scholarly journals Crystal structures of four isomeric hydrogen-bonded co-crystals of 6-methylquinoline with 2-chloro-4-nitrobenzoic acid, 2-chloro-5-nitrobenzoic acid, 3-chloro-2-nitrobenzoic acid and 4-chloro-2-nitrobenzoic acid

2020 ◽  
Vol 76 (11) ◽  
pp. 1701-1707
Author(s):  
Kazuma Gotoh ◽  
Hiroyuki Ishida
Keyword(s):  
Hydrogen Bond ◽  
Intermolecular Interactions ◽  
Layer Structure ◽  
Three Dimensional ◽  
Shape Index ◽  
Nitrobenzoic Acid ◽  
Acid And Base ◽  
Short Hydrogen Bond ◽  
Substituted Benzoic Acids ◽  
Hydrogen Bonded

The structures of the four isomeric compounds of 6-methylquinoline with chloro- and nitro-substituted benzoic acids, C7H4ClNO4·C10H9N, namely, 2-chloro-4-nitrobenzoic acid–6-methylquinoline (1/1), (I), 2-chloro-5-nitrobenzoic acid–6-methylquinoline (1/1), (II), 3-chloro-2-nitrobenzoic acid–6-methylquinoline (1/1), (III), and 4-chloro-2-nitrobenzoic acid–6-methylquinoline (1/1), (IV), have been determined at 185–190 K. In each compound, the acid and base molecules are linked by a short hydrogen bond between a carboxyl O atom and an N atom of the base. The O...N distances are 2.5452 (12), 2.6569 (13), 2.5640 (17) and 2.514 (2) Å, respectively, for compounds (I)–(IV). In the hydrogen-bonded acid–base units of (I), (III) and (IV), the H atoms are each disordered over two positions with O site:N site occupancies of 0.65 (3):0.35 (3), 0.59 (4):0.41 (4) and 0.48 (5):0.52 (5), respectively, for (I), (III) and (IV). The H atom in the hydrogen-bonded unit of (II) is located at the O-atom site. In all of the crystals of (I)–(IV), π–π interactions between the quinoline ring system and the benzene ring of the acid molecule are observed. In addition, a π–π interaction between the benzene rings of adjacent acid molecules and a C—H...O hydrogen bond are observed in the crystal of (I), and C—H...O hydrogen bonds and O...Cl contacts occur in the crystals of (III) and (IV). These intermolecular interactions connect the acid and base molecules, forming a layer structure parallel to the bc plane in (I), a column along the a-axis direction in (II), a layer parallel to the ab plane in (III) and a three-dimensional network in (IV). Hirshfeld surfaces for the title compounds mapped over d norm and shape index were generated to visualize the weak intermolecular interactions.

scholarly journals Role of pK a in establishing the crystal structures of six hydrogen-bonded compounds of 4-methylquinoline with different isomers of chloro- and nitro-substituted benzoic acids

2021 ◽  
Vol 77 (11) ◽  
Author(s):  
Hiroyuki Ishida
Keyword(s):  
Hydrogen Bond ◽  
Shape Index ◽  
Benzoic Acids ◽  
Quinoline Ring ◽  
Nitrobenzoic Acid ◽  
Layer Structures ◽  
Acid And Base ◽  
Short Hydrogen Bond ◽  
Substituted Benzoic Acids ◽  
Hydrogen Bonded

