Unexpected Structural Diversity in Alkali Metal Azide-Crown Ether Complexes: Syntheses, X-ray Structures, and Quantum-Chemical Calculations

2006 ◽  
Vol 12 (9) ◽  
pp. 2620-2629 ◽  
Author(s):  
Michael D. Brown ◽  
John M. Dyke ◽  
Francesco Ferrante ◽  
William Levason ◽  
J. Steven Ogden ◽  
...  
Keyword(s):  
Crown Ether ◽  
Alkali Metal ◽  
Quantum Chemical Calculations ◽  
Quantum Chemical ◽  
Structural Diversity ◽  
X Ray ◽  
Metal Azide ◽  
Crown Ether Complexes

Crown ether complexes exhibiting unusual 1:2 macrocycle salt ratios: X-ray crystal structures of cyclohexano-15-crown-5•2LiOPh, cyclohexano-15-crown-5•2NaOPh, and 15-crown-5•2NaOPh

1991 ◽  
Vol 69 (4) ◽  
pp. 687-695 ◽  
Author(s):  
Kimberly A. Watson ◽  
Suzanne Fortier ◽  
Michael P. Murchie ◽  
John W. Bovenkamp
Keyword(s):  
Crown Ether ◽  
Alkali Metal ◽  
Crystal Structures ◽  
Direct Methods ◽  
The Other ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
Host Guest Complex ◽  
Crown Ether Complexes

The crystal structures of three crown ether complexes (cyclohexano-15•crown-5•2LiOPh (1): Li2O7C26H36, Mr = 474.45, λ(CuKα)filt. = 1.5418 Å; cyclohexano-15-crown-5•2NaOPh (2): Na2O7C26H36, Mr = 504.54, λ(CuKα)filt. = 1.5418 Å; and 15-crown-5•2NaOPh (3): Na2O7C22H30, Mr = 452.46, λ(CuKα)mono. = 1.5418 Å) have been determined by X-ray diffraction at room temperature (T = 298 K). Complex 1 crystallizes in space group P21/n with a = 15.032(5), b = 13.332(2), c = 13.533(3) Å, β = 106.28(2)°, V = 2603.2 Å3, and Z = 4. Complex 2 crystallizes in space group P21/n with a = 15.94(1), b = 12.194(7), c = 14.068(7) Å, β = 102.84(5)°, V = 2666.3 Å3, and Z = 4. Complex 3 crystallizes in space group P21/c with a = 12.451(3), b = 17.263(3), c = 12.659(6) Å, β = 115.74(3)°, V = 2450.8 Å3, and Z = 4. The three structures were solved by direct methods and refined by full-matrix least-squares calculations to residuals, R, of 0.080, 0.069, and 0.081 for complexes 1, 2, and 3, respectively. In each structure the macrocycle forms a 1:2 host–guest complex with the alkali metal. Each structure exhibits a dimer of the general form (MAC•2MOPh)2 where M = Li+ and Na+ for structures 1 and 2, respectively, and MAC = cyclohexano-15-crown-5, while M = Na+ and MAC = 15-crown-5 for structure 3. In each case the two metals of the monomeric unit have different crystallographic and chemical environments. In structures 1 and 3 one alkali metal is coordinated to all five oxygens of the macrocycle and to one of the phenoxide oxygens, while the other alkali metal is coordinated to only one oxygen of the macrocycle and to three phenoxide oxygens. In structure 2, one alkali metal is coordinated to only four of the five oxygens of the macrocycle and to two of the phenoxide oxygens, while the other alkali metal is coordinated to only one oxygen of the macrocycle and to three phenoxide oxygens (as in 1 and 3). Key words: crown ether, host–guest complexes, X-ray crystallography.

scholarly journals Synthesis of Bis(Carboranyl)amides 1,1′-μ-(CH2NH(O)C(CH2)n-1,2-C2B10H11)2 (n = 0, 1) and Attempt of Synthesis of Gadolinium Bis(Dicarbollide)

Molecules ◽  
2021 ◽  
Vol 26 (5) ◽  
pp. 1321
Author(s):  
Yasunobu Asawa ◽  
Aleksandra V. Arsent’eva ◽  
Sergey A. Anufriev ◽  
Alexei A. Anisimov ◽  
Kyrill Yu. Suponitsky ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Single Crystal ◽  
Quantum Chemical Calculations ◽  
Quantum Chemical ◽  
X Ray Diffraction ◽  
Stable Conformation ◽  
Acyl Chlorides ◽  
X Ray ◽  
Cesium Fluoride ◽  
The Stability

