Crystal structures, thermal stabilities, and dissolution behaviours of tinidazole and the tinidazole–vanillic acid cocrystal: insights from energy frameworks

2020 ◽  
Vol 76 (5) ◽  
pp. 389-397
Author(s):  
Kang Zheng ◽  
Changjian Xie ◽  
Xiaowei Li ◽  
Weiwei Wu ◽  
Ao Li ◽  
...  
Keyword(s):  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Vanillic Acid ◽  
Strong Interactions ◽  
Framework Analysis ◽  
Thermal Stabilities ◽  
X Ray ◽  
Naturally Occurring ◽  
Carboxylic Acid Dimer ◽  
Methoxybenzoic Acid

The crystal structures of the antimicrobial drug tinidazole [TNZ; systematic name: 1-(2-ethylsulfonylethyl)-2-methyl-5-nitroimidazole, C8H13N3O4S] and the 1:1 cocrystal of TNZ with the naturally occurring compound vanillic acid (VA; systematic name: 4-hydroxy-3-methoxybenzoic acid, C8H8O4), namely, the TNZ–VA cocrystal, were determined by single-crystal X-ray analysis at 100 K. The supramolecular structure of the TNZ–VA cocrystal is composed of a carboxylic acid dimer and an O—H...N(heterocycle) synthon in the form of layers made up of O—H...N and O—H...O hydrogen bonds. The layers are joined via C—H...O hydrogen bonds, π–π stacking and C—H...π interactions. The energy framework analysis, together with interaction energy calculations using the DLPNO-CCSD(T) method, indicates that the TNZ–VA cocrystal inherits strong interactions from the TNZ and VA crystals, which accounts for the enhanced thermal stability and reduced dissolution rate. To the best of our knowledge, this is the first example of a cocrystal containing TNZ.

Supramolecular architectures in two 1:1 cocrystals of 5-fluorouracil with 5-bromothiophene-2-carboxylic acid and thiophene-2-carboxylic acid

2017 ◽  
Vol 73 (6) ◽  
pp. 481-485 ◽  
Author(s):  
Marimuthu Mohana ◽  
Packianathan Thomas Muthiah ◽  
Colin D. McMillen
Keyword(s):  
Solid State ◽  
Carboxylic Acid ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
X Ray Diffraction ◽  
Base Pairs ◽  
X Ray ◽  
Supramolecular Architectures ◽  
Acid Acid ◽  
Carboxylic Acid Dimer

In solid-state engineering, cocrystallization is a strategy actively pursued for pharmaceuticals. Two 1:1 cocrystals of 5-fluorouracil (5FU; systematic name: 5-fluoro-1,3-dihydropyrimidine-2,4-dione), namely 5-fluorouracil–5-bromothiophene-2-carboxylic acid (1/1), C5H3BrO2S·C4H3FN2O2, (I), and 5-fluorouracil–thiophene-2-carboxylic acid (1/1), C4H3FN2O2·C5H4O2S, (II), have been synthesized and characterized by single-crystal X-ray diffraction studies. In both cocrystals, carboxylic acid molecules are linked through an acid–acid R 2 2(8) homosynthon (O—H...O) to form a carboxylic acid dimer and 5FU molecules are connected through two types of base pairs [homosynthon, R 2 2(8) motif] via a pair of N—H...O hydrogen bonds. The crystal structures are further stabilized by C—H...O interactions in (II) and C—Br...O interactions in (I). In both crystal structures, π–π stacking and C—F...π interactions are also observed.

Synthese und Kristallstrukturen einiger Tetramethylstibonium-Hydrogendicarboxylate / Synthesis and Crystal Structures of Some Tetramethylstibonium Hydrogendicarboxylates

1982 ◽  
Vol 37 (11) ◽  
pp. 1393-1401 ◽  
Author(s):  
Beatrix Milewski-Mahrla ◽  
Hubert Schmidbaur
Keyword(s):  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Spectroscopic Data ◽  
Molar Ratio ◽  
Ionic Structure ◽  
X Ray Diffraction ◽  
X Ray ◽  
Carboxylate Oxygen ◽  
Donor Acceptor ◽  
New Compounds

Reactions of pentamethylantimony (CH3)5Sb with carboxylic acids in the molar ratio 1:2 afford one equivalent of methane and essentially quantitative yields of crystalline tetramothylstibonium hydrogendicarboxylates. Six new compounds of this series have been synthesized using benzoic, o-phthalic, salicylic, 4-ethoxy-salicylic, oxalic, and malic acid, and characterized by analytical and spectroscopic data. An ionic structure with strong hydrogen bonds in the anionic components is proposed.The crystal structures of the hydrogen-dibenzoato (1), hydrogen-ortho-plithalato (2) and 4-ethoxy-hydrogen-salicylate (3) were determined by single crystal X-ray diffraction. The compounds can be described as having ionic lattices with some donor-acceptor inter­actions between the stibonium centers and the carboxylate oxygen atoms. The anions are characterized by strong hydrogen bonds O...H...O. Thus, the (CH3)4Sb-tetrahedron in 1 is distorted by two benzoate oxygon atoms (at 304(2) and 340(2) pin). The cation in 2 is largely undistorted and the anion has a hydrogenphthalate hydrogen bond of d(O...H...O) = 232 pm. The cation-anion contact in 3 is as short as d(Sb-O) = 289 pm rendering the Sb atom pentacoordinate.

