Synthesis and structure of 9-(di-methyl-amino)-1,10-phenanthrolin-1-ium nitrate
Batirbay Torambetov1, Mukhammedaliy Allaniyazov1, Jamshid Ashurov2
1National University of Uzbekistan named after Mirzo Ulugbek 4 University St Tashkent 100174 Uzbekistan.
Summary
This study details the crystal structure of a nitrate salt, revealing a planar cation with conjugated aromatic systems. Hydrogen bonds and pi-stacking interactions stabilize the structure, with H-H and H-O bonds being key contributors.
Area of Science:
- Crystallography
- Supramolecular Chemistry
- Materials Science
Background:
- Understanding the crystal packing of organic salts is crucial for predicting their physical properties.
- The interplay of non-covalent interactions dictates the stability and arrangement of molecules in the solid state.
Purpose of the Study:
- To elucidate the crystal structure and intermolecular interactions of a specific nitrate salt (C14H14N3+·NO3-).
- To analyze the contribution of various interactions, including hydrogen bonding and pi-stacking, to the overall crystal packing.
Main Methods:
- Single-crystal X-ray diffraction was employed to determine the three-dimensional structure.
- Hirshfeld surface analysis was utilized to quantify the contributions of different intermolecular interactions.
Main Results:
- The cation exhibits near planarity, indicating significant conjugation within the aromatic system.
- N-H···O and C-H···O hydrogen bonds form infinite chains along the b-axis.
- Aromatic π-π stacking interactions (3.5773(12) and 3.5889(12) Å) contribute to crystal consolidation.
- Hirshfeld analysis highlights H···H (39.2%) and H···O/O···H (31.6%) as dominant interactions.
Conclusions:
- The crystal structure is stabilized by a combination of hydrogen bonding and π-π stacking interactions.
- Hirshfeld surface analysis provides quantitative insights into the hierarchy of intermolecular forces governing crystal packing.
- The findings contribute to the understanding of structure-property relationships in organic nitrate salts.
Related Concept Videos
01:371° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism
Nitrous acid is a relatively weak and unstable acid prepared in situ by the reaction of sodium nitrite and cold, dilute hydrochloric acid. In an acidic solution, the nitrous acid undergoes protonation when it loses water to form a nitrosonium ion—an electrophile. Nitrous acid reacts with primary amines to give diazonium salts. The reaction is called diazotization of primary amines.
01:19Structure of Amines
The hybridized nitrogen atom in amines possesses a lone pair of electrons and is bound to three substituents with a bond angle of around 108°, which is less than the tetrahedral angle of 109.5°. However, the C–N–H bond angle is slightly larger at 112°, with a carbon–nitrogen bond length of 147 pm. This carbon–nitrogen bond length of of amines is longer than the carbon–oxygen bond of alcohols (143 pm) but shorter than alkanes’ carbon–carbon bond (154 pm). These aspects are illustrated in Figure...
01:261° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Overview
Nitrous acid and nitric acids are two types of acids containing nitrogen, among which nitrous acid is weaker than nitric acid. Nitrous acid with a pKa value of 3.37 ionizes in water to give a nitrite ion and the hydronium ion.
The nitrous acid is unstable. Hence, it is formed in situ from a solution of sodium nitrite and cold aqueous acids such as hydrochloric or sulfuric acid. In an acidic solution, the –OH group of nitrous acid undergoes protonation to give oxonium ion, followed by water loss...
The nitrous acid is unstable. Hence, it is formed in situ from a solution of sodium nitrite and cold aqueous acids such as hydrochloric or sulfuric acid. In an acidic solution, the –OH group of nitrous acid undergoes protonation to give oxonium ion, followed by water loss...
01:10Nomenclature of Aryl and Heterocyclic Amines
The simplest aromatic amine is phenylamine, which contains an –NH2 functionality directly attached to an aromatic ring. The name aniline is designated for this skeleton. As shown in Figure 1, the common names of the functionalized anilines involve prefixes ortho-, meta-, and para- to indicate the substitution position. Different functionalized aniline derivatives also have notable trivial names.
01:202° Amines to N-Nitrosamines: Reaction with NaNO2
Secondary amines react with nitrous acid to form N-nitrosamines, as depicted in Figure 1. Nitrous acid, a weak and unstable acid, is formed in situ from an aqueous solution of sodium nitrite and strong acids, such as hydrochloric acid or sulfuric acid, in cold conditions. In the presence of an acid, the nitrous acid gets protonated. The subsequent loss of water results in the formation of the electrophile known as nitrosonium ion.
01:12Preparation of Nitriles
One of the common methods to prepare nitriles is the dehydration of amides. This method requires strong dehydrating agents like phosphorous pentoxide or boiling acetic anhydride for converting amides to nitriles. Another reagent namely, thionyl chloride also accomplishes the dehydration of amides, where amide acts as a nucleophile. The first step of the mechanism involves the nucleophilic attack by the amide on the thionyl chloride to form an intermediate. In the next step, the electron pairs...