Bis(carboranyl)amides 1,1′-μ-(CH2NH(O)C(CH2)n-1,2-C2B10H11)2 (n = 0, 1) were prepared by the reactions of the corresponding carboranyl acyl chlorides with ethylenediamine. Crystal molecular structure of 1,1′-μ-(CH2NH(O)C-1,2-C2B10H11)2 was determined by single crystal X-ray diffraction. Treatment of bis(carboranyl)amides 1,1′-μ-(CH2NH(O)C(CH2)n-1,2-C2B10H11)2 with ammonium or cesium fluoride results in partial deboronation of the ortho-carborane cages to the nido-carborane ones with formation of [7,7′(8′)-μ-(CH2NH(O)C(CH2)n-7,8-C2B9H11)2]2−. The attempted reaction of [7,7′(8′)-μ-(CH2NH(O)CCH2-7,8-C2B9H11)2]2− with GdCl3 in 1,2-dimethoxy- ethane did not give the expected metallacarborane. The stability of different conformations of Gd-containing metallacarboranes has been estimated by quantum-chemical calculations using [3,3-μ-DME-3,3′-Gd(1,2-C2B9H11)2]− as a model. It was found that in the most stable conformation the CH groups of the dicarbollide ligands are in anti,anti-orientation with respect to the DME ligand, while any rotation of the dicarbollide ligand reduces the stability of the system. This makes it possible to rationalize the design of carborane ligands for the synthesis of gadolinium metallacarboranes on their base.

Electrochemical aromatization of dihydroazines. Effect of chalcogenophosphoryl (CGP) substituents on anodic oxidation of 9-CGP-9,10-dihydroacridines

Synthesis ◽  
2021 ◽  
Author(s):  
Alexander Schepochkin ◽  
Oleg N. Chupakhin ◽  
Nadezhda Demina ◽  
Maxim Averkov ◽  
Tatyana Shimanovskaya ◽  
...  
Keyword(s):  
Cyclic Voltammetry ◽  
Structural Analysis ◽  
Quantum Chemical Calculations ◽  
Anodic Oxidation ◽  
Quantum Chemical ◽  
X Ray

The effect of chalcogenophosphoryl fragments on the anodic oxidation of 9-chalcogenophosphoryl-9,10-dihydroacridines was studied in detail. The data of X-ray structural analysis, quantum chemical calculations and cyclic voltammetry obtained for these compounds provide an explanation of the observed features. The direct electrochemical phosphorylation of acridine was first carried out successfully.

Emergence of Symmetry and Chirality in Crown Ether Complexes with Alkali Metal Cations

2010 ◽  
Vol 114 (26) ◽  
pp. 7048-7054 ◽  
Author(s):  
Bruno Martínez-Haya ◽  
Paola Hurtado ◽  
Ana R. Hortal ◽  
Said Hamad ◽  
Jeffrey D. Steill ◽  
...  
Keyword(s):  
Crown Ether ◽  
Alkali Metal ◽  
Metal Cations ◽  
Alkali Metal Cations ◽  
Crown Ether Complexes

Structure and Reactivity of [Mo3-μ3S-(μS2)3]4+Complexes. Quantum Chemical Calculations, X-ray Structural Characterization, and Raman Spectroscopic Measurements

1998 ◽  
Vol 37 (11) ◽  
pp. 2633-2644 ◽  
Author(s):  
María J. Mayor-López ◽  
Jacques Weber ◽  
Kaspar Hegetschweiler ◽  
Marc D. Meienberger ◽  
Felix Joho ◽  
...  
Keyword(s):  
Quantum Chemical Calculations ◽  
Structural Characterization ◽  
Quantum Chemical ◽  
Spectroscopic Measurements ◽  
X Ray ◽  
Raman Spectroscopic

Evaluation of Aspects Controlling Crystallization of Nitrofurantoin

2019 ◽  
Vol 800 ◽  
pp. 9-13
Author(s):  
Aija Trimdale ◽  
Agris Bērziņš
Keyword(s):  
Gibbs Energy ◽  
Quantum Chemical Calculations ◽  
Organic Solvents ◽  
Quantum Chemical ◽  
Polymer Additives ◽  
Factors Affecting ◽  
X Ray

Nitrofurantoin was crystallized from multiple mixtures of water and organic solvents with and without additives to try to find and identify factors affecting phase obtained in crystallization and provide possible information on crystallization control. Obtained crystals were identified with powder X-ray diffractometry. Crystallization control possibilities were evaluated by using polymer additives and crystallization additives, by also using quantum chemical calculations to investigate the association of nitrofurantoin and additive molecules and calculate Gibbs energy of association.

The synergy of different solid-state techniques to elucidate the supramolecular assembly of two 1H-benzotriazole polymorphs

2019 ◽  
Vol 21 (36) ◽  
pp. 19879-19889
Author(s):  
María Mar Quesada-Moreno ◽  
Juan Ramón Avilés-Moreno ◽  
Juan Jesús López-González ◽  
Fco. Javier Zúñiga ◽  
Dolores Santa María ◽  
...  
Keyword(s):  
Solid State ◽  
Quantum Chemical Calculations ◽  
Absolute Configuration ◽  
Quantum Chemical ◽  
Supramolecular Structure ◽  
Supramolecular Assembly ◽  
X Ray ◽  
X Ray Crystallography ◽  
The Absolute

4aα (chiral) and 4aβ (achiral) polymorphs of 1H-benzotriazole are studied by X-ray crystallography, SSNMR, IR, Raman, VCD, and quantum chemical calculations. The absolute configuration of the supramolecular structure of 4aα polymorph is determined.

Sign in / Sign up

Export Citation Format

Share Document