. In the ammoniopentyl case, intermolecular hydrogen bonds build up a two-dimensional network which contains centrosymmetric dimers held together by NH ··· O=C-aryl hydrogen bonds.

Different forms of antiparallel stacking of hydrogen-bonded antidromic rings in the solid state: polymorphism with virtually the same unit cell and two-dimensional isostructurality with alternating layers

2004 ◽  
Vol 60 (6) ◽  
pp. 755-762 ◽  
Author(s):  
Alajos Kálmán ◽  
László Fábián ◽  
Gyula Argay ◽  
Gábor Bernáth ◽  
Zsuzsanna Cs. Gyarmati
Keyword(s):  
Hydrogen Bonding ◽  
Solid State ◽  
Single Crystal ◽  
Unit Cell ◽  
Two Dimensional ◽  
Acta Cryst ◽  
Space Group ◽  
Layer Stacking ◽  
Parallel Mode

As a continuation of a systematic structural analysis of 2-hydroxycycloalkanecarboxylic acids and their carboxamide analogs, the effects of antidromic rings [Jeffrey & Saenger (1991). Hydrogen Bonding in Biological Structures. Berlin, Heidelberg: Springer Verlag] upon the layer stacking of cyclopentane and cycloheptane derivatives are compared. Determination of the structure of trans-2-hydroxycycloheptanecarboxylic acid (2) led to the discovery of two polymorphs with virtually the same unit cell [Kálmán et al. (2003). J. Am. Chem. Soc. 125, 34–35]. (i) The layer stacking of the antidromic rings for the whole single crystal is antiparallel (2b). (ii) The antidromic rings and the 21 axis are parallel (2a), consequently the domains of the single crystal must be antiparallel. While their polymorphism is solvent-controlled, they illustrate a novel form of two-dimensional isostructurality. Antiparallel layer stacking is again demonstrated by trans-2-hydroxycycloheptanecarboxamide (3) (space group Pbca). It is built up from layers isostructural with those in the homologous trans-2-hydroxycyclopentanecarboxamide (4) [Kálmán et al. (2001). Acta Cryst. B57, 539–550], but in this structure (space group Pca21) the layers are stacked in parallel mode. Similar to (2a) and (2b), the antiparallel layer stacking in (3) versus their parallel array in (4) illustrates the two-dimensional isostructurality with alternating layer orientations. Although (3) and (4) display isostructurality, they are not isomorphous.

Di- bis Pentahydrate von fünf Alkylendiaminen. Eine Fallstudie zu ein- und zweidimensionalen Wasserpolymeren in Festkörpern/Di- to Pentahydrates of Five Alkylenediamines. A Case Study of One- and Two-Dimensional Water Polymers in Solids

1999 ◽  
Vol 54 (1) ◽  
pp. 103-108 ◽  
Author(s):  
Stephanie Janeda ◽  
Dietrich Mootz
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Three Dimensional ◽  
Unit Cell ◽  
Water Molecules ◽  
Two Dimensional ◽  
Group I ◽  
Low Dimensional

The crystal structures of five low-melting hydrates of n-alkane-α,ω-diamines, H2N(CH2)nNH2 · x H2O, for short Cn · x W, have been determined. As a common feature, the water molecules are mutually linked by hydrogen bonds O-H· · ·O to form low-dimensional polymers. These are a meandering chain in C2 · 2 W (space group I 2/a, Z = 4 formula units per unit cell), a zig zag chain in C6 · 2 W (P 21/c, Z = 2), a ribbon of consecutively condensed five-membered rings in C3 · 3 W (P 21/c, Z = 4) and a layer of condensed and spiro-linked rings of varying size each in C7 · 3 W (P 1̄, Z = 4) and C4 · 5 W (C 2/c, Z = 4). Further hydrogen bonding, between the water polymers and the bifunctional amine molecules, leads to overall connectivities which are three-dimensional in each structure.

scholarly journals Solid-state conformations of linear depsipeptide amides with an alternating sequence of α,α-disubstituted α-amino acid and α-hydroxy acid

2019 ◽  
Vol 76 (1) ◽  
pp. 1-9
Author(s):  
Anthony Linden ◽  
J. E. Florian Magirius ◽  
Heinz Heimgartner
Keyword(s):  
Amino Acid ◽  
Solid State ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Hydroxy Acid ◽  
Mandelic Acid ◽  
Type I ◽  
Two Dimensional ◽  
Phenyllactic Acid ◽  
Torsion Angles

