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.

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.

Inhibitors of the geotropic response in plants. The crystal structures of 2-[(Naphthalen-2-yl)carbamoyl]benzoic acid (β-Naptalam), 2-(Phenylcarbamoyl)-benzoic acid and 2-(5-Phenyl-1,3,4-oxadiazol-2-yl)benzoic acid

1983 ◽  
Vol 36 (12) ◽  
pp. 2455 ◽  
Author(s):  
G Smith ◽  
CHL Kennard ◽  
GF Katekar
Keyword(s):  
Hydrogen Bonding ◽  
Carboxylic Acid ◽  
Benzoic Acid ◽  
Crystal Structures ◽  
Carboxylic Acids ◽  
Intermolecular Hydrogen Bonding ◽  
X Ray Diffraction ◽  
X Ray ◽  
Carboxylic Acid Groups ◽  
Phthalamic Acid

The crystal structures of three geotropically active phthalamic acid derivatives have been determined by means of X-ray diffraction and the structural systematics for the series compared. The three acids are conformationally similar and, in contrast to the tendency among carboxylic acids to form hydrogen-bonded dimers, they exist as monomers with intermolecular hydrogen bonding between the carboxylic acid groups and the nitrogen or oxygen of the amide side chains.

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. 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].

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.

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.

Formamidinium Salts of Low Valent Metal Halide Anions MX3 – (M = Ge, Sn) and M2X62– (M = Ga, In)

2004 ◽  
Vol 59 (11-12) ◽  
pp. 1524-1531 ◽  
Author(s):  
Xin Tian ◽  
Tania Pape ◽  
Norbert W. Mitzel
Keyword(s):  
Hydrogen Bonds ◽  
Single Crystal ◽  
Crystal Structures ◽  
Raman Spectra ◽  
X Ray Diffraction ◽  
X Ray ◽  
Bond Lengths ◽  
Metal Metal ◽  
Weak Hydrogen Bonds ◽  
Low Valent

Tetramethylformamidinium trichlorogermanite, [CH(NMe2)2][GeCl3], tetramethylformamidinium trichlorostannite, [CH(NMe2)2][SnCl3], bis-(tetramethylformamidinium hexaiododigallate, [CH(NMe2)2]2[Ga2I6] and bis-(tetramethylformamidinium hexachlorodiindate, [CH(NMe2)2]2[In2Cl6] have been prepared by the reactions between tetramethylformamidinium chloride, [CH(NMe2)2]Cl, and the corresponding low valent halides GeCl2 (as dioxane adduct), SnCl2, “GaI” and InCl. Their crystal structures have been determined by single crystal X-ray diffraction. [CH(NMe2)2][GeCl3] aggregates in a centrosymmetric dimeric structure, in which two trigonal pyramidal GeCl3 units are connected together by two weak Ge···Cl bonds and each Ge atom is bonded to one cation by a weak Ge···N contact. Two sets of weak hydrogen bonds C-H···Cl are observed with bond lengths of 2.87(2) Å and 2.85(2) Å . In [CH(NMe2)2][SnCl3], the SnCl3 − units adopts a (3+3) coordination with three normal Sn-Cl bonds and three weak Sn···Cl contacts. [CH(NMe2)2]2[Ga2I6] and [CH(NMe2)2]2[In2Cl6] contain metal-metal bonded anions with distorted staggered ethane-like conformations. The metal-metal bond lengths are 2.423(1) Å (Ga-Ga) and 2.719(1) Å (In-In). Their Raman spectra contain intense bands at 118.7 cm−1(Ga-Ga) and 174.7 cm−1(In-In) associated with metal-metal stretching modes.

