scholarly journals 5-Nitrosalicylic Acid and its Proton-Transfer Compounds with Aliphatic Lewis Bases

2005 ◽  
Vol 58 (1) ◽  
pp. 47 ◽  
Author(s):  
Graham Smith ◽  
Andy W. Hartono ◽  
Urs D. Wermuth ◽  
Peter C. Healy ◽  
Jonathan M. White ◽  
...  
Keyword(s):  
Hydrogen Bonds ◽  
Proton Transfer ◽  
Lewis Base ◽  
Unusual Structure ◽  
Lewis Bases ◽  
Carboxylate Oxygen ◽  
Hydrogen Bonding Interactions ◽  
Polymer Compound ◽  
Proton Transfer Compounds ◽  
Centrosymmetric Dimers

The crystal structures of the proton-transfer compounds of 5-nitrosalicylic acid (5-nsa) with morpholine (morph), hexamethylenetetramine (hmt), and ethylenediamine (en) have been determined and their solid-state packing structures described. The compounds are [(morph)+(5-nsa)–] 1, [(hmt)+(5-nsa)–·H2O] 2, and [(en)2+2(5-nsa)–·H2O] 3. In all compounds, protonation of the hetero-nitrogen of the Lewis base occurs. With 1, the 5-nsa anions and the morpholine cations lie, respectively, in or across crystallographic mirror planes and are linked within the planes by hydrogen-bonding interactions through the aminium group and the carboxylic and phenolic oxygens of the anionic 5-nsa species giving a two-dimensional sheet polymer. Compound 2 is an unusual structure with the planar 5-nsa anions lying within pseudo mirror planes and cyclically linked by duplex water bridges through a single carboxylate oxygen into centrosymmetric dimers. The hmt cation molecules are disordered across the pseudo mirror and are strongly linked by N+–H···O hydrogen bonds only to the water molecules with peripheral weak hmt C–H···O hydrogen bonds extending the dimer within and between the dimer planes. Compound 3 is a network polymer comprised of the 5-nsa anions, the en dianions, and the water molecule in an extensive hydrogen-bonded structure.

Structure-Making with 3,5-Dimitrosalicylic Acid. I. The Proton Transfer Compounds of 3,5-Dinitrosalicylic Acid with a Series of Aliphatic Amines

2002 ◽  
Vol 55 (5) ◽  
pp. 349 ◽  
Author(s):  
G. Smith ◽  
U. D. Wermuth ◽  
P. C. Healy ◽  
R. C. Bott ◽  
J. M. White
Keyword(s):  
Hydrogen Bonding ◽  
Proton Transfer ◽  
Lewis Base ◽  
Aliphatic Amines ◽  
Tertiary Amines ◽  
Carboxylate Oxygen ◽  
Phenolic Oxygen ◽  
Phenolic Group ◽  
Intramolecular Hydrogen ◽  
Proton Transfer Compounds

The crystal structures of the proton-transfer compounds of 3,5-dinitrosalicylic acid (dnsa) with ammonia (two polymorphs) and a series of common aliphatic amines (methylamine, triethylamine, hexamethylenetetramine and ethylenediamine) have been determined and the hydrogen-bonding associations in each analysed. The compounds are [(NH4)+(dnsa)-] (1A, 1B), [(CH3NH3)+(dnsa)-] (2), [{(C2H5)3NH}+(dnsa)-] (3), [(C6H12 N4H)+(dnsa)-] (4) and [{(CH2 NH3) 2}2+(dnsa)2-�H2O] (5). It is of interest that with hydrate (5) the phenolic proton of dnsa is also lost on reaction, giving a rare dianionic species. In all compounds, protonation of the amino group of the Lewis base occurs, with subsequent hydrogen bonding via this and other hydrogens variously to the carboxylic, nitro and phenolic oxygens of dnsa, and in the case of (5), the lattice water. The result is the formation of simple linear associations with the tertiary amines, or network polymers with the less-substituted examples. Short intramolecular hydrogen bonds between the phenolic group and the carboxylate group are found in all compounds except (5), with the proton localized on the carboxylate oxygen rather than on the phenolic oxygen, but in the case of (3), delocalized within the hydrogen bond.

scholarly journals Zero-, one- and two-dimensional hydrogen-bonded structures in the 1:1 proton-transfer compounds of 4,5-dichlorophthalic acid with the monocyclic heteroaromatic Lewis bases 2-aminopyrimidine, nicotinamide and isonicotinamide