Hydrogen Bonds in "Carboxyoximes": the Case of Bomane Derivatives

2000 ◽  
Vol 55 (8) ◽  
pp. 677-684 ◽  
Author(s):  
Maciej Kubicki ◽  
Teresa Borowiak ◽  
Wiesław Z. Antkowiak
Keyword(s):  
Carboxylic Acid ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Carboxylic Acids ◽  
Supramolecular Structures ◽  
X Ray Diffraction ◽  
X Ray ◽  
Carboxylic Groups ◽  
Acid Function

Abstract The tendency of forming mixed carboxyl-to-oxime hydrogen bonds was tested on the series of bornane derivatives: one with the acid function only (bornane-2-endo-carboxylic acid), one with the oxime function (2,2′-diethylthiobomane-3-oxime), and one with both oxime and carboxylic functions (bornane-2-oxime-3-endo-carboxylic acid). The crystal structures of these compounds were determined by means of X-ray diffraction. In bornane-2-endo-carboxylic acid and 2,2′-diethylthiobornane-3-oxime 'homogenic' hydrogen bonds were found, and these hydrogen bonds close eight-and six-membered rings, respectively. By contrast, in bornane-2-oxime-3-endo-carboxylic acid 'heterogenic' hydrogen bonds between carboxylic and oxime bonds were found. This carboxylic-oxime, or 'carboxyoxime' system is almost always present in compounds which have both oxime and carboxylic groups; therefore it can be regarded as an element of supramolecular structures (synthon). The presence of such synthons can break the tendency of carboxylic acids and oximes towards crystallizing in centrosymmetric structures.

Crystal Structures of Seven Terephthaldiamide Derivatives

2002 ◽  
Vol 57 (8) ◽  
pp. 914-921 ◽  
Author(s):  
P. G. Jones ◽  
J. Ossowski ◽  
P. Kus
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Layer Structure ◽  
Inversion Symmetry ◽  
Asymmetric Unit ◽  
X Ray ◽  
Layer Structures ◽  
Structure Determinations ◽  
Independent Molecules

N,N′-Dibutyl-terephthaldiamide (1), N,N′-dihexyl-terephthaldiamide (2), N,N′-di(tert-butyl)- terephthaldiamide (3), N,N,N′,N′-tetrabutyl-terephthaldiamide (4), 1,1′-terephthaloylbis- pyrrolidine (5), 1,1′-terephthaloyl-bis-piperidine (6), and 4,4′-terephthaloyl-bis-morpholine (7) have been synthesised and physicochemically characterised. The X-ray structure determinations reveal imposed inversion symmetry for compounds 1-6; compound 3 has two independent molecules with inversion symmetry in the asymmetric unit. Compounds 1-3 form classical hydrogen bonds of the type N-H···O=C, leading to a ribbon-like arrangement of molecules (1 and 2) or a layer structure (3). Compound 3 also displays a very short C-H···O interaction, a type of hydrogen bond that is also observed in compounds 4-7, which lack classical donors; thereby compounds 4-6 form layer structures and 7 a complex threedimensional network.

Heterocyclic Tautomerism. II. 4-Acylpyrazolones. X-Ray Crystal Structures of 4-Benzoyl-5-methyl-2-phenylpyrazol-3(2H)-one and 4-Acetoacetyl-3-methyl-1-phenylpyrazol-5-ol

1985 ◽  
Vol 38 (3) ◽  
pp. 401 ◽  
Author(s):  
MJ O'Connell ◽  
CG Ramsay ◽  
PJ Steel
Keyword(s):  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Room Temperature ◽  
Crystalline Form ◽  
Intermolecular Hydrogen Bonds ◽  
Intramolecular Hydrogen Bonds ◽  
X Ray ◽  
Intramolecular Hydrogen

The colourless crystalline form of the benzoylpyrazolone (2) has molecules with the NH structure (2c) stabilized by intermolecular hydrogen bonds. At room temperature crystals are monoclinic: P21/c, a 13.508(5), b 9.124(4), c 11.451(3)Ǻ, β 90.80(3)°, Z4; the structure was refined to R 0.059, Rw 0.048. The acetoacetylpyrazolone (3) has the OH structure (3c) with two intramolecular hydrogen bonds. At 193 K crystals are triclinic: Pī , a 7.142(2), b 13.704(8), c 14.699(7)Ǻ, α 117.36(3), β 96.87(3), γ 93.73(3)°, Z 4; the structure was refined to R 0.049, Rw 0.054.

