Crystal Engineering Studies on Ionic Crystals of Pyridine and Carboxylic Acid Derivatives Containing Amide Functional Groups

2010 ◽  
Vol 63 (4) ◽  
pp. 578 ◽  
Author(s):  
Lalit Rajput ◽  
Ramkinkar Santra ◽  
Kumar Biradha
Keyword(s):  
Crystal Engineering ◽  
Intramolecular Hydrogen Bonding ◽  
Supramolecular Synthon ◽  
Pyromellitic Acid ◽  
Trimesic Acid ◽  
Supramolecular Architectures ◽  
Pyridinium Cations ◽  
Intramolecular Hydrogen ◽  
Hydroxy Groups ◽  
Planar Geometries

Seven crystal structures of pyromellitic acid or trimesic acid salts of molecules that contain pyridine and amide functionalities were determined and their structures were analyzed in detail in terms of various intermolecular interactions. The presence of multiple functionalities (acid, pyridine, amide, and hydroxy groups) in these structures resulted in diversified supramolecular architectures. Amide-to-amide hydrogen bonds are not observed in any of these structures because of interference by the anions, water molecules, or pyridinium cations. The symmetry of the components was found to be important in determining the resultant supramolecular synthon and, therefore, the overall architecture. The pyromellitate anions exhibited four types of geometries which, differ in valencies and intramolecular hydrogen bonding, and these anions also exhibit self stacks when they have planar geometries.

1,1-Diphenylbutane-1,3-diol: the First Structurally Characterized Example of an Intramolecularly Hydrogen-Bonded Open-Chain 1,3-diol

1996 ◽  
Vol 49 (11) ◽  
pp. 1251
Author(s):  
CF Carvalho ◽  
DP Arnold ◽  
RC Bott ◽  
G Smith
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Intramolecular Hydrogen Bonding ◽  
Orthorhombic Space Group ◽  
Open Chain ◽  
Space Group ◽  
A Cell ◽  
Intramolecular Hydrogen ◽  
Hydroxy Groups ◽  
Hydrogen Bonded

The crystal structure of the asymmetric 1,3-diol 1,1-diphenylbutane-1,3-diol has been determined and refined to a residual R of 0.039 for 795 observed reflections. Crystals are orthorhombic, space group P212121, with four molecules in a cell of dimensions a 9.625(4), b 16.002(3), c 8.834(3) Ǻ. The compound is unique among the known crystallographically characterized open-chain 1,3-diols in having only intramolecular hydrogen bonding involving the hydroxy groups [O-- -O 2.602(5) Ǻ].

Differential reactivity of carbohydrate hydroxyls in glycosylations. II. The likely role of intramolecular hydrogen bonding on glycosylation reactions. Galactosylation of nucleoside 5′-hydroxyls for the syntheses of novel potential anticancer agents

1994 ◽  
Vol 72 (11) ◽  
pp. 2225-2238 ◽  
Author(s):  
Dennis M. Whitfield ◽  
Stephen P. Douglas ◽  
Ting-Hua Tang ◽  
Imre G. Csizmadia ◽  
Henrianna Y.S. Pang ◽  
...  
Keyword(s):  
Anticancer Agents ◽  
Hydrogen Abstraction ◽  
Intramolecular Hydrogen Bonding ◽  
Nucleophilic Attack ◽  
Side Reactions ◽  
Silver Triflate ◽  
Differential Reactivity ◽  
Intramolecular Hydrogen ◽  
Hydroxy Groups ◽  
First Time

Contrary to expectations, many primary hydroxy groups are completely unreactive in glycosylation reactions, or give the desired glycosides in very low yields accompanied by products of many side reactions. Hydrogens of such primary hydroxyls are shown to be intramolecularly hydrogen bonded. Intermediates formed by nucleophilic attack by these hydroxyls on activated glycosylating agents may resist hydrogen abstraction. This resistance to proton loss is postulated to be the origin of the observed unreactivity. It is shown that successful glycosylations take place under acidic conditions under which such hydrogen bonds cease to exist. Accordingly, direct galactosylations of the normally unreactive 5′-hydroxyls of nucleosides were accomplished for the first time with a galactose trichloroacetimidate donor in chloroform under silver triflate promotion. It is noted that such galactosylated anticancer nucleosides may have improved biological specificity.

catena-Poly[[(2,9-dimethyl-1,10-phenanthroline-κ2 N,N′)lead(II)]-di-μ-2-hydroxybenzoato-κ3 O 1,O 1′:O 2;κ3 O 2:O 1,O 1′]

2007 ◽  
Vol 63 (11) ◽  
pp. m2678-m2678 ◽  
Author(s):  
Xiao-Peng Xuan ◽  
Pei-Zheng Zhao
Keyword(s):  
Hydrogen Bonding ◽  
Crystal Packing ◽  
Rotation Axis ◽  
Intramolecular Hydrogen Bonding ◽  
Polymeric Chain ◽  
Π Interactions ◽  
Intramolecular Hydrogen ◽  
Hydroxy Groups