The structures of the six hydrogen-bonded 1:1 compounds of 4-methylquinoline (C10H9N) with chloro- and nitro-substituted benzoic acids (C7H4ClNO4), namely, 4-methylquinolinium 2-chloro-4-nitrobenzoate, C10H10N+·C7H3ClNO4 −, (I), 4-methylquinoline–2-chloro-5-nitrobenzoic acid (1/1), C10H9N·C7H4ClNO4, (II), 4-methylquinolinium 2-chloro-6-nitrobenzoate, C10H9.63N0.63+·C7H3.37ClNO4 0.63−, (III), 4-methylquinolinium 3-chloro-2-nitrobenzoate, C10H9.54N0.54+·C7H3.46ClNO4 0.54−, (IV), 4-methylquinolinium 4-chloro-2-nitrobenzoate, C10H10N+·C7H3ClNO4 −, (V), and 4-methylquinolinium 5-chloro-2-nitrobenzoate, C10H10N+·C7H3ClNO4 −, have been determined at 185–190 K. In each compound, the acid and base molecules are linked by a short hydrogen bond between a carboxy (or carboxylate) O atom and an N atom of the base. The O...N distances are 2.5652 (14), 2.556 (3), 2.5485 (13), 2.5364 (13), 2.5568 (13) and 2.5252 (11) Å, respectively, for compounds (I)–(VI). In the hydrogen-bonded acid–base units of (III) and (IV), the H atoms are each disordered over two positions with O site:N site occupancies of 0.37 (3):0.63 (3) and 0.46 (3):0.54 (4), respectively, for (III) and (IV). The H atoms in the hydrogen-bonded units of (I), (V) and (VI) are located at the N-atom site, while the H atom in (II) is located at the O-atom site. In all the crystals of (I)–(VI), π–π stacking interactions between the quinoline ring systems and C—H...O hydrogen bonds are observed. Similar layer structures are constructed in (IV)–(VI) through these interactions together with π–π interactions between the benzene rings of the adjacent acid molecules. A short Cl...Cl contact and an N—O...π interaction are present in (I), while a C—H...Cl hydrogen bond and a π–π interaction between the benzene ring of the acid molecule and the quinoline ring system in (II), and a C—H...π interaction in (III) are observed. Hirshfeld surfaces for the title compounds mapped over d norm and shape index were generated to visualize the weak intermolecular interactions.

scholarly journals Crystal structure of 4-chloro-2-nitrobenzoic acid with 4-hydroxyquinoline: a disordered structure over two states of 4-chloro-2-nitrobenzoic acid–quinolin-4(1H)-one (1/1) and 4-hydroxyquinolinium 4-chloro-2-nitrobenzoate

2019 ◽  
Vol 75 (12) ◽  
pp. 1853-1856
Author(s):  
Kazuma Gotoh ◽  
Hiroyuki Ishida
Keyword(s):  
Hydrogen Bond ◽  
Title Compound ◽  
Three Dimensional ◽  
Shape Index ◽  
Bond Forming ◽  
Nitrobenzoic Acid ◽  
Disordered Structure ◽  
Compound C ◽  
Acid And Base ◽  
Short Hydrogen Bond

The title compound, C9H7.5NO·C7H3.5ClNO4, was analysed as a disordered structure over two states, viz. co-crystal and salt, accompanied by a keto–enol tautomerization in the base molecule. The co-crystal is 4-chloro-2-nitrobenzoic acid–quinolin-4(1H)-one (1/1), C7H4ClNO4·C9H7NO, and the salt is 4-hydroxyquinolinium 4-chloro-2-nitrobenzoate, C9H8NO+·C7H3ClNO4 −. In the compound, the acid and base molecules are held together by a short hydrogen bond [O...O = 2.4393 (15) Å], in which the H atom is disordered over two positions with equal occupancies. In the crystal, the hydrogen-bonded acid–base units are linked by N—H...O and C—H...O hydrogen bonds, forming a tape structure along the a-axis direction. The tapes are stacked into a layer parallel to the ab plane via π–π interactions [centroid–centroid distances = 3.5504 (8)–3.9010 (11) Å]. The layers are further linked by another C—H...O hydrogen bond, forming a three-dimensional network. Hirshfeld surfaces for the title compound mapped over shape-index and d norm were generated to visualize the intermolecular interactions.

scholarly journals Crystal structures of two hydrogen-bonded compounds of chloranilic acid–ethyleneurea (1/1) and chloranilic acid–hydantoin (1/2)

