untitled European Journal of Chemistry 8 (2) (2017) 101‐104 European Journal of Chemistry ISSN 2153‐2249 (Print) / ISSN 2153‐2257 (Online)  2017 Atlanta Publishing House LLC ‐ All rights reserved ‐ Printed in the USA http://dx.doi.org/10.5155/eurjchem.8.2.101-104.1544 European Journal of Chemistry Journal webpage: www.eurjchem.com Crystal structure and characterization of new cadmium complex from 4‐pyridin‐carbohydrazide and 2‐chlorobenzaldehyde Saeedeh Hashemian * and Mahbobah Mangeli Department of Chemistry, Islamic Azad University, Yazd Brunch, Yazd, 89195‐155, Iran * Corresponding author at: Department of Chemistry, Islamic Azad University, Yazd Brunch, Yazd, 89195‐155, Iran Tel.: +98.35.31872572. Fax: +98.35.37266065. E‐mail address: sa_hashemian@iauyazd.ac.ir (S. Hashemian). ARTICLE INFORMATION ABSTRACT DOI: 10.5155/eurjchem.8.2.101-104.1544 Received: 15 January 2017 Received in revised form: 27 February 2017 Accepted: 02 March 2017 Published online: 30 June 2017 Printed: 30 June 2017   Reaction of 4‐pyridincarbohydrazide, 2‐chlorobenzaldehyde and Cd(II) ion in ethanol resulted the complex trans‐[Cd(H2O)4(C13H10N3ClO)2](NO3)2. The title complex was characte‐ rized by elemental analyses, UV‐Vis and IR spectroscopy. The structure of complex also was established by single crystal X‐ray diffraction analysis. The [Cd(H2O)4(C13H10N3ClO)2](NO3)2 complex has monomeric structure with monoclinic crystal system and space group of P21/n, a = 7.7720(16) Å, b = 17.594(4) Å, c = 11.823(2) Å, β = 97.29(3)° with Z = 2. The cadmium atom in the crystal structure has octahedral geometry by coordination of the two nitrogen atoms of ligand and four oxygen atoms of water molecules. KEYWORDS Cd complex Trans‐complex Octahedral geometry 2‐Chlorobenzaldehyde Single crystal structure 4‐Pyridin‐carbohydrazide Cite this: Eur. J. Chem. 2017, 8(2), 101‐104 1. Introduction The hydrazone produced from isonicotinic acid hydrazide was initially synthesized in 1954 [1]. Hydrazones derived from condensation of isoniazid with pyridine‐aldehydes and keto‐ nes have shown different medical, physiological and biological activity. There has been growing interest in the study of hydra‐ zones for their physiological activity, coordinative capability, and applications in analytical chemistry [2,3]. Isonicotinyl hydrazine (INH) also known as isoniazid is an organic compound that is the first‐line medication in preven‐ tion and treatment of tuberculosis. Hydrazones are used as intermediates in synthesis, as functional groups in metal carbonyls, in organic compounds [4,5] and in particular in hydrazone Schiff base ligands. It was proved that isoniazid has also has an anti‐depressive effect, one of the first anti depressive drugs discovered. It is also used in a wide range of bacterial diseases [6‐9]. Hydrazones exhibit physiological activities in the treatment of several diseases such as tubercu‐ losis. This activity is attributed to the formation of stable chelate complexes with transition metals, which catalyze physiological processes [10,11]. In context to previous research a number of complexes of transition metals with isonicotinoyl hydrazone ligands were obtained and charac‐ terized [12,13]. The variety complexes such as mononuclear [14], binuclear [15] and tetranuclear [16] with Cd(II) by different ligand were prepared and studied. 2. Experimental 2.1. Instrumentation Melting points were determined on an Electrothermal 9100 apparatus. The elemental analyses (C, H, N) were realized with an elemental combustion system CHN, using a Costech device, type ECS 4010, and the metal contents were determined by atomic absorption spectroscopy. For study of electronic spectra, UV‐Vis spectrophotometer 160 A Shimadzu was used. The IR spectra (4000‐400 cm‐1) were recorded in KBr pellets using a Shimadzu IR‐470 spectrophotometer. Single crystal X‐ray diffraction data for Cd(II) complex of N'‐(2‐ chlorobenzylidene)isonicotino hydrazide was collected at 293(2) K on a STOE‐IPDS II CCD diffractometer using MoKα radiation (λ = 0.71073 Å). The structure was solved by the direct method and refined by full‐matrix least‐squares fitting on F2 by SHELX‐97 [17]. 