Molecular Cocrystals of Carboxylic Acids. XV. Preparation and Characterization of Heterocyclic Base Adducts With a Series of Carboxylic Acids, and the Crystal Structures of the Adducts of 2-Aminopyrimidine With 2,6-Dihydroxybenzoic Acid, 4-Aminobenzoic Acid, Phenoxyacetic Acid, (2,4-Dichlorophenoxy)acetic Acid, (3,4-Dichlorophenoxy)-acetic Acid and Salicylic Acid, and 2-Aminopyridine With 2,6-Dihydroxybenzoic Acid

1994 ◽  
Vol 47 (6) ◽  
pp. 1097 ◽  
Author(s):  
DE Lynch ◽  
G Smith ◽  
D Freney ◽  
KA Byriel ◽  
CHL Kennard
Keyword(s):  
Acetic Acid ◽  
Salicylic Acid ◽  
Carboxylic Acids ◽  
Phenoxyacetic Acid ◽  
Aminobenzoic Acid ◽  
X Ray Diffraction ◽  
Dihydroxybenzoic Acid ◽  
Heterocyclic Base ◽  
X Ray ◽  
Dichlorophenoxy Acetic Acid

The molecular adducts of the heterocyclic base 2-aminopyrimidine with the aromatic and aromatic aliphatic carboxylic acids salicylic acid, 2,6-dihydroxybenzoic acid and 4-aminobenzoic acid, phenoxyacetic acid, (2,4-dichlorophenoxy)acetic acid, and (3,4-dichlorophenoxy)acetic acid have been prepared, and their interactive modes characterized by single-crystal X-ray diffraction methods. In addition, the complexes with (4-chlorophenoxy)acetic acid, (2,3-dichlorophenoxy)acetic acid, (4-chloro-2-methylphenoxy)acetic acid and (2,4,5- trichlorophenoxy)acetic acid have been characterized by analytical methods, including infrared spectroscopy. Except for the phenoxyacetic acid adduct (2:1), all form 1:1 molecular associations in which the carboxylic acid shows a variable tendency to protonate the hetero nitrogen of the base. The 1:1 complex of 2-aminopyridine with 2,6-dihydroxybenzoic acid has also been characterized by single-crystal X-ray diffraction.

Conformational Comparisons Between Phenoxyacetic Acid Derivatives in Adducts and in the Free Form

1999 ◽  
Vol 52 (7) ◽  
pp. 695 ◽  
Author(s):  
Graham Smith ◽  
Catherine J. Cooper ◽  
Veena Chauhan ◽  
Daniel E. Lynch ◽  
Simon Parsons ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Single Crystal ◽  
Free Acid ◽  
Molecular Complexes ◽  
The Other ◽  
Free Form ◽  
Phenoxyacetic Acid ◽  
X Ray Diffraction ◽  
X Ray ◽  
Dichlorophenoxy Acetic Acid

Six molecular complexes containing the herbicidally active (2,4-dichlorophenoxy)acetic acid (2,4-d) and (2,4,5-trichlorophenoxy)acetic acid (2,4,5-t) have been prepared and studied by using single-crystal X-ray diffraction techniques. These adduct structures are 2,4-d with 4,4′-dipyridine (2 : 1 complex), and 2,4,5-t with respectively 5-nitroquinoline (1 : 1), 4,4′-dipyridine (2 : 1), 2-amino-2-thiazoline (1 : 1), 2-aminobenzothiazole (1 : 1) and 2-amino-5-ethyl-1,3,4-thiadiazole (1 : 1). The conformations of the phenoxyacetic acid molecules were found to be either synclinal (in three cases) or antiperiplanar (in the other three cases). A general review is also made about the conformational aspects of previously reported adducts of phenoxyacetic acid derivatives and how they compare to their free acid structures.

Molecular Cocrystals of Carboxylic Acids. IX. Carboxylic Acid Interactions With Organic Heterocyclic Bases. The Crystal Structures of the Adducts of (2,4-Dichlorophenoxy)acetic Acid With 3-Hydroxypyridine, 2,4,6-Trinitrobenzoic Acid With 2-Aminopyrimidine, and 4-Nitrobenzoic Acid With 3-Amino-1,2,4-triazole

1992 ◽  
Vol 45 (6) ◽  
pp. 969 ◽  
Author(s):  
KA Byriel ◽  
CHL Kennard ◽  
DE Lynch ◽  
G Smith ◽  
JG Thompson
Keyword(s):  
Acetic Acid ◽  
Carboxylic Acid ◽  
Crystal Structures ◽  
Carboxylic Acids ◽  
Spectroscopic Techniques ◽  
X Ray Diffraction ◽  
X Ray ◽  
Nitrobenzoic Acid ◽  
Dichlorophenoxy Acetic Acid ◽  
Heterocyclic Bases

The cocrystal adducts of a number of carboxylic acids with organic heterocyclic bases have been prepared, and their structures and intermolecular interactions interpreted through X-ray diffraction and infrared spectroscopic techniques. The crystal structures of three of these compounds, the 1 : 1 adducts [{(2,4-dich1orophenoxy)acetic acid)(3-hydroxypyridine)] (1), [(2,4,6-trinitrobenzoie acid)(2-aminopyrimidine)] (2), and [(4-nitrobenzoic acid)(3-amino- 1,2,4-trimole)] (3), have been determined by single-crystal X-ray diffraction and refined to residuals R 0.026, 0.033 and 0.040 for 1814, 1531 and 727 observed reflections, respectively.

