Tetrahydroberberine pharmaceutical salts/cocrystals with dicarboxylic acids: Charge-assisted hydrogen bond recognitions and solubility regulation

2019 ◽  
Vol 1197 ◽  
pp. 377-385 ◽  
Author(s):  
Yu-nan Zhang ◽  
Ying-li Liu ◽  
Li-xin Liu ◽  
Yan-ru Feng ◽  
Da-jun Zhang ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Dicarboxylic Acids ◽  
Pharmaceutical Salts

Pharmaceutical salts of emoxypine with dicarboxylic acids

2018 ◽  
Vol 74 (7) ◽  
pp. 797-806 ◽  
Author(s):  
Alex N. Manin ◽  
Alexander P. Voronin ◽  
Ksenia V. Drozd ◽  
Andrei V. Churakov ◽  
German L. Perlovich
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Dicarboxylic Acids ◽  
Lattice Energy ◽  
State Density ◽  
Functional Theory ◽  
One Dimensional ◽  
Fusion Enthalpy ◽  
Pharmaceutical Salts ◽  
Salt Forms

New salt forms of the antioxidant drug emoxypine (EMX, 2-ethyl-6-methylpyridin-3-ol) with pharmaceutically acceptable maleic (Mlt), malonic (Mln) and adipic (Adp) acids were obtained {emoxypinium maleate, C8H12NO+·C4H3O4 −, [EMX+Mlt], emoxypinium malonate, C8H12NO+·C3H3O4 −, [EMX+Mln], and emoxypinium adipate, C8H12NO+·C6H9O4 −, [EMX+Adp]} and their crystal structures determined. The molecular packing in the three EMX salts was studied by means of solid-state density functional theory (DFT), followed by QTAIMC (quantum theory of atoms in molecules and crystals) analysis. It was found that the major contribution to the packing energy comes from pyridine–carboxylate and hydroxy–carboxylate heterosynthons forming infinite one-dimensional ribbons, with [EMX+Adp] additionally stabilized by hydrogen-bonded C(9) chains of Adp− ions. The melting processes of the [EMX+Mlt] (1:1), [EMX+Mln] (1:1) and [EMX+Adp] (1:1) salts were studied and the fusion enthalpy was found to increase with the increase of the calculated lattice energy. The dissolution process of the EMX salts in buffer (pH 7.4) was also studied. It was found that the formation of binary crystals of EMX with dicarboxylic acids increases the EMX solubility by more than 30 times compared to its pure form.

Pharmaceutical salts of ciprofloxacin with dicarboxylic acids

2015 ◽  
Vol 77 ◽  
pp. 112-121 ◽  
Author(s):  
Artem O. Surov ◽  
Alex N. Manin ◽  
Alexander P. Voronin ◽  
Ksenia V. Drozd ◽  
Anna A. Simagina ◽  
...  
Keyword(s):  
Dicarboxylic Acids ◽  
Pharmaceutical Salts

scholarly journals Crystal structures of two nickel compounds comprising neutral NiIIhydrazone complexes and dicarboxylic acids

2017 ◽  
Vol 73 (2) ◽  
pp. 103-106 ◽  
Author(s):  
Takumi Nakanishi ◽  
Osamu Sato
Keyword(s):  
Hydrogen Bond ◽  
Metal Ions ◽  
Dicarboxylic Acid ◽  
Crystal Structures ◽  
Coordination Sphere ◽  
Dicarboxylic Acids ◽  
Carboxyl Groups ◽  
Inversion Symmetry ◽  
Nickel Compounds ◽  
Atom Position