2009 ◽  
Vol 65 (3) ◽  
pp. o103-o107 ◽  
Author(s):  
Graham Smith ◽  
Urs D. Wermuth ◽  
Jonathan M. White
Keyword(s):  
Proton Transfer ◽  
Lewis Base ◽  
Two Dimensional ◽  
Compound I ◽  
Lewis Bases ◽  
Amide Carbonyl ◽  
Low Dimensionality ◽  
Low Dimensional ◽  
Proton Transfer Compounds ◽  
Hydrogen Bonded

The structures of the anhydrous 1:1 proton-transfer compounds of 4,5-dichlorophthalic acid (DCPA) with the monocyclic heteroaromatic Lewis bases 2-aminopyrimidine, 3-(aminocarbonyl)pyridine (nicotinamide) and 4-(aminocarbonyl)pyridine (isonicotinamide), namely 2-aminopyrimidinium 2-carboxy-4,5-dichlorobenzoate, C4H6N3+·C8H3Cl2O4−, (I), 3-(aminocarbonyl)pyridinium 2-carboxy-4,5-dichlorobenzoate, C6H7N2O+·C8H3Cl2O4−, (II), and the unusual salt adduct 4-(aminocarbonyl)pyridinium 2-carboxy-4,5-dichlorobenzoate–methyl 2-carboxy-4,5-dichlorobenzoate (1/1), C6H7N2O+·C8H3Cl2O4−·C9H6Cl2O4, (III), have been determined at 130 K. Compound (I) forms discrete centrosymmetric hydrogen-bonded cyclic bis(cation–anion) units having bothR22(8) andR12(4) N—H...O interactions. In (II), the primary N—H...O-linked cation–anion units are extended into a two-dimensional sheet structureviaamide–carboxyl and amide–carbonyl N—H...O interactions. The structure of (III) reveals the presence of an unusual and unexpected self-synthesized methyl monoester of the acid as an adduct molecule, giving one-dimensional hydrogen-bonded chains. In all three structures, the hydrogen phthalate anions are essentially planar with short intramolecular carboxyl–carboxylate O—H...O hydrogen bonds [O...O = 2.393 (8)–2.410 (2) Å]. This work provides examples of low-dimensional 1:1 hydrogen-bonded DCPA structure types, and includes the first example of a discrete cyclic `heterotetramer.' This low dimensionality in the structures of the 1:1 aromatic Lewis base salts of the parent acid is generally associated with the planar DCPA anion species.

scholarly journals A dianionic 5-sulfonatosalicylate species in the proton-transfer compound bis(benzylaminium) 3-carboxylato-4-hydroxybenzenesulfonate

2006 ◽  
Vol 62 (5) ◽  
pp. o1863-o1865 ◽  
Author(s):  
Graham Smith ◽  
Urs D. Wermuth ◽  
Peter C. Healy
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Proton Transfer ◽  
Two Dimensional ◽  
Sulfosalicylic Acid ◽  
Lewis Bases ◽  
Hydrogen Bonding Interactions ◽  
Dimensional Network ◽  
Proton Transfer Compound ◽  
Proton Transfer Compounds

The crystal structure of anhydrous bis(benzylaminium) 5-sulfonatosalicylate, 2C7H10N+·C7H4O6S2−, from the reaction of benzylamine with 5-sulfosalicylic acid, shows the presence of a dianionic 5-sulfonatosalicylate species, uncommon among proton-transfer compounds of this acid with organic Lewis bases. Hydrogen-bonding interactions between both aminium N+—H groups of the two cations and both the sulfonate and carboxylate O-atom acceptors of the anions give a layered two-dimensional network structure.

scholarly journals 3,5-Dinitrosalicylic Acid in Molecular Assembly. III. Proton-Transfer Compounds of 3,5-Dinitrosalicylic Acid with Polycyclic Aromatic and Heteroaromatic Amines, and Overall Series Structural Systematics

2007 ◽  
Vol 60 (4) ◽  
pp. 264 ◽  
Author(s):  
Graham Smith ◽  
Urs D. Wermuth ◽  
Peter C. Healy ◽  
Jonathan M. White
Keyword(s):  
Hydrogen Bonding ◽  
Proton Transfer ◽  
Crystal Structures ◽  
Molecular Assembly ◽  
Lewis Base ◽  
Amino Group ◽  
Π Interactions ◽  
Hydrogen Donors ◽  
Polycyclic Aromatic ◽  
Proton Transfer Compounds