2.2. Synthesis All chemicals were reagent grade and were used without further purification. 4‐Pyridin‐carbohydrazide, 2‐chlorobenz‐ 102 Hashemian and Mangeli / European Journal of Chemistry 8 (2) (2017) 101‐104 Scheme 1 Figure 1. Chemical structure of N'‐(2‐chlorobenzylidene)isonicotino hydrazide. aldehyde and all of other chemicals were purchased from Merck. Distillated water and ethanol were used as solvents. N'‐(2‐Chlorobenzylidene)isonicotinohydrazide was obta‐ ined by refluxing of an aqueous solution of 1 mmol (0.14 g) of 4‐pyridin‐carbohydrazide and 0.5 mmol of NaOH (5%) and 1 mmol (0.14 g) of 2‐chlorobenzaldehyde (Scheme 1). Ethanol and water (30 mL, 1:3, v:v) was used as solvents. After the completion of the reaction, as indicated by the TLC, the sample was filtered and washed with ethanol and then filter off. The product was purified by crystallization technique to afford the pure product. Title complex was synthesized as the same procedure but 1 mmol (0.24 or 0.30 g) Cd(II) nitrate was added. Single crystal of the title complex was formed. They were subjected to a single crystal X‐ray diffraction study whereby their crystal structure was determined. Color: Light yellow. Yield: 85%. M.p.: 220‐225 °C. FT‐IR (KBr, , cm‐1): 3350‐3054 (NHas, NHsym,), 1670 and 1460 (amide group), 860 (N‐N). Anal. calcd. for C26H28CdCl2N8O12: C, 37.94; H, 3.26; N, 13.43. Found: C, 37.80; H, 3.42; N, 13.50%. UV/Vis (CHCl3, λmax, nm): 232, 275. 3. Results and discussion In the present paper, at single step, the new complex of Cd(II) with 4‐pyridin‐carbohydrazide, 2‐chloro benzaldehyde was synthesized. N'‐(2‐Chlorobenzylidene)isonicotino hydra‐ zide and its Cd complex were characterized by elemental analysis and IR spectroscopy methods. The results of elemental analysis confirmed formation of the title compound. The chemical structure of ligand is shown in Figure 1. The IR spectra for the N'‐(2‐chlorobenzylidene)isonicotino hydrazide ligand and its Cd complex are recorded between 400‐4000 cm‐1. In the IR spectrum of N'‐(2‐chlorobenzylidene) isonicotino hydrazide, the average intensity bands appears at 3350 and 3080 cm‐1, which were assigned to the ν(NHas) and ν(NHsym) vibrations, and bands at 1670 and 1460 cm‐1, which were assigned to amide groups [2]. The average intensity band at 864 cm‐1 is due to the N‐N vibration frequency. In the IR spectra of complex, a very intense band appears in 1383‐1389 cm‐1 range, which is assigned to nitrate anion. The bands in the 3380‐3420 and 1080 cm‐1 domain, from IR spectra of the Cd complex, suggest the existence of coordination of water molecule. The vibration frequencies νN‐H are strongly displaced in complex (3054 cm‐1) suggesting the involvement of the amino nitrogen in coordination with Cd(II) ion. In accordance with this is the fact that the vibration frequency νN‐N is displaced towards lower values as compared with the ligand spectrum in IR spectra of complex [18,19]. The electronic spectrum of ligand and complex were studied. The isoniazid presents in UV two bands at 225 and 260 nm, assigned to transitions of n→π* and π→π*, respectively. The electronic spectra of complex showed that the same bands, displaced at higher wave number 232 and 275 nm, respectively. This suggests the coordination of ligand to the metallic ion. The structure of Cd(II) complex of N'‐(2‐chlorobenzyli dene)isonicotino hydrazide was determined in a single crystal X‐ray diffraction study. Figure 2 shows the labelled