Depsipeptides and cyclodepsipeptides are analogues of the corresponding peptides in which one or more amide groups are replaced by ester functions. Reports of crystal structures of linear depsipeptides are rare. The crystal structures and conformational analyses of four depsipeptides with an alternating sequence of an α,α-disubstituted α-amino acid and an α-hydroxy acid are reported. The molecules in the linear hexadepsipeptide amide in (S)-Pms-Acp-(S)-Pms-Acp-(S)-Pms-Acp-NMe2 acetonitrile solvate, C47H58N4O9·C2H3N, (3b), as well as in the related linear tetradepsipeptide amide (S)-Pms-Aib-(S)-Pms-Aib-NMe2, C28H37N3O6, (5a), the diastereoisomeric mixture (S,R)-Pms-Acp-(R,S)-Pms-Acp-NMe2/(R,S)-Pms-Acp-(R,S)-Pms-Acp-NMe2 (1:1), C32H41N3O6, (5b), and (R,S)-Mns-Acp-(S,R)-Mns-Acp-NMe2, C30H37N3O6, (5c) (Pms is phenyllactic acid, Acp is 1-aminocyclopentanecarboxylic acid and Mns is mandelic acid), generally adopt a β-turn conformation in the solid state, which is stabilized by intramolecular N—H...O hydrogen bonds. Whereas β-turns of type I (or I′) are formed in the cases of (3b), (5a) and (5b), which contain phenyllactic acid, the torsion angles for (5c), which incorporates mandelic acid, indicate a β-turn in between type I and type III. Intermolecular N—H...O and O—H...O hydrogen bonds link the molecules of (3a) and (5b) into extended chains, and those of (5a) and (5c) into two-dimensional networks.

scholarly journals The crystal structures of benzylammonium phenylacetate and its hydrate

2019 ◽  
Vol 75 (2) ◽  
pp. 194-201
Author(s):  
David Hess ◽  
Peter Mayer
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Phenylacetic Acid ◽  
Two Dimensional ◽  
Aromatic Rings ◽  
Crystal Water ◽  
Bonding System ◽  
Hydrogen Bonding System

The title compounds benzylammonium phenylacetate, C7H10N+·C8H7O2 − (1), and its monohydrate, C7H10N+·C8H7O2 −·H2O (2), can be obtained by evaporating methanolic solutions containing equimolar amounts of benzylamine and phenylacetic acid in the absence and presence of water, respectively. N—H...O hydrogen bonds in the crystal structure of 1 lead to the formation of hydrophilic channels running along the b-axis direction. The hydrogen-bonding system is best described by fused R 3 4(10) ring patterns, often observed in ammonium carboxylate salts. In 2, the presence of the crystal water leads to the formation of a two-dimensional hydrogen-bonding network. The benzyl moieties in 1 and 2 form hydrophobic layers in the crystal structures with the aromatic rings adopting edge-to-face arrangements.

scholarly journals 1,4-Dibromo-2,5-bis(phenylalkoxy)benzene Derivatives: C–Br...π(arene) Versus C–H...Br and Br...Br Interactions in the Solid State

Crystals ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 325
Author(s):  
Giacomo Manfroni ◽  
Alessandro Prescimone ◽  
Edwin Constable ◽  
Catherine Housecroft
Keyword(s):  
Solid State ◽  
Hydrogen Bonds ◽  
Single Crystal ◽  
Crystal Structures ◽  
Molecular Level ◽  
Benzene Derivatives ◽  
Single Crystal Structures ◽  
Π Stacking ◽  
Adjacent Molecule ◽  
Packing Interactions

We have prepared and characterized 1,4-dibromo-2,5-bis(2-phenylethoxy)benzene (1) and 1,4-dibromo-2,5-bis(3-phenylpropoxy)benzene (2). Their single-crystal structures confirm that, at the molecular level, they are similar with the phenylalkoxy chains in extended conformations. However, there are significant differences in packing interactions. The packing in 1 is dominated by C–Br...π(arene) interactions, with each Br located over one C–C bond of the central arene ring of an adjacent molecule. In contrast, the packing of molecules of 2 involves a combination of C–H...Br hydrogen bonds, Br...Br interactions, and arene–arene π-stacking. The single-crystal structures of both orthorhombic and triclinic polymorphs of 1 have been determined and the packing interactions are shown to be essentially identical.

scholarly journals Crystal structures of 4-chloropyridine-2-carbonitrile and 6-chloropyridine-2-carbonitrile exhibit different intermolecular π-stacking, C—H...Nnitrileand C—H...Npyridineinteractions

2015 ◽  
Vol 71 (7) ◽  
pp. 852-856 ◽  
Author(s):  
Matthew J. Montgomery ◽  
Thomas J. O'Connor ◽  
Joseph M. Tanski
Keyword(s):  
Solid State ◽  
Crystal Structures ◽  
Pyridine Ring ◽  
Nitrile Group ◽  
Two Dimensional ◽  
One Dimensional ◽  
Face To Face ◽  
Π Stacking

The two title compounds are isomers of C6H3ClN2containing a pyridine ring, a nitrile group, and a chloro substituent. The molecules of each compound pack together in the solid state with offset face-to-face π-stacking, and intermolecular C—H...Nnitrileand C—H...Npyridineinteractions. 4-Chloropyridine-2-carbonitrile, (I), exhibits pairwise centrosymmetric head-to-head C—H...Nnitrileand C—H...Npyridineinteractions, forming one-dimensional chains, which are π-stacked in an offset face-to-face fashion. The intermolecular packing of the isomeric 6-chloropyridine-2-carbonitrile, (II), which differs only in the position of the chloro substituent on the pyridine ring, exhibits head-to-tail C—H...Nnitrileand C—H...Npyridineinteractions, forming two-dimensional sheets which are π-stacked in an offset face-to-face fashion. In contrast to (I), the offset face-to-face π-stacking in (II) is formed between molecules with alternating orientations of the chloro and nitrile substituents.

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