Molecular Cocrystals of Carboxylic Acids. XVII. Spectral Characterization of the Adducts of Triphenylphosphine Oxide With Substituted Phenoxyacetic Acids and the Crystal Structure of the 1 : 1 Adduct With (4-Chloro-2-methylphenoxy)acetic Acid

1994 ◽  
Vol 47 (7) ◽  
pp. 1401 ◽  
Author(s):  
DE Lynch ◽  
G Smith ◽  
KA Byriel ◽  
CHL Kennard ◽  
AK Whittaker ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Acetic Acid ◽  
Triphenylphosphine Oxide ◽  
X Ray Diffraction ◽  
X Ray ◽  
Acid Proton ◽  
Phosphoryl Oxygen ◽  
Phenoxyacetic Acids ◽  
Dichlorophenoxy Acetic Acid ◽  
Molecular Adducts

A series of 1:1 molecular adducts of triphenylphosphine oxide ( tppo ) with substituted phenoxyacetic acids has been prepared and characterized by using infrared, solid-state 1H and 31P n.m.r. spectroscopy, and X-ray powder diffraction methods. The crystal structure of one of these, with the herbicidally active (4-chloro-2-methylphenoxy)acetic acid ( mcpa ),[( tppo )( mcpa )], has been determined by X-ray diffraction methods. This compound is isomorphous with the tppo adduct of (2,4-dichlorophenoxy)acetic acid. The title compound has two independent and different molecular adducts in the asymmetric unit each with strong hydrogen-bonding interactions between the carboxylic acid proton and the phosphoryl oxygen of tppo [O...O, 2.579, 2.647(9)Ǻ].

Preparation and Crystal Structure of the Potentially Tridentate Substituted Phenoxyacetic Acid (2-Benzoyl-5-methoxyphenoxy)acetic Acid and Its Complex Adduct With Sodium

1995 ◽  
Vol 48 (4) ◽  
pp. 869 ◽  
Author(s):  
G Smith ◽  
EJ Oreilly ◽  
SA See ◽  
KA Byriel ◽  
CHL Kennard
Keyword(s):  
Crystal Structure ◽  
Acetic Acid ◽  
Carboxy Group ◽  
Intramolecular Hydrogen Bonding ◽  
Ligand Molecule ◽  
Phenoxyacetic Acid ◽  
X Ray Diffraction ◽  
X Ray ◽  
Intramolecular Hydrogen ◽  
Hydrogen Bonded

The ring-substituted phenoxyacetic acid (2-benzoyl-5-methoxyphenoxy)acetic acid (HL) (3) and its complex adduct dimer (4) with sodium, [Na2(L)2(HL)2].2HL, have been synthesized and their structures determined by X-ray diffraction. The acid (3) does not have the usual cyclic hydrogen-bonded dimer association, but instead has three-centre intramolecular hydrogen bonding between the carboxyl proton and both the ether and keto oxygens [O---O, 2.602(3), 2.711(3) Ǻ respectively]. Each sodium in the centrosymmetric complex dimer (4) is seven-coordinate [Na-O, 2.313(5)-2.612(5) Ǻ], involving the 'inner' three oxygens of both a protonated and an ionic ligand molecule. In addition, one of these carboxyl oxygens forms a bridge to the inversion-related sodium, while the uncoordinated carboxyl oxygen is hydrogen-bonded to a protonated carboxy group [O---O, 2.464(8) Ǻ]. The molecules of the lattice acid have only one hydrogen-bonded association with the second uncoordinated carboxy group in the dimer [O---O, 2.513(7) Ǻ].