structure and Figure 3 shows unit cell‐packing diagram of [Cd(H2O)4 (C13H10N3ClO)2](NO3)2 complex. Details of crystal structure determination are summarized in Table 1, and the bond lengths and angles in Table 2 and hydrogen‐bonding geometry at Table 3. The results show that the cadmium has six‐ coordinated by two pyridine N atoms of two N'‐(2‐chloro benzylidene)isonicotino hydrazide and four coordinated water oxygen atoms. The equatorial plane is formed by oxygen atoms, while the axial positions are occupied by nitrogen atoms. The two hydrazone ligands are in trans configuration. Table 1. Crystallographic data, details of data collection and structure refinement parameters for [Cd(H2O)4 (C13H10N3ClO)2](NO3)2. Empirical formula C26H28CdCl2N8O12 Formula weight 827.87 Temperature/K 120(2) Crystal system Monoclinic Space group P21/n a/Å 7.7720(16) b/Å 17.594(4) c/Å 11.823(2) α/° 90.00 β/° 97.29(3) γ/° 90.00 Volume/Å3 1603.6(6) Z 2 ρcalc g/cm3 1.715 μ/mm‐1 0.923 F(000) 836.0 Crystal size/mm3 0.20 × 0.20 × 0.17 Radiation Mo Kα (λ = 0.71073) 2Θ range for data collection/° 5.78 to 50 Index ranges ‐8 ≤ h ≤ 9 ‐20 ≤ k ≤ 18 ‐14 ≤ l ≤ 14 Reflections collected 7674 Independent reflections 2810 [Rint = 0.0912] Data/restraints/parameters 2810/3/238 Goodness‐of‐fit on F2 0.951 Final R indexes [I≥2σ (I)] R1 = 0.0490, wR2 = 0.0635 Final R indexes [all data] R1 = 0.0926, wR2 = 0.0698 Largest diff. peak/hole / e Å‐3 0.59/‐0.51 Full‐matrix least‐squares on F2 Refinement Hashemian and Mangeli / European Journal of Chemistry 8 (2) (2017) 101‐104 103 Figure 2. The labelled structure of complex [Cd(H2O)4(C13H10N3ClO)2](NO3)2. Figure 3. Unit cell‐packing diagram of [Cd(H2O)4(C13H10N3ClO)2](NO3)2. Table 2. Selected bond lengths and angles for the complex of [Cd(H2O)4(C13H10N3ClO)2](NO3)2. Bond angles, ° BondBond lengths, Å Bond 180.0 O(1)‐Cd(1)‐O(1) 2.281(4) Cd(1)‐O(1) 84.83(13) O(1)‐Cd(1)‐O(2)2.281(4) Cd(1)‐O(1) 95.17(13) O(1) ‐Cd(1)‐O(2) 2.303(3) Cd(1)‐O(2) 95.17(13) O(1)‐Cd(1)‐O(2)2.303(3) Cd(1)‐O(2) 84.83(13) O(1) ‐Cd(1)‐O(2)2.324(4) Cd(1)‐N(1) 180.0 O(2)‐Cd(1)‐O(2 2.324(4) Cd(1)‐N(1) 92.50(14) O(1)‐Cd(1)‐N(1)1.755(5) Cl(1)‐C(9) 87.50(14) O(1)‐Cd(1)‐N(1)0.805(19) O(1)‐H(1A) 87.50(14) O(2)‐Cd(1)‐N(1) 0.76(5) O(1)‐H(1B) 92.09(12) O(2) ‐Cd(1)‐N(1)0.87(5) O(2)‐H(2A) 87.50(14) O(1)‐Cd(1)‐N(1) 0.807(19) O(2)‐H(2B) 92.50(14) O(1)‐Cd(1)‐N(1) 1.218(6) O(3)‐C(6) 92.09(12) O(2)‐Cd(1)‐N(1)1.238(5) O(4)‐N(4) 87.91(12) O(2)‐Cd(1)‐N(1) 1.254(5 O(5)‐N(4) 180.000(1) N(1)‐Cd(1)‐N(1) 1.265(5) O(6)‐N(4) 107(4) Cd(1)‐O(1)‐H(1A) 1.334(6) N(1)‐C(5) 122(4) Cd(1)‐O(1)‐H(1B)1.350(6) N(1)‐C(1) 101(5) H(1A)‐O(1)‐H(1B) 1.356(6) N(2)‐C(6) 135(3) Cd(1)‐O(2)‐H(2A)1.368(5) N(2)‐N(3) 115(3) Cd(1)‐O(2)‐H(2B)0.82(2) N(2)‐H(2C) 109(4) H(2A)‐O(2)‐H(2B) 1.279(6) N(3)‐C(7) 117.3(4) C(5)‐N(1)‐C(1)1.384(7) C(1)‐C(2) Table 3. Hydrogen‐bonding geometry for [Cd(H2O)4(C13H10N3ClO)2](NO3)2. D–HA d(D–H), Å d(HA), Å d(DA), Å (D–HA), ° O(1)‐H(1A)...O(6) 0.805(19) 1.97(2) 2.752(5) 166(5) O(1)‐H(1B)...O(6) 0.76(5) 2.04(5) 2.763(5) 161(5) O(2)‐H(2A)...O(3) 0.87(5) 1.94(5) 2.752(5) 155(4) O(2)‐H(2B)...O(4) 0.807(19) 2.04(2) 2.835(5) 168(5) N(2)‐H(2C)...O(5) 0.82(2) 2.23(3) 2.999(5) 156(5) C(1)‐H(1)...O(3) 0.95 2.39 3.341(6) 156(5) C(2)‐H(2)...O(5) 0.95 2.47 3.386(6) 161.2 C(7)‐H(7)...O(5) 0.95 2.44 3.275(6) 147.2 104 Hashemian and Mangeli / European Journal of Chemistry 8 (2) (2017) 101‐104 4. Conclusion The Cd(II) complex of N'‐(2‐chlorobenzylidene)isonicotino hydrazide was prepared and characterized by elemental analysis, IR, UV‐Vis and single crystal X‐ray diffraction analysis. Cd(II) coordinated with two of N'‐(2‐chlorobenzyli dene)isonicotino hydrazide ligand and four aqua molecules. Results showed the prepared complex had octahedral geometry, monoclinic and space group P21/n. 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