Zur Kenntnis der Sulfite und Sulfithydrate des Zinks, Mangans, Magnesiums und Cobalts — Röntgenographische, spektroskopische und thermoanalytische Untersuchungen / Sulfites and Sulfite Hydrates of Zinc, Manganese, Magnesium and Cobalt-X-ray, Spectroscopic and Thermoanalytical Data

1977 ◽  
Vol 32 (11) ◽  
pp. 1230-1238 ◽  
Author(s):  
Heinz Dieter Lutz ◽  
Saleh M. El-Suradi ◽  
Bernward Engelen
Keyword(s):  
Thermal Analysis ◽  
Hydrogen Bonds ◽  
Ir Spectra ◽  
Single Crystal ◽  
Crystal Structures ◽  
Crystal Data ◽  
X Ray ◽  
Thermoanalytical Data ◽  
O 175 ◽  
Manganese Magnesium

IR, Raman, and X-ray data of ZnSO3 · 2½ H2O, ZnSO3 · 2 H2O, ZnSO3 ·½ H2O, ZnSO3, MnSO3 · 3 H2O, MnSO3 · H2O, MnSO3, MgSO3 · 6 H2O, MgSO3 · 3 H2O, CoSO3 · 3 H2O, CoSO3 · 2½ H2O, and CoSO3·2 H2O are presented. Except of MgSO3·6 H2O and ZnSO3 · 2½ H2O the crystal structures of these compounds are yet unknown. The following crystal data could be determined by single crystal measurements: ZnSO3 · 2 H2O (monoclinic, P21/n) : a = 642.1, b = 852.4, c = 757.4 pm, β = 98.93°, Z = 4, MnSO3 · 3 Η2Ο (monoclinic, Ρ21/n) : a = 665.0, b = 890.6, c = 879.3 pm, ß = 96.11°, Z = 4, MnSO3 · Η2Ο (orthorhombic) : a = 2565.1, b = 483.9, c = 576.0 pm, Z = 8, CoSO3 · 3 Η2Ο (orthorhombic, Pna21, isotype with MgSO3 · 3 H2O): a = 952.7, b = 942.0, c = 552.1 pm, Z = 4, CoSO3• 2½ H2O (tetragonal) : a = b = 946.4, c = 1021.1 pm, Z = 8, CoSO3 · 2 H2O (isotype with ZnSO3 · 2 H2O) : a = 639.7, b = 855.3, c = 753.7 pm, β = 98.85°, Z = 4. The IR spectra show that with exception of MnSO3· H2O strong hydrogen bonds are present in the sulfite hydrates. The decomposition of the sulfites has been examined by thermal analysis. Dehydration of the sulfite hydrates starts at 90 (ZnSO3 · 2½ H2O), 120 (ZnSO3 · 2 H2O), 175 (ZnSO3 · 1/2 H2O), 85 (MnSO3 · 3 H2O), 205 (MnSO3 · H2O), 70 (MgSO3 · 6 H2O), 130 (MgSO3 · 3 H2O), 120 (CoSO3 · 3 H2O), 140 (CoSO3 · 2½ H2O), and 150 °C (CoSO3 · 2 H2O). Decomposition of the anhydrous sulfites occurs at 300-350 (ZnSO3), 390-460 (MnSO3), and 400-530 °C (MgSO3).

Structure and hydrogen bonding in 2,4-dihydroxybenzoic acid at 90, 100, 110 and 150 K; a theoretical and single-crystal X-ray diffraction study

2007 ◽  
Vol 63 (2) ◽  
pp. 303-308 ◽  
Author(s):  
Andrew Parkin ◽  
Martin Adam ◽  
Richard I. Cooper ◽  
Derek S. Middlemiss ◽  
Chick C. Wilson
Keyword(s):  
Hydrogen Bonding ◽  
Solid State ◽  
Hydrogen Bonds ◽  
X Ray Diffraction ◽  
Dihydroxybenzoic Acid ◽  
X Ray ◽  
Hydrogen Bond System ◽  
Proton Disorder ◽  
Intramolecular Hydrogen ◽  
Carboxylic Acid Dimer

A new polymorph of 2,4-dihydroxybenzoic acid is reported. The structure was characterized by multiple-temperature X-ray diffraction and solid-state DFT computations. The material shows a geometric pattern of hydrogen bonding consistent with cooperativity between the intermolecular carboxylic acid dimer and intramolecular hydrogen bonds. The presence of proton disorder within this hydrogen-bond system, which would support such a cooperative model, was not fully ruled out by the initial X-ray studies. However, solid-state calculations on the three possible end-point tautomers indicate that the dominant crystallographically observed configuration is substantially lower in energy than the other tautomers (by at least 9 kJ mol−1), indicating that no disorder should be expected. It is therefore concluded that no disorder is observed either in the intra- or intermolecular hydrogen bonds of the title compound and that the cooperativity between the hydrogen bonds is not present within the temperature range studied.

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