2018 ◽  
Vol 74 (12) ◽  
pp. 1727-1730 ◽  
Author(s):  
Kazuma Gotoh ◽  
Hiroyuki Ishida
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Layer Structure ◽  
Asymmetric Unit ◽  
Acid Base ◽  
Chloranilic Acid ◽  
Base Interaction ◽  
Acid And Base ◽  
Acid Base Interaction ◽  
Hydrogen Bonded

The structures of the hydrogen-bonded 1:1 co-crystal of chloranilic acid (systematic name: 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone) with ethyleneurea (systematic name: imidazolidin-2-one), C6H2Cl2O4·C3H6N2O, (I), and the 1:2 co-crystal of chloranilic acid with hydantoin (systematic name: imidazolidine-2,4-dione), C6H2Cl2O4·2C3H4N2O2, (II), have been determined at 180 K. In the crystals of both compounds, the base molecules are in the lactam form and no acid–base interaction involving H-atom transfer is observed. The asymmetric unit of (I) consists of two independent half-molecules of chloranilic acid, with each of the acid molecules lying about an inversion centre, and one ethyleneurea molecule. The asymmetric unit of (II) consists of one half-molecule of chloranilic acid, which lies about an inversion centre, and one hydantoin molecule. In the crystal of (I), the acid and base molecules are linked via O—H...O and N—H...O hydrogen bonds, forming an undulating sheet structure parallel to the ab plane. In (II), the base molecules form an inversion dimer via a pair of N—H...O hydrogen bonds, and the base dimers are further linked through another N—H...O hydrogen bond into a layer structure parallel to (\overline{1}01). The acid molecule and the base molecule are linked via an O—H...O hydrogen bond.

scholarly journals Crystal structures of the two isomeric hydrogen-bonded cocrystals 2-chloro-4-nitrobenzoic acid–5-nitroquinoline (1/1) and 5-chloro-2-nitrobenzoic acid–5-nitroquinoline (1/1)

2019 ◽  
Vol 75 (11) ◽  
pp. 1694-1699
Author(s):  
Kazuma Gotoh ◽  
Hiroyuki Ishida
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Shape Index ◽  
Quinoline Ring ◽  
Acid Base ◽  
Π Interactions ◽  
Bond Forming ◽  
Nitrobenzoic Acid ◽  
Base Units ◽  
Hydrogen Bonded

The structures of two isomeric compounds of 5-nitroquinoline with chloro- and nitro-substituted benzoic acid, namely, 2-chloro-4-nitrobenzoic acid–5-nitroquinoline (1/1), (I), and 5-chloro-2-nitrobenzoic acid–5-nitroquinoline (1/1), (II), both C7H4ClNO4·C9H6N2O2, have been determined at 190 K. In each compound, the acid and base molecules are held together by an O—H...N hydrogen bond. In the crystal of (I), the hydrogen-bonded acid–base units are linked by a C—H...O hydrogen bond, forming a tape structure along [1\overline{2}0]. The tapes are stacked into a layer parallel to the ab plane via N—O...π interactions between the nitro group of the base molecule and the quinoline ring system. The layers are further linked by other C—H...O hydrogen bonds, forming a three-dimensional network. In the crystal of (II), the hydrogen-bonded acid–base units are linked into a wide ribbon structure running along [1\overline{1}0] via C—H...O hydrogen bonds. The ribbons are further linked via another C—H...O hydrogen bond, forming a layer parallel to (110). Weak π–π interactions [centroid–centroid distances of 3.7080 (10) and 3.7543 (9) Å] are observed between the quinoline ring systems of adjacent layers. Hirshfeld surfaces for the 5-nitroquinoline molecules of the two compounds mapped over shape index and d norm were generated to visualize the weak intermolecular interactions.

scholarly journals Molecular Recognition in Proton-Transfer Compounds of Brucine with Achiral Substituted Salicylic Acid Analogues