The crystal structures of the 1:1 proton-transfer compounds of 3,5-dinitrosalicylic acid (dnsa) with a series of common polycyclic aromatic and heteroaromatic amines (quinoline, 1-naphthylamine, 1,2,3,4-tetrahydroquinoline, quinaldic acid, benzimidazole, 1,10-phenanthroline, and 2,2′-bipyridine) have been determined and the hydrogen-bonding associations in each analyzed. The compounds are [(C9H8N)+(dnsa)–] 1, [(C10H10N)+(dnsa)–] 2, [(C9H12N)+(dnsa)–] 3, [(C10H8NO2)+(dnsa)–] 4, [(C7H7N2)+(dnsa)–] 5, [(C12H9N2)+(dnsa)–] 6, and [(C10H9N2)+(dnsa)–] 7. In all compounds, protonation of either the substituent amino group or the hetero-N of the Lewis base occurs, with subsequent hydrogen bonding via this and other hydrogen donors variously to the carboxylate, phenate, and nitro oxygen acceptors of the dnsa anions. The result is the formation of primary N+–H···O associations which with secondary peripheral interactions, which within this set of compounds includes an increased incidence of aromatic C–H···O associations, give framework polymer structures. In three of the compounds [1, 4, and 6], cation–anion π–π interactions are also found. The completion of this series of compounds has now allowed the categorization of the molecular assembly modes in the proton-transfer compounds of 3,5-dinitrosalicylic acid.

Intermolecular interactions of proton transfer compounds: synthesis, crystal structure and Hirshfeld surface analysis

2015 ◽  
Vol 71 (4) ◽  
pp. 427-436 ◽  
Author(s):  
Amani Direm ◽  
Angela Altomare ◽  
Anna Moliterni ◽  
Nourredine Benali-Cherif
Keyword(s):  
Crystal Structure ◽  
Proton Transfer ◽  
Surface Analysis ◽  
Three Dimensional ◽  
Hirshfeld Surface ◽  
Hirshfeld Surface Analysis ◽  
X Ray Diffraction ◽  
Hydrogen Bonding Interactions ◽  
Proton Transfer Compounds ◽  
Close Contacts

Three new proton transfer compounds, [2-ammonio-5-methylcarboxybenzene perchlorate (1), (C8H10NO2+·ClO4−), 4-(ammoniomethyl)carboxybenzene nitrate (2), (C8H10NO2+·NO3−), and 4-(ammoniomethyl)carboxybenzene perchlorate (3), (C8H10NO2+·ClO4−)], have been synthesized, their IR modes of vibrations have been assigned and their crystal structures studied by means of single-crystal X-ray diffraction. Their asymmetric units consist of one cation and one anion for both compounds (1) and (2). However, the crystal structure of compound (3) is based on a pair of cations and a pair of anions in its asymmetric unit. The three-dimensional Hirshfeld surface analysis and the two-dimensional fingerprint maps revealed that the three structures are dominated by H...O/O...H and H...H contacts. The strongest hydrogen-bonding interactions are associated with O—H...O and N—H...O constituting the highest fraction of approximately 50%, followed by those of the H...H type contributing 20%. Other close contacts are also present, including weak C...H/H...C contacts (with about 10%).

scholarly journals Stacking Structure of Quinolinium Hydrogensquarate

2011 ◽  
Vol 8 (2) ◽  
pp. 603-608
Author(s):  
M. M Belombe ◽  
J. Nenwa ◽  
F. Emmerling
Keyword(s):  
Hydrogen Bonds ◽  
Proton Transfer ◽  
Organic Salt ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
X Ray ◽  
Pile Up ◽  
Bulk Structure ◽  
Stacking Structure ◽  
Centrosymmetric Dimers

A new proton-transfer organic salt, quinolinium hydrogensquarate (C13H9NO4), has been synthesized and fully characterized by single crystal x-ray diffraction. The salt crystallizes in the monoclinic space groupP21/n with the parameters: a = 3.8290(12) Å,b= 20.960(6) Å,c= 13.802(4) Å,β= 95.452(5)°,V= 1102.7(6) Å3,Z= 4 formula units. The structure consists of uncommon supramolecular neutral dimers which pile up parallel to [100] forming infinite sheets. These centrosymmetric dimers are held together by lateral hydrogen-bonds whereby two neighboring coplanar hydrogensquarate anions act as a bridge between two terminal quinolinium cations and C-H...O bridgings interlink next neighboring sheets. The bulk structure of this salt is consolidated by weak π—π interactions within the sheets which are neatly ordered side-by-side relative to one another.

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