Two isostructural NiIIcompounds, bis{N-[1-(pyridin-2-yl-κN)ethylidene]pyridine-4-carbohydrazonato-κ2N′,O}nickel(II)–2,5-dichloroterephthalic acid (1/1), [Ni(C13H11N4O)2](C8H4Cl2O4), and bis{N-[1-(pyridin-2-yl-κN)ethylidene]pyridine-4-carbohydrazonato-κ2N′,O}nickel(II)–2,5-dibromoterephthalic acid (1/1), [Ni(C13H11N4O)2](C8H4Br2O4), were synthesized and their crystal structures determined. The pair ofN,N′,O-tridentateN-[1-(pyridin-2-yl-κN)ethyl]pyridine-4-carbohydrazonateLligands result in acis-NiO2N4octahedral coordination sphere for the metal ions. The asymmetric units consist of two half-molecules of the dicarboxylic acids, which are completed by crystallographic inversion symmetry. In the respective crystals, the 2,5-dichloroterephthalic acid (H2Cl2TPA,1-Cl) molecules form zigzag hydrogen-bonded chains with the [Ni(L)2] molecules, with the hydrogen-bond distances in1-Brslightly longer than those in1-Cl. The packing is consolidated by aromatic π–π stacking between the dicarboxylic acid molecules and terminal pyridine rings in [Ni(L)2] and short halogen–halogen interactions are also observed. The qualitative prediction of the H-atom position from the C—N—C angles of the terminal pyridine rings inLand the C—O distances in the carboxyl groups show that1-Cland1-Brare co-crystals rather than salts.

Characteristic Vibrational Pattern for the Cyclic Dimer Carboxylic Acid Function in the Solid State

1996 ◽  
Vol 50 (8) ◽  
pp. 1000-1006 ◽  
Author(s):  
Ilse Wolfs ◽  
Herman O. Desseyn
Keyword(s):  
Hydrogen Bond ◽  
Solid State ◽  
Carboxylic Acid ◽  
Dicarboxylic Acids ◽  
Cyclic Dimer ◽  
Secondary Amide ◽  
Hydrogen Bond Pattern ◽  
Vibrational Characteristics ◽  
Vibrational Bands ◽  
Acid Function

The infrared and Raman characteristics of the cyclic dimer hydrogen-bonded carboxylic acid function in the solid state are fully reported. Some dicarboxylic acids (e.g., malonic, methylmalonic, di-methylmalonic, succinic, glutaric, and adipic acid) are reported as typical examples. The vibrational characteristics of the cyclic dimer hydrogen-bond pattern are studied through the effect of deuteration on the position of infrared and Raman bands and through the temperature effect on the behavior of the vibrational bands. The fundamentals can very well be compared with the fundamentals of the trans secondary amide function, and are therefore assigned as the acid I to acid VII fundamentals.

Inspiration for revival of old drug: Improving solubility and avoiding hygroscopicity of pipemidic acid by forming two pharmaceutical salts based on charge-assisted hydrogen bond recognitions

2021 ◽  
Author(s):  
Yunan Zhang ◽  
Yu Duan ◽  
Jin Su ◽  
Lixin Liu ◽  
Yanru Feng ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Aqueous Solubility ◽  
Pipemidic Acid ◽  
Pharmaceutical Salts

In order to improve the solubility of pipemidic acid (PPA) which belongs to quinolones and becomes an "old drug" due to it possesses low aqueous solubility which restricting its application,...

Geometric conditions for the formation of short intramolecular hydrogen bonds in dicarboxylic acids and their acid salts. Crystal structures of two cyclopropane derivatives containing such bonds: ammonium hydrogen caronate and potassium hydrogen caronate hydrate

1993 ◽  
Vol 203 (2) ◽  
Author(s):  
H. Küppers ◽  
S. M. Jessen
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Dicarboxylic Acids ◽  
Intramolecular Hydrogen Bonds ◽  
Geometric Conditions ◽  
Ammonium Hydrogen ◽  
Potassium Hydrogen ◽  
Intramolecular Hydrogen ◽  
Cyclopropane Derivatives

Abstract(I) Ammonium hydrogen 3,3-dimethyl-cis-1,2-cyclopropanedicarboxylate (NHBoth compounds show short intramolecular hydrogen bonds with O…O distances of 2.477(5) Å in (I) and 2.425(3) Å in (II). The present structures complement a series of comparable chelate systems. The different geometries in these chelates influence the hydrogen bond lengths (O…O) and produce distortions of the anions to different extents. These considerations, which make the tendency to form

Kurze inter-und intramolekulare W asserstoffbrückenbindungen in sauren Salzen halogensubstituierter Orthophthalsäuren/ Short Inter-and Intramolecular Hydrogen Bonds in Acid Salts of Halogen-Substituted o-Phthalic Acids