2006 ◽  
Vol 59 (5) ◽  
pp. 320 ◽  
Author(s):  
Graham Smith ◽  
Urs D. Wermuth ◽  
Peter C. Healy ◽  
Jonathan M. White
Keyword(s):  
Proton Transfer ◽  
Three Dimensional ◽  
Water Molecules ◽  
Sulfosalicylic Acid ◽  
X Ray ◽  
X Ray Crystallography ◽  
Guest Species ◽  
Substituted Benzoic Acids ◽  
Proton Transfer Compounds ◽  
Hydrogen Bonded

The 1:1 proton-transfer brucinium compounds from the reaction of the alkaloid brucine with 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, and 5-sulfosalicylic acid, namely anhydrous brucinium 5-nitrosalicylate (1), brucinium 3,5-dinitrosalicylate monohydrate (2), and brucinium 5-sulfosalicylate trihydrate (3) have been prepared and their crystal structures determined by X-ray crystallography. All structures further demonstrate the selectivity of brucine for meta-substituted benzoic acids and comprise three-dimensional hydrogen-bonded framework polymers. Two of the compounds (1 and 3) have the previously described undulating brucine sheet host-substructures which incorporate interstitially hydrogen-bonded salicylate anion guest species and additionally in 3 the water molecules of solvation. The structure of 2 differs in having a three-centre brucinium–salicylate anion bidentate N+–H···O(carboxyl) hydrogen-bonding association linking the species through interstitial associations involving also the water molecules of solvation. A review of the crystallographic structural literature on strychnine and brucine is also given.

The influence of intermolecular interactions and molecular packings on mechanochromism and mechanoluminescence – a tetraphenylethylene derivative case

2019 ◽  
Vol 7 (40) ◽  
pp. 12709-12716 ◽  
Author(s):  
Guangxi Huang ◽  
Yuqing Jiang ◽  
Jianguo Wang ◽  
Zhen Li ◽  
Bing Shi Li ◽  
...  
Keyword(s):  
Single Crystals ◽  
Intermolecular Interactions ◽  
Three Dimensional ◽  
Hydrogen Bonded

Compact packing and intact three-dimensional hydrogen-bonded networks in single crystals are favorable for ML properties.

Two polymorphs and the diethylammonium salt of the barbiturate eldoral

2012 ◽  
Vol 68 (2) ◽  
pp. o65-o70 ◽  
Author(s):  
Thomas Gelbrich ◽  
Denise Rossi ◽  
Ulrich J. Griesser
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Barbituric Acid ◽  
Layer Structure ◽  
Chain Structure ◽  
Hydrogen Bond Acceptor ◽  
Layer Structures ◽  
A Chain ◽  
Derivatives Of ◽  
Hydrogen Bonded

Polymorph (Ia) of eldoral [5-ethyl-5-(piperidin-1-yl)barbituric acid or 5-ethyl-5-(piperidin-1-yl)-1,3-diazinane-2,4,6-trione], C11H17N3O3, displays a hydrogen-bonded layer structure parallel to (100). The piperidine N atom and the barbiturate carbonyl group in the 2-position are utilized in N—H...N and N—H...O=C hydrogen bonds, respectively. The structure of polymorph (Ib) contains pseudosymmetry elements. The two independent molecules of (Ib) are connectedviaN—H...O=C(4/6-position) and N—H...N(piperidine) hydrogen bonds to give a chain structure in the [100] direction. The hydrogen-bonded layers, parallel to (010), formed in the salt diethylammonium 5-ethyl-5-(piperidin-1-yl)barbiturate [or diethylammonium 5-ethyl-2,4,6-trioxo-5-(piperidin-1-yl)-1,3-diazinan-1-ide], C4H12N+·C11H16N3O3−, (II), closely resemble the corresponding hydrogen-bonded structure in polymorph (Ia). Like many other 5,5-disubstituted derivatives of barbituric acid, polymorphs (Ia) and (Ib) contain theR22(8) N—H...O=C hydrogen-bond motif. However, the overall hydrogen-bonded chain and layer structures of (Ia) and (Ib) are unique because of the involvement of the hydrogen-bond acceptor function in the piperidine group.