In the title polymeric comound, [Pb(C7H5O3)2(C14H12N2)] n , the PbII atom is located on a twofold rotation axis and is coordinated by two N atoms from one 2,9-dimethyl-1,10-phenanthroline (dmphen) ligand and six O atoms from four 2-hydroxybenzoate anions. The compound forms a zigzag polymeric chain along the c axis through bridging hydroxy groups of two 2-hydroxybenzoate ligands. The crystal packing is stabilized by the intramolecular hydrogen bonding and π–π interactions between dmphen rings of neighboring molecules, with a distance between the ring planes of 3.385 (3) Å.

Heteroleptic palladium(II) complexes of dipyrrin-1,9-dione supported by intramolecular hydrogen bonding

2020 ◽  
Vol 24 (01n03) ◽  
pp. 112-120 ◽  
Author(s):  
Clayton J. Curtis ◽  
Elisa Tomat
Keyword(s):  
Hydrogen Bonding ◽  
Chemical Characterization ◽  
Intramolecular Hydrogen Bonding ◽  
Palladium Complexes ◽  
Primary Amines ◽  
Redox Active ◽  
Electron Reduction ◽  
Intramolecular Hydrogen ◽  
Planar Geometries

The dipyrrin-1,9-dione framework, which is characteristic of the propentdyopent pigments deriving from heme metabolism, coordinates metal ions as monoanionic bidentate donors. The resulting analogs of dipyrrinato complexes undergo reversible ligand-based reductions, thus showcasing the ability of the dipyrrindione scaffold to act as an electron reservoir. Herein we report the synthesis and characterization of three heteroleptic palladium complexes of the redox-active dipyrrindione ligand. Primary amines were chosen as additional ligands so as to assemble complexes of planar geometries with complementary interligand hydrogen-bonding. Full chemical characterization confirms the hydrogen bonding interactions between the primary amine ligands and the acceptor carbonyl groups on the dipyrrolic ligand. The resulting heteroleptic compounds display reversible one-electron reduction events that are centered on the dipyrrindione ligand as revealed by voltammetry and spectroelectrochemistry data. Within these planar Pd(II) complexes, the propentdyopent motif therefore combines reversible ligand-based redox chemistry with interligand hydrogen bonding in the primary coordination sphere of the metal center.

scholarly journals Multicentered hydrogen bonding in 1-[(1-deoxy-β-D-fructopyranos-1-yl)azaniumyl]cyclopentanecarboxylate (`D-fructose-cycloleucine')

2019 ◽  
Vol 75 (8) ◽  
pp. 1096-1101 ◽  
Author(s):  
Valeri V. Mossine ◽  
Charles L. Barnes ◽  
Thomas P. Mawhinney
Keyword(s):  
Hydrogen Bonding ◽  
Intramolecular Hydrogen Bonding ◽  
Side Chain ◽  
Slow Rotation ◽  
H Nmr ◽  
Compound C ◽  
Nmr Data ◽  
Cyclopentane Ring ◽  
Intramolecular Hydrogen ◽  
Hydroxy Groups

The title compound, C12H21NO7, (I), is conformationally unstable; the predominant form present in its solution is the β-pyranose form (74.3%), followed by the β- and α-furanoses (12.1 and 10.2%, respectively), α-pyranose (3.4%), and traces of the acyclic carbohydrate tautomer. In the crystalline state, the carbohydrate part of (I) adopts the 2 C 5 β-pyranose conformation, and the amino acid portion exists as a zwitterion, with the side chain cyclopentane ring assuming the E 9 envelope conformation. All heteroatoms are involved in hydrogen bonding that forms a system of antiparallel infinite chains of fused R 3 3(6) and R 3 3(8) rings. The molecule features extensive intramolecular hydrogen bonding, which is uniquely multicentered and involves the carboxylate, ammonium and carbohydrate hydroxy groups. In contrast, the contribution of intermolecular O...H/H...O contacts to the Hirshfeld surface is relatively low (38.4%), as compared to structures of other D-fructose-amino acids. The 1H NMR data suggest a slow rotation around the C1—C2 bond in (I), indicating that the intramolecular heteroatom contacts survive in aqueous solution of the molecule as well.