1986 ◽  
Vol 41 (7) ◽  
pp. 808-814 ◽  
Author(s):  
Rainer Mattes ◽  
Angela Dorau
Keyword(s):  
Hydrogen Bond ◽  
Phenyl Ring ◽  
Dicarboxylic Acids ◽  
Type B ◽  
X Ray ◽  
Carboxylate Groups ◽  
Phthalic Acids ◽  
Short Hydrogen Bond ◽  
Intramolecular Hydrogen ◽  
Acid Salts

AbstractThe hydrogen bonding in several acid salts of 4,5-dichlorophthalic, 3,6-dichlorophthalic and 3-fluorophthalic acid have been studied by IR spectroscopy and X-ray structure analysis. NH4H [3,6-Cl2C8H2O4] and KH[3-FC8H3O4], with O···O distances of 247 and 254.1(4) pm, respectively, belong to Speakman’s type B2 of acid salts of dicarboxylic acids. In NH4H[4,5-Cl2C8H2O4] · H2O a short hydrogen bond of 253(1) pm is formed to the H2O molecule. A very short intramolecular hydrogen bond of only 234.0(10) pm length was found in N(C4H9)4H[4,5-Cl2C8H2O4], In the [3,6-Cl2C8H2O4]2- dianion both carboxylate groups are nearly orthogonal to the phenyl ring.

scholarly journals The Impact of Halogen Substituents on the Synthesis and Structure of Co-Crystals of Pyridine Amides

Molecules ◽  
2021 ◽  
Vol 26 (4) ◽  
pp. 1147
Author(s):  
Amila M. Abeysekera ◽  
Abhijeet S. Sinha ◽  
Christer B. Aakeroy
Keyword(s):  
Hydrogen Bond ◽  
Halogen Bond ◽  
A Priori ◽  
Dicarboxylic Acids ◽  
Halogen Bonds ◽  
Target Molecules ◽  
Crystal Synthesis ◽  
Py Motif ◽  
The Impact ◽  
Structural Influence

Strategies for co-crystal synthesis tend to employ either hydrogen- or halogen-bonds between different molecules. However, when both interactions are present, the structural influence that they may exert on the resulting assembly is difficult to predict a priori. To shed some light on this supramolecular challenge, we attempted to co-crystallize ten aliphatic dicarboxylic acids (co-formers) with three groups of target molecules; N-(pyridin-2-yl)picolinamides (2Pyr-X), N-(pyridin-2-yl)nicotinamides (3Pyr-X), N-(pyridin-2-yl)isonicotinamides (4Pyr-X); X=Cl/ Br/ I. The structural outcomes were compared with co-crystals prepared from the non-halogenated targets. As expected, none of the reactions with 2Pyr-X produced co-crystals due to the presence of a very stable intramolecular N-H···N hydrogen bond. In the 3Pyr series, all six structures obtained showed the same synthons, –COOH···N(py) and –COOH···N(py)-NH, that were found in the non-halogenated parent 3Pyr and were additionally accompanied by structure directing X···O(OH) interactions (X=Br/I). The co-crystals of the unhalogenated parent 4Pyr co-crystals assembled via intermolecular –COOH···N(py) and –COOH···N(py)-NH synthons. Three of the analogues 4Pyr-X co-crystals displayed only COOH···N(py) and –COOH···N(py)-NH interactions. The three co-crystals of 4Pyr-X with fumaric acid (for which no analogues structures with 4Pyr are known) formed –COOH···N(py)-NH and –NH···O=C hydrogen bonds and showed no structure-directing halogen bonds. In three co-crystals of 4Pyr-I in which –COOH···N(py)-NH hydrogen bond was present, a halogen-bond based –I···N(py) synthon replaced the –COOH···N(py) motif observed in the parent structures. The structural influence of the halogen atoms increased in the order of Cl < Br < I, as the size of σ-holes increased. Finally, it is noteworthy that isostructurality among structures of the homomeric targets was not translated to structural similarities between their respective co-crystals.

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