Sulfur as hydrogen-bond acceptor in cocrystals of 2-thio-modified thymine

2018 ◽  
Vol 74 (1) ◽  
pp. 21-30 ◽  
Author(s):  
Wilhelm Maximilian Hützler ◽  
Michael Bolte
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Crystal Engineering ◽  
Rational Design ◽  
Three Dimensional ◽  
Good Reliability ◽  
Hydrogen Bond Acceptor ◽  
Hydrogen Bonding Interactions ◽  
Hydrogen Bonding Site ◽  
Hydrogen Bonded

Doubly and triply hydrogen-bonded supramolecular synthons are of particular interest for the rational design of crystal and cocrystal structures in crystal engineering since they show a high robustness due to their high stability and good reliability. The compound 5-methyl-2-thiouracil (2-thiothymine) contains an ADA hydrogen-bonding site (A = acceptor and D = donor) if the S atom is considered as an acceptor. We report herein the results of cocrystallization experiments with the coformers 2,4-diaminopyrimidine, 2,4-diamino-6-phenyl-1,3,5-triazine, 6-amino-3H-isocytosine and melamine, which contain complementary DAD hydrogen-bonding sites and, therefore, should be capable of forming a mixed ADA–DAD N—H...S/N—H...N/N—H...O synthon (denoted synthon 3s N·S;N·N;N·O), consisting of three different hydrogen bonds with 5-methyl-2-thiouracil. The experiments yielded one cocrystal and five solvated cocrystals, namely 5-methyl-2-thiouracil–2,4-diaminopyrimidine (1/2), C5H6N2OS·2C4H6N4, (I), 5-methyl-2-thiouracil–2,4-diaminopyrimidine–N,N-dimethylformamide (2/2/1), 2C5H6N2OS·2C4H6N4·C3H7NO, (II), 5-methyl-2-thiouracil–2,4-diamino-6-phenyl-1,3,5-triazine–N,N-dimethylformamide (2/2/1), 2C5H6N2OS·2C9H9N5·C3H7NO, (III), 5-methyl-2-thiouracil–6-amino-3H-isocytosine–N,N-dimethylformamide (2/2/1), (IV), 2C5H6N2OS·2C4H6N4O·C3H7NO, (IV), 5-methyl-2-thiouracil–6-amino-3H-isocytosine–N,N-dimethylacetamide (2/2/1), 2C5H6N2OS·2C4H6N4O·C4H9NO, (V), and 5-methyl-2-thiouracil–melamine (3/2), 3C5H6N2OS·2C3H6N6, (VI). Synthon 3s N·S;N·N;N·O was formed in three structures in which two-dimensional hydrogen-bonded networks are observed, while doubly hydrogen-bonded interactions were formed instead in the remaining three cocrystals whereby three-dimensional networks are preferred. As desired, the S atoms are involved in hydrogen-bonding interactions in all six structures, thus illustrating the ability of sulfur to act as a hydrogen-bond acceptor and, therefore, its value for application in crystal engineering.

The heterobifunctional ligand 5-[4-(1,2,4-triazol-4-yl)phenyl]-1H-tetrazole and its role in the construction of a CdIImetal–organic chain structure

2012 ◽  
Vol 68 (10) ◽  
pp. m291-m294
Author(s):  
Andrey B. Lysenko
Keyword(s):  
Hydrogen Bond ◽  
Three Dimensional ◽  
Organic Ligand ◽  
Chain Structure ◽  
Polar Space ◽  
Hydrogen Bond Donor ◽  
Donor Acceptor ◽  
A Chain ◽  
Water Ligands ◽  
Hydrogen Bonded

