The structure of compound has also been examined crystallographically. It crystallizes in the monoclinic space group P 21/c. The title compound has been synthesized from the reaction of 4-ethyl-N-((pyridin-2-yl) methylene) benzeneamine with ZnBr2 metal salt. It has been characterized by using elemental analysis, MS, IR and UV-Visible spectroscopic techniques

Mahboobeh Manoochehri

Maryam Daghighi Asli

Seyed Jalal Hoseyni

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Chem Rev Lett 5 (2022) 99-105  Corresponding author. e-mail: dr.Manoochehri@yahoo.com 99   Research Article  Journal of Chemistry Letters journal  ho mepage:  www.chemrevlet t . co m ISSN (online): 2645-4947 (print) 2676-7279  Synthesis and Crystal Structure of Dibromido{[(2-Pyridyl) methyl] (p-ethylphenyl)amine} Zinc Seyed Jalal Hoseynia, Mahboobeh Manoochehria*, Maryam Daghighi Aslia aDepartment of Chemistry, Central Tehran Branch, Islamic Azad University, Tehran, Iran 1. Introduction Owing to their chemical stability, biological functions, suitable photophysical properties, and easy production, researchers have focused on zinc (II) complexes which have diimine ligands [1–3]. Also, such complexes have important bioinorganic chemistry since they are similar to oxygen and nitrogen after they exist as a ligator atom in model or biochemically relevant compounds [4].  The biological potentials of such complexes are impacted by the metal ions and their physiochemical properties are modified as well. For more than 150 years, Schiff’ base ligands have been in chemistry catalogues. One of the leading causes of advancement in chemistry science is the carbon-nitrogen double bond’s chemistry [5]. Medical substrates and fine chemicals are potential applications of Schiff base compounds. Nickel and iron’ multidentate complexes have recently exhibited great activity for ethylene polymerization and oligomerization [6]. As a significant class of organic compounds, Schiff’ bases are considered significant in medicine and pharmaceutics. Therefore, medicinal and organic chemists have turned their attention to the synthesis and development of new derivates of Schiff’ bases [7]. Researchers have tested numerous Schiff’ bases for herbicidal, anti-cancer, anti-fungal and anti-bacterial activities [8]. Researchers first discovered the metal complexes of Schiff’ bases in the 19th century. Within material science and  chemical research, most effort has been put into investigating metal-organic complexes [9, 10]. Having a azomethine functional group, Schiff’ bases are formed when active carbonyl groups and promary amines are condensated and they are a important class of organic compounds. 2. Experimental Details 2.1. Materials        The chemicals that were used were of reagent grade and were utilized after they were received. The method adopted in the literature was used for purifying the solvents which were utilized in the reactions [11]. CHN-O-RAPID analyzer was employed to perform the elemental analysis. On a Bruker Tensor 27spectrophotometer, we recorded the infrared spectra and on a JASCO V-570 spectrophotometer, we recorded the electronic absorption spectra. Based on the ART ICLE  INFO  AB ST R ACT  Article history: Received  Received in revised form  Accepted   Available online  Within this work, the crystallographic investigation of the structure of compound was carried out. The compound was crystallized in the monoclinic space group P 21/c. The compound was then synthesized from the reaction of ZnBr2 metal salt with 4-ethyl-N-((pyridin-2-yl) methylene) benzeneamine. Finally, UV-Vis, IR and MS spectroscopic techniques and elemental analysis were employed for characterizing the compound.  Keywords: ZnBr2 Schiff base monoclinic Zinc (II) Complexes Chem Rev Lett 5 (2022) 99-105 100  procedures [12], we prepared the ligand, 4- ethyl-N-((pyridin-2-yl) methylene) benzeneamine, L [12]. 