Characterization of Carboxylic Acids: Identification of Their Anilide Derivatives by X-ray Diffractometry

1976 ◽  
Vol 30 (2) ◽  
pp. 204-209 ◽  
Author(s):  
Kenneth J. Garska
Keyword(s):  
Mass Spectrometry ◽  
Carboxylic Acid ◽  
Qualitative Analysis ◽  
Carboxylic Acids ◽  
Isomeric Form ◽  
X Ray Diffraction ◽  
X Ray ◽  
Diffraction Patterns ◽  
Derivatives Of

In order to extend the data available for the characterization of carboxylic acids, an x-ray diffraction technique has been used for the identification of their anilide derivatives. This technique often makes possible the identification of carboxylic acids that cannot be examined readily by other techniques such as gas chromotography and mass spectrometry. Reference x-ray diffraction patterns have been obtained for the anilide derivatives of 32 carboxylic acids containing up to 18 carbon atoms. Detailed descriptions are given for obtaining and qualitatively using the x-ray diffraction patterns of these anilides. The x-ray diffraction patterns of these anilides are unique; even closely related acids which differ only in isomeric form produce anilide derivatives which exhibit different and characteristic x-ray diffraction patterns. In the qualitative analysis of single or multicomponent carboxylic acid-containing mixtures, this x-ray diffraction technique is used either alone or with infrared spectrometric techniques.

Molekülstrukturen, Schwingungsspektren und Konformation der Thiooxalsäurederivate CH3S-CO-CONH2, CH3S-CS-CONH2, C2H5O-CO-CSNH2 und K[OSC-CONH2] / Molecular Structure, Vibrational Spectra and Conformation of the Thiooxalic Acid Derivatives CH3S-CO-CONH2, CH3S-CS-CONH2, C2H5O-CO-CSNH2 and K[OSC-CONH2]

1983 ◽  
Vol 38 (3) ◽  
pp. 335-340 ◽  
Author(s):  
Rainer Mattes ◽  
Franz Waldmann
Keyword(s):  
Molecular Structure ◽  
Hydrogen Bonds ◽  
Single Crystal ◽  
Crystal Structures ◽  
Sulfur Atom ◽  
Vibrational Spectra ◽  
Torsional Angle ◽  
X Ray Diffraction ◽  
X Ray ◽  
Centrosymmetric Dimers

Abstract The crystal structures of CH3S-CO-CONH2 (1), CH3S-CS-CONH2 (2), C2H5O-CO-CSNH2 (3) and K[OSC-CONH2] (4) have been determined by single crystal X-ray diffraction. The molecules 1, 2 and 3 are nearly planar and form centrosymmetric dimers by N H···O or N-H···S hydrogen bonds with the amidic oxygen or sulfur atom as acceptor atoms. The anion of 4 is not quite planar. The torsional angle around the C-C bond is 18.4°. The conformations of the title compounds are E, Z' (1 and 2), Z, Z' (3) and Z (4). According to the vibrational spectra, which are discussed briefly, 1 and 3 retain their conformation also in solution.

Fluoride und Fluorosäuren, IX [1]. Verbindungsbildung im System NOF–HF sowie Kristallstrukturen von NOF·3 HF und NOF·4 HF / Fluorides and Fluoro Acids, IX [1]. Compound Formation in the System NOF–HF and Crystal Structures of NOF·3HF and NOF·4HF

1984 ◽  
Vol 39 (10) ◽  
pp. 1300-1305 ◽  
Author(s):  
Dietrich Mootz ◽  
Wolfgang Poll
Keyword(s):  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Melting Diagram ◽  
X Ray Diffraction ◽  
Melting Points ◽  
Orientational Disorder ◽  
Rich Region ◽  
Compound Formation ◽  
X Ray ◽  
Solid Phases

The melting diagram of the system NOF-HF (HF-rich region) was studied by DTA and X-ray diffraction. The compounds NOF·3HF and NOF·4HF were confirmed as intermediate solid phases, and formation of a new one, NOF·7HF , was observed. The melting points are -1 °C (dec.), 5 °C and -106 °C (dec.), respectively. The crystal structures of NOF·3HF (space group R3c ,Z = 6 , a = 7.396 Å , c = 12.678 Å) and NOF·4HF (141/a, Z = 4, a = 6.316 Å , c = 13.301 Å) were determined as those of nitrosonium hydrogen fluorides, NO[F(HF)3] and NO[F(HF)4], with orientational disorder of the cations and very strong F-H···F hydrogen bonds in the anions.

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