Molecular Cocrystals of Carboxylic Acids. XXXI Adducts of 2-Aminopyrimidine and 3-Amino-1,2,4-triazole with Heterocyclic Carboxylic Acids

1998 ◽  
Vol 51 (5) ◽  
pp. 403 ◽  
Author(s):  
Daniel E. Lynch ◽  
Tariq Latif ◽  
Graham Smith ◽  
Karl A. Byriel ◽  
Colin H. L. Kennard ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Carboxylic Acid ◽  
Single Crystal ◽  
Carboxylic Acids ◽  
Powder Diffraction ◽  
X Ray Diffraction ◽  
X Ray ◽  
Indole 3 Acetic Acid ◽  
Molecular Adducts

A series of molecular adducts of 2-aminopyrimidine and 3-amino-1,2,4-triazole with heterocyclic carboxylic acids have been prepared and characterized by using X-ray powder diffraction and in four cases by single-crystal X-ray diffraction methods. These four compounds are the (1 : 1) adducts of 2-aminopyrimidine with indole-3-acetic acid [(C4H5N3)(C10H9NO2)], N-methylpyrrole-2-carboxylic acid [(C4H5N3)(C6H7NO2)] and thiophen-2-carboxylic acid [(C4H5N3)(C5H4O2S)], and the (1 : 1) adduct of 3-amino-1,2,4-triazole with thiophen-2-carboxylic acid [(C2H4N4)(C5H4O2S)]. Other compounds described are the (1 : 1) adducts of 3-amino-1,2,4-triazole with indole-3-acetic acid and N-methylpyrrole-2-carboxylic acid.

scholarly journals Systematic synthesis of a 6-component organic-salt alloy of naftopidil, and pentanary, quaternary and ternary multicomponent crystals

IUCrJ ◽  
2018 ◽  
Vol 5 (6) ◽  
pp. 816-822 ◽  
Author(s):  
Rambabu Dandela ◽  
Srinu Tothadi ◽  
Udaya Kiran Marelli ◽  
Ashwini Nangia
Keyword(s):  
Single Crystal ◽  
Carboxylic Acids ◽  
Active Pharmaceutical Ingredient ◽  
Organic Salt ◽  
X Ray Diffraction ◽  
Dihydroxybenzoic Acid ◽  
Scanning Calorimetry ◽  
Organic Salts ◽  
X Ray ◽  
Substituted Benzoic Acids

The single-crystal X-ray structure of a 6-component organic-salt alloy (hexanary) of naftopidil (1) (an active pharmaceutical ingredient) with benzoic acid (2) and four different hydroxy-substituted benzoic acids, i.e. salicylic acid (3), 2,3-dihydroxybenzoic acid (4), 2,4-dihydroxybenzoic acid (5) and 2,6-dihydroxybenzoic acid (6), is reported. The hexanary assembly originates from the observation that the binary salts of naftopidil with the above acids are isostructural. In addition to the 6-component solid, we also describe five 5-component, ten 4-component, and ten 3-component organic-salt alloys of naftopidil (1) with carboxylic acids (2)–(6). These alloys were obtained from different combinations of the acids with the drug. The synthetic design of the multicomponent organic alloys is based on the rationale of geometrical factors (shape and size) and chemical interactions (hydrogen bonds). The common supramolecular synthon in all these crystal structures was the cyclic N+—H...O− and O—H...O hydrogen-bonded motif of R_2^2(9) graph set between the 2-hydroxyammonium group of naftopidil and the carboxylate anion. This ionic synthon is strong and robust, directing the isostructural assembly of naftopidil with up to five different carboxylic acids in the crystal structure together with the lower-level multicomponent adducts. Solution crystallization by slow evaporation provided the multicomponent organic salts and alloys which were characterized by a combination of single-crystal X-ray diffraction, powder X-ray diffraction, NMR and differential scanning calorimetry techniques.

Molecular Cocrystals of Carboxylic Acids. XXVIII. Nitro-Substituted Carboxylic Acids with Lewis Bases: the Crystal Structures of the Adducts of 3,5-Dinitrobenzoic Acid with N-Methylaniline (1 : 1), (4-Nitrophenyl)acetic Acid with Cyclohexane-1,4-diamine (2 : 1), and 5-Nitrosalicylic Acid with 2-Imidazolidone (2 : 1)

1998 ◽  
Vol 51 (2) ◽  
pp. 159 ◽  
Author(s):  
Graham Smith ◽  
Daniel E. Lynch ◽  
Raymond C. Bott
Keyword(s):  
Acetic Acid ◽  
Infrared Spectroscopy ◽  
Carboxylic Acid ◽  
Proton Transfer ◽  
Crystal Structures ◽  
Carboxylic Acids ◽  
Aromatic Acids ◽  
X Ray Diffraction ◽  
X Ray ◽  
Lewis Bases

A number of molecular adducts of nitro-substituted aromatic acids with Lewis bases have been prepared and characterized by infrared spectroscopy and in three cases by X-ray diffraction methods. These three compounds are the adducts of: 3,5-dinitrobenzoic acid (dnba) with N-methylaniline (nma), [(dnba)-(nma)+] (1); (4-nitrophenyl)acetic acid (4-npa) with cyclohexane-1,4-diamine (dach), [(4-npa)22-(dach)2+] (4); 5-nitrosalicylic acid (5-nsa) with 2-imidazolidone (idaz), [(5-nsa)2(idaz)] (5). Other compounds are the adducts of 3,5-dinitrobenzoic acid with 2,6-dimethylpyridine (dmp), [(dnba)(dnba)-(dmp)+] (2), and with 1-methylpyrrole-2-carboxylic acid (cmp), [(dnba)-(cmp)+] (3). Compounds (1) and (3) have 1 : 1 stoichiometry, while (2), (4) and (5) are 2 : 1 adducts. Proton transfer occurs in most examples [complex (5) is the exception].