2.2. [Zn(L)Br2] synthesis While stirring, we added aZnBr2 (22.5 mg, 0.1mmol) aqueous solution to an L acetonitrile solution (1 mmol, 212 mg).  Later, we filtered the solution and let it evaporate gradually in the air, from which we isolated light yellow crystals of 1 suitable for single-crystal X-ray diffraction (XRD) after several days. Found: C, 38.65; H, 3.70; N, 6.43%. ). Anal. Calc. for C14H14Br2N2Zn: C, 38.52; H, 3.46; N, 6.42, %. UV–Vis: (DMSO; log ε): 233 (4.10), 276 (3.85), 292 (3.63(. Yield 65%. IR (KBr; v/cm-1): v(C=N), 1603 Scheme 1. [Zn(L)Br2] synthesis 2.3. X-ray Diffraction Analysis (XRD) As described earlier, for X-ray crystallography, we obtained the suitable crystals of the complexes. Table 1 summarized crystallographic information. By using monochromated Mo Kα radiation, we collected diffraction data for 1 on a Bruker–Nonius Kappa-CCD diffractometer and measured them by employing a ω and Φ scan combination with κ offsets for filling the Ewald sphere. Denzo-SMN software was utilized for processing the data [13]. SORTAV was utilized for carrying out the absorption corrections [14]. SHELXTL V6.1 was used for solving and refining the structure [15] on F2 through full-matrix least-squares. We included all of the H atoms in the computed positions and let them refine in a riding-motion approximation with Uiso tied to the carrier atom. CDS was utilized for depositing the data with the deposition number CCDC 1485923. The above-mentioned data is accessible for free at http://www.ccdc.cam.ac.uk/conts/retrieving.html or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK (fax: +44 1223 336 033; e-mail: deposit@ccdc.cam.ac.uk). 3. Computational Methods Following some previous reports about the organic synthesis of heterocycles [2, 3-f, 16-19], we performed all of the all calculations here using the GAMESS software [20]. The systems’ computations with main group elements were described through the standard basis set 6-311G (d, p) [21-23]. The standard basis set Def2-TZVPPD was utilized for zinc element [20]. Modified Perdew-Wang Exchange and Correlation (MPW1PW91) was utilized in order to perform the geometry optimization [24]. We performed a vibrational analysis at each stationary point to conform that it is an energy minimum. The works reporting an agreement between theoretical and experimental results were also cited along with some useful theoretical papers for the synthesis of these types of projects [25,26].  4. Results and Discussion 4.1. Analysis of X-ray Within this work, Zn(II) iminopirydin complexes were synthesized from the ZnBr2 metal salt reaction in methanol solution with 4-ethyl-N-((pyridin-2-yl) methylene) benzeneamine (L). IR spectrophotometry, UV–Vis, elemental analyses were employed for the characteriziation of the complexes. There were discrete [ZnBr2(C14H15N2)] complex molecules within the structure,in which the metal centre had a tetrahedral coordination geometry. It exhbited considerable Chem Rev Lett 5 (2022) 99-105 101  distortion which was promarily attricbuted to the existence of the 5-membered chelate ring (Figure 1). As provided in Table 2, The endocyclic N1—Zn1—N2 angle (81.31°) (Table 2) was considerably narrower compared to the ideal tetrahedral angle(109.5°). However, the Br1—Zn1—Br2 angle (114.75°) was considerably wider. The calculated bond lengths including the z atom were consistent with the bond lnegths for tetrahedral zinc (II) complexes reported in the literature. The dihedral angle that was formed through the benzene and pyridine was 15.15 (13)°. Only van der waals interactions enforced the crystal structure .Figure 1. The crystal structure ORTEP view demonstrating the atom labeling scheme with thermal ellipsoids enclosing fifty percent of the electronic