5-[4-(1,2,4-Triazol-4-yl)phenyl]-1H-tetrazole, C9H7N7, (I), an asymmetric heterobifunctional organic ligand containing triazole (tr) and tetrazole (tz) termini linked directly through a 1,4-phenylene spacer, crystallizes in the polar space groupPc. The heterocyclic functions, serving as single hydrogen-bond donor (tz) or acceptor (tr) units, afford hydrogen-bonded zigzag chains with no crystallographic centre of inversion. In the structure ofcatena-poly[[diaquacadmium(II)]bis{μ2-5-[4-(1,2,4-triazol-4-yl)phenyl]tetrazol-1-ido-κ2N1:N1′}], [Cd(C9H6N7)2(H2O)2]n, (II), the CdIIdication resides on a centre of inversion in an octahedral {N4O2} environment. In the equatorial plane, the CdIIpolyhedron is built up from four N atoms of two kinds, namely oftrans-coordinating tr and tz fragments [Cd—N = 2.2926 (17) and 2.3603 (18) Å], and the coordinating aqua ligands occupy the two apical sites. The metal centres are separated at a distance of 11.1006 (7) Å by means of the double-bridging tetrazolate anion,L−, forming a chain structure. The water ligands and tz fragments interact with one another, like a double hydrogen-bond donor–acceptor synthon, leading to a hydrogen-bonded three-dimensional array.

Different supramolecular architectures mediated by different weak interactions in the crystals of three N-aryl-2,5-dimethoxybenzenesulfonamides

2017 ◽  
Vol 73 (10) ◽  
pp. 833-844 ◽  
Author(s):  
K. Shakuntala ◽  
S. Naveen ◽  
N. K. Lokanath ◽  
P. A. Suchetan ◽  
M. Abdoh
Keyword(s):  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Intermolecular Interactions ◽  
Weak Interactions ◽  
Three Dimensional ◽  
Shape Index ◽  
Intramolecular Interactions ◽  
Molecular Conformations ◽  
Supramolecular Architectures ◽  
The Relationship

The synthesis and evaluation of the pharmacological activities of molecules containing the sulfonamide moiety have attracted interest as these compounds are important pharmacophores. The crystal structures of three closely related N-aryl-2,5-dimethoxybenzenesulfonamides, namely N-(2,3-dichlorophenyl)-2,5-dimethoxybenzenesulfonamide, C14H13Cl2NO4S, (I), N-(2,4-dichlorophenyl)-2,5-dimethoxybenzenesulfonamide, C14H13Cl2NO4S, (II), and N-(2,4-dimethylphenyl)-2,5-dimethoxybenzenesulfonamide, C16H19NO4S, (III), are described. The asymmetric unit of (I) consists of two symmetry-independent molecules, while those of (II) and (III) contain one molecule each. The molecular conformations are stabilized by different intramolecular interactions, viz. C—H...O interactions in (I), N—H...Cl and C—H...O interactions in (II), and C—H...O interactions in (III). The crystals of the three compounds display different supramolecular architectures built by various weak intermolecular interactions of the types C—H...O, C—H...Cl, C—H...π(aryl), π(aryl)–π(aryl) and Cl...Cl. A detailed Hirshfeld surface analysis of these compounds has also been conducted in order to understand the relationship between the crystal structures. The d norm and shape-index surfaces of (I)–(III) support the presence of various intermolecular interactions in the three structures. Analysis of the fingerprint plots reveals that the greatest contribution to the Hirshfeld surfaces is from H...H contacts, followed by H...O/O...H contacts. In addition, comparisons are made with the structures of some related compounds. Putative N—H...O hydrogen bonds are observed in 29 of the 30 reported structures, wherein the N—H...O hydrogen bonds form either C(4) chain motifs or R 2 2(8) rings. Further comparison reveals that the characteristics of the N—H...O hydrogen-bond motifs, the presence of other interactions and the resultant supramolecular architecture is largely decided by the position of the substituents on the benzenesulfonyl ring, with the nature and position of the substituents on the aniline ring exerting little effect. On the other hand, the crystal structures of (I)–(III) display several weak interactions other than the common N—H...O hydrogen bonds, resulting in supramolecular architectures varying from one- to three-dimensional depending on the nature and position of the substituents on the aniline ring.

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