Anisatin: a Crystallographic, N.M.R. and Theoretical Conformation Study

1988 ◽  
Vol 41 (7) ◽  
pp. 1071 ◽  
Author(s):  
MG Wong ◽  
JM Gulbis ◽  
MF Mackay ◽  
DJ Craik ◽  
PR Andrews
Keyword(s):  
Molecular Geometry ◽  
Intramolecular Hydrogen Bonding ◽  
Coupling Constants ◽  
Solution Conformation ◽  
Proton Proton ◽  
X Ray Crystallography ◽  
Yield Information ◽  
Intramolecular Hydrogen ◽  
Experimental Geometry ◽  
Hydroxy Groups

The convulsant compound anisatin has been studied by 1H n.m.r ., and X- ray crystallography, to establish its molecular geometry. The n.m.r . measurements included an analysis of proton-proton vicinal coupling constants and saturation transfer experiments which monitored exchange of the hydroxy groups of anisatin. The former analysis was used to obtain a solution conformation via the Karplus equation while the latter experiments yield information on intramolecular hydrogen bonding. The experimental geometry is compared to that obtained by several theoretical methods, including MINDO/3, MNDO, AM1 and MM2. The AM1 optimized geometry was closest to that of the crystal structure.

Linear aromatic amide foldamer-derived supramolecular architectures and materials

2012 ◽  
Vol 84 (4) ◽  
pp. 965-978 ◽  
Author(s):  
Zhan-Ting Li ◽  
Kang-Da Zhang ◽  
Zhu-Ming Shi ◽  
Lu Wang ◽  
Cen Zhou ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Intramolecular Hydrogen Bonding ◽  
Butyl Methacrylate ◽  
Materials Chemistry ◽  
Acceptor Interaction ◽  
Molecular Tweezers ◽  
Supramolecular Architectures ◽  
Methacrylate Copolymers ◽  
Donor Acceptor ◽  
Intramolecular Hydrogen

Intramolecular hydrogen bonding in oligomeric aromatic amides may induce the backbones to adopt folded, zigzag, or other extended conformations, depending on the positions of the amide units and the hydrogen-bonding sites on the aromatic rings. This article summarizes our efforts in exploring the applications of this family of preorganized oligomers in supramolecular and materials chemistry. Several series of preorganized frameworks or foldamers have been developed as efficient acyclic receptors for binding both neutral and ionic guests. The backbones have been modified with discrete functional groups from the ends or the side chains. The resulting molecules have been applied for designing new molecular tweezers, assembling ordered supramolecular architectures (organogels and vesicles), and directing the formation of complicated macrocyclic and capsular systems. When the hydrogen-bonded folded segments are connected to n-butyl methacrylate copolymers as cross-links, the resulting copolymers display unique reversible mechanical properties owing to the breaking and recovering of the intramolecular hydrogen bonds. When the folded segments are incorporated into the dumbbell components of the donor–acceptor interaction-based pseudo[2]rotaxanes and [2]rotaxanes, they are capable of tuning the slippage/deslippage and switching of the ring component between the discrete “stations” in their dumbbell component.

scholarly journals Crystal structure of a supramolecular lithium complex of p-tert-butylcalix[4]arene

2018 ◽  
Vol 74 (5) ◽  
pp. 575-579 ◽  
Author(s):  
Manabu Yamada ◽  
Muniyappan Rajiv Gandhi ◽  
Kazuhiko Akimoto ◽  
Fumio Hamada
Keyword(s):  
Crystal Structure ◽  
Supramolecular Assembly ◽  
Intramolecular Hydrogen Bonding ◽  
Methanol Molecule ◽  
Cone Conformation ◽  
Oh Groups ◽  
Π Interactions ◽  
Lithium Complex ◽  
Intramolecular Hydrogen ◽  
Hydroxy Groups

Crystals of a supramolecular lithium complex with a calix[4]arene derivative, namely tetramethanollithium 5,11,17,23-tetra-tert-butyl-25,26,27-trihydroxy-28-oxidocalix[4]arene methanol monosolvate, [Li(CH3OH)4](C44H55O4)·CH3OH or [Li(CH3OH)4]+·(calix[4]arene−)]·CH3OH (where calix[4]arene− represents a mono-anion species because of deprotonation of one H atom of the calixarene hydroxy groups), were obtained from p-tert-butylcalix[4]arene reacted with LiH in tetrahydrofuran, followed by recrystallization from methanol. The asymmetric unit comprises one mono-anionic calixarene molecule, one Li+ cation coordinated to four methanol molecules, and one methanol molecule included in the calixarene cavity. The calixarene molecule maintains a cone conformation by intramolecular hydrogen bonding between one phenoxide (–O−) and three pendent calixarene hydroxy groups (–OH). The coordinated methanol molecules around the metal cation play a significant role in forming the supramolecular assembly. The crystal structure of this assembly is stabilized by three sets of intermolecular interactions: (i) hydrogen bonds involving the –OH and –O− moieties of the calixarene molecules, the –OH groups of the coordinated methanol molecules, and the –OH group of the methanol molecule included in the calixarene cavity; (ii) C—H...π interactions between the calixarene molecules and/or the coordinated methanol molecules; (iii) O—H...π interactions between the calixarene molecule and the included methanol molecule.

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