density  Table 1. Crystal data and refinement details of single-crystal XRD  Complex 1 Empirical formula C14H15Br2N2Zn Formula weight  435.46 Temperature (K) 150(1) K Wavelength(Å) 0.71073 Crystal system Monoclinic Space group P 21/c a(Å) 16.019(3) b (Å) 7.4640(15) Chem Rev Lett 5 (2022) 99-105 102  c (Å) 13.551(3) β (°) 106.806(4) Volume(Å3) 1551.0(5) Z 4 Calculated density (Mg/m3) 1.865 Mg/m3 Absorption coefficient (mm-1) 6.723 mm-1 F(000)  848 Crystal size (mm3) 0.26 x 0.22 x 0.16 Theta range for data collection (°) 2.66 to 27.54  Table 2. The selected bond angles [°] and bond lengths [Å]           4.2. Computational Analysis Figure 1 presents the structure of the synthesized complex. Also, some of the calculated parameters including Zero-point vibration energy, vibrational frequency, X, Y, Z-Cartesian axes, and dipole moment are listed in Table 3. The selected structural parameters of synthesized complex in vacuum are shown in figure 2. According to the theoretical values, we can observe that in gas phase, the bond angle and bond length are shorter rather than the aqueous phase. Evidently, most of the         optimized bond lengths are larger compared to the experimental values to a slight degree [29]. This is because the experimental values are associated with molecules either in solutions or solid states, but our computational values are associated with isolated in the gas phase [30]. Molecular orbital analysis calculations show that the HOMO energy is -0.24503 a.u and that of the LUMO is -0.11686 a.u. Therefore, HOMO-LUMO gap is 3.49 eV. On the other hand, hardness, chemical potential and electrophilicity of this complex are: 1.74, - 4.92, 6.95 eV.Bond length (Å )  Bond Angle (°)  Zn(1)-N(1)  2.045(3) N(1)- Zn (1)-N(2) 81.31(14) Zn (1)-N(2)  2.072(3) N(1)-Zn(1)-Br(1) 110.65(9) Zn(1)-Br(1) 2.3363(8) N(2)-Zn(1)-Br(1) 115.48(10) Zn(1)-Br(2) 2.3632(7) N(1)-Zn(1)-Br(2) 112.84(10) Chem Rev Lett 5 (2022) 99-105 103  Table 3. The selected parameters of the optimized complex  Complex 1  Zero point vibration energy (Joules/Mol)   663214.7 Vibrational frequency (cm-1) X  Y   Z  Dipole moment (Debye)  169.151 0.1905 10.4925 -1.5829 10.6130    Figure 2. The selected structural parameters of the synthesized complex Chem Rev Lett 5 (2022) 99-105 104  4.3. Vibrational analysis Figure 3 presents IR-spectrum of synthesized complex. This experimental spectrum shows peaks in 2933, 1593, 1287, 777 nm. The peak is placed in 2933 attributed to C-H stretching of aromatic. These peaks are placed in 1593 and 1287 attributed to C=N and C=C of complex. The peak is placed in 777 nm attributed to C-H bending of benzene.    Figure 3. The experimental (a) and the theoretical IR spectrum (b) of the studied complex   5. Conclusion  Within this study, we investigated the crystal structure as well as the synthesis of Dibromido{[(2-Pyridyl) methyl] (p-ethylphenyl) amine} Zinc, which was applied to one-pot synthesis from the reaction of the ZnBr2 metal salt with 4-ethyl-N-((pyridin-2-yl) methylene) benzeneamine. UV-Visible spectroscopic techniques, IR, MS, and elemental analysis were used for characterization.  Acknowledgments  We thank the Islamic Azad University, Buinzahra Branch Research Council for supporting this research project. Chem Rev Lett 5 (2022) 99-105 105   References  [1] H. C. Lukaski, Dietary magnesium depletion affects metabolic response during submaximal exercise in postmenopausal women. Am. J. Clin. Nutr., 72 (2000) 585-593. [2] M. Jonsson, S. 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Synthesis and Crystal Structure of Dibromido{[(2-Pyridyl) methyl](p-ethylphenyl)amine}Zinc

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Synthesis and Crystal Structure of Dibromido{[(2-Pyridyl) methyl](p-ethylphenyl)amine}Zinc

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