Molecular Cocrystals of Carboxylic Acids. XXV The Utility of Urea in Structure Making with Carboxylic Acids and the Crystal Structures of a Set of Six Adducts with Aromatic Acids

1997 ◽  
Vol 50 (7) ◽  
pp. 727 ◽  
Author(s):  
Graham Smith ◽  
Katherine E. Baldry ◽  
Karl A. Byriel ◽  
Colin H. L. Kennard
Keyword(s):  
Hydrogen Bonding ◽  
Infrared Spectroscopy ◽  
Dicarboxylic Acid ◽  
Carboxylic Acids ◽  
Phthalic Acid ◽  
Aromatic Acids ◽  
Aminobenzoic Acid ◽  
X Ray Diffraction ◽  
X Ray ◽  
Polymeric Structures

Molecular adducts of urea with six aromatic carboxylic acids have been prepared and characterized by using X-ray diffraction methods and infrared spectroscopy. These compounds are with 5-nitrosalicylic acid [(C7H5NO5)2(CH4N2O)] (1), 3,5-dinitrosalicylic acid [(C7H4N2O7)(CH4N2O)] (2), 4-aminobenzoic acid [(C7H7NO2)2(CH4N2O)] (3), o-phthalic acid [(C8H6O4)(CH4N2O)] (4), pyrazine-2,3-dicarboxylic acid [(C4H4N2O4)(CH4N2O)] (5) and pyridine-2,6-dicarboxylic acid [(C7H5NO4)(CH4N2O)2] (6). In the majority of the adducts, all six potential interactive sites on the urea molecules are utilized in hydrogen bonding, giving polymeric structures.

An unusual reaction of a bridged triterpenoid α-diketone with acetic anhydride

1991 ◽  
Vol 56 (12) ◽  
pp. 2917-2935 ◽  
Author(s):  
Eva Klinotová ◽  
Václav Křeček ◽  
Jiří Klinot ◽  
Miloš Buděšínský ◽  
Jaroslav Podlaha ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Nmr Spectroscopy ◽  
Acetic Anhydride ◽  
Spectral Methods ◽  
X Ray Diffraction ◽  
X Ray ◽  
Mild Conditions ◽  
Condensation Products ◽  
Unsaturated Lactones ◽  
C Nmr

3β-Acetoxy-21,22-dioxo-18α,19βH-ursan-28,20β-olide (IIIa) reacts with acetic anhydride in pyridine under very mild conditions affording β-lactone IVa and γ-lactones Va and VIIa as condensation products. On reaction with pyridine, lactones Va and VIIa undergo elimination of acetic acid to give unsaturated lactones VIIIa and IXa, respectively. Similarly, the condensation of 20β,28-epoxy-21,22-dioxo-18α,19βH-ursan-3β-yl acetate (IIIb) with acetic anhydride leads to β-lactone IVb and γ-lactone Vb; the latter on heating with pyridine affords unsaturated lactone VIIIb and 21-methylene-22-ketone Xb. The structure of the obtained compounds was derived using spectral methods, particularly 1H and 13C NMR spectroscopy; structure of lactone IVa was confirmed by X-ray diffraction.

scholarly journals Tautomerisation in 1-(4-Methylphenylazo)naphthalen-2-ol and 2-(4-Methylphenylazo)-4-methylphenol: A Crystallographic and 13C{1H}NMR Study

1999 ◽  
Vol 23 (3) ◽  
pp. 178-179
Author(s):  
Wendy I. Cross ◽  
Kevin R. Flower ◽  
Robin G. Pritchard
Keyword(s):  
Acetic Acid ◽  
Nmr Spectroscopy ◽  
Resonant Frequency ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Nmr Study ◽  
Acetic Acid Esters ◽  
Acid Esters ◽  
Equivalent Carbon

The acetic acid esters of 1-(4-methylphenylazo)naphthalen-2-ol 1 and 2-(4-methylphenylazo)-4-methylphenol 3 are prepared and characterised by single crystal X-ray diffraction studies and 13C{1H}NMR spectroscopy; the position of the C(2)13C resonance for the ester is used to predict the position of resonant frequency of the equivalent carbon in the parent alcohols and hence, calculate the position of the azo-hydrazone equilibrium in these compounds.

Sign in / Sign up

Export Citation Format

Share Document