Synthesis, spectral properties, crystal structure and theoretical calculations of a new geminal diamine: 2,2,2-Trichloro-N,N׳-bis(2-nitrophenyl)-ethane-1,1-diamine

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Highlights

  • Synthesis, spectral properties, crystal structure and theoretical calculations of a new geminal diamine: 2,2,2-Trichloro-N, N׳-bis(2-nitrophenyl) ethane-1,1-diamine is reported.

  • X-ray single crystal and molecular structure were determined.

  • Molecular electrostatic potential (MEP) map, the frontier orbitals (FOMs; HOMO and LUMO) analysis, Mulliken's charges distributions and thermodynamic properties were examined by using the B3LYP/6–311G(d,p) approach.

  • The global reactivity properties of title compound were theoretically calculated.

Abstract

A new 2,2,2-trichloro-N,N׳-bis(2-nitrophenyl)-ethane-1,1-diamine was synthesized by the reaction of 2-nitroaniline in DCM with the chloral formed by distillation of chloral hydrate over concentrated H2SO4. The structure of the title compound was identified by means of FT-IR, 1H NMR, and 13C NMR spectroscopic techniques. The crystal structure of the title compound has also been examined by using X-ray crystallographic techniques and found to be crystallized in the monoclinic crystal system and space group P21/n with the unit cell parameters: a = 7.7075(12) Å, b = 7.7396(10) Å, c = 28.247(4) Å, β = 93.602(5)°, V = 1681.7(4) Å3, Dx = 1.602 Mg m  3, and Z = 4 respectively. The calculated electronic structure properties of the title molecule such as HOMO-LUMO analysis, molecular electrostatic potential (MEP) map, and the Mulliken charge distributions were investigated by using the density functional theory (DFT) method. Theoretically calculated values exhibit the chemically hard, high kinetic stable and less reactive molecule.

Introduction

Chloral, known as 2,2,2-trichloroacetaldehyde or 2,2,2-tri-chloroethanal, is an organic compound with the formula Cl3CCHO, which is a colorless oily liquid. Due to the presence of two functional groups such as carbonyl and trichloromethyl and their mutual activating effect, the chloral molecule has been used in a wide variety of syntheses [1]. It is soluble in a wide range of solvents, but it is very unstable in water and reacts with an equivalent of water to form chloral hydrate. Chloral hydrate is a reagent and it is used in industries to prepare organic compounds such as isatin, DDT, etc. [2,3]. In medicine, it used for short-term treatment of insomnia and has anticonvulsant and muscle relaxant properties. It was once used as a sedative and hypnotic substance in pharmaceutical drugs [4], [5], [6], [7].

Compounds known as Schiff bases are usually formed by the condensation reaction of a carbonyl compound such as aldehyde or ketone with a primary amine. Schiff bases, firstly reported by Hugo Schiff in 1864, that contain an azomethine group (-HCdouble bondN-) are also identified as imines (>Cdouble bondNH-) [8]. Schiff bases of aliphatic aldehydes are relatively unstable and readily undergo polymerization, while those of aromatic aldehydes, having a conjugation system, are more stable [9], [10], [11] .

A geminal diamine compound contains two amino groups bound to the same carbon atom. It usually acts as a reactive intermediate product. Therefore, studies on the formation of substituted geminal diamine derivatives are limited [12], [13], [14], [15], [16].

Herein, a new gem‑diamine compound named as 2,2,2-trichloro-N,N׳-bis(2-nitrophenyl)-ethane-1,1-diamine (3) was synthesized from a Schiff base obtained by the reaction of chloral with 2-nitroaniline (Scheme 1) and its structure was characterized by elemental analysis, FT-IR, 1H NMR and 13C NMR spectroscopic techniques and structurally single crystal XRD method. Hydrogen bond geometry of the molecule was determined by the X-ray technique. Additionally, optimized geometrical parameters, molecular electrostatic potential (MEP), Mulliken charges, HOMO-LUMO energy gap and the global reactivity from the frontier orbitals of the title molecule have been performed by using the density functional theory (DFT) B3LYP method with the 6–311G(d,p) basis set. The standard thermodynamic functions: heat capacity (Cp), entropy (S⁰) and enthalpy (ΔH⁰) were calculated to investigate thermodynamical properties of the title compound.

Section snippets

Materials and measurements

All reagents for synthesis were commercially obtained and were used without further purification. The 1H- and 13C NMR spectra were recorded in deuterated chloroform (CDCl3) at 25 °C on a JEOL NMR spectrometer operating at 400 and 100 MHz. Infrared absorption spectra were obtained by a Perkin Elmer BX II spectrometer and reported in cm−1 units. The melting point was measured in an Electro Thermal IA 9100 instrument using a capillary tube. Elemental analysis was conducted on a LECO-932 CHNS

Results and discussion

Synthesis of the title compound (3) is confirmed from the spectroscopic characterization and the X-ray crystal structure of the compound. The structure of the synthesized compound is defined as a geminal diamine. As shown in Scheme 2, we can summarize that the synthesis occurs with the cascade reactions. An imine has formed in the first step of the reaction. In second step of the reaction, 2-nitroaniline has reacted with obtained imine due to the resonance effect of 2-nitropheyl moiety and the

Conclusions

In the present study, a new geminal diamine molecule named as 2,2,2-trichloro-N,N׳-bis(2-nitrophenyl)-ethane-1,1-diamine, (C14H11Cl3N4O4) has been synthesized and structurally characterized by elemental analysis, FT-IR, 1H NMR and 13C NMR spectroscopic techniques. The crystal structure of the compound was determined by the single crystal X-ray diffraction technique. According to the X-ray data, the Csingle bondH…O and Csingle bondH…Cl weak intermolecular interactions have been observed, besides the formation of Nsingle bondH

CRediT authorship contribution statement

Fatma Aydın: Methodology, Conceptualization, Data curation, Writing - original draft, Writing - review & editing. N Burcu Arslan: Formal analysis, Visualization.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work “Synthesis, spectral properties, crystal structure and theoretical calculations of a new geminal diamine: 2,2,2-Trichloro-N, N׳-bis(2-nitrophenyl) ethane-1,1-diamine” reported in this paper.

Acknowledgments

This work was supported by the Scientific Research Coordination Unit of Çanakkale Onsekiz Mart University, [Project No: FYL-2016–672].

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