untitled European Journal of Chemistry 5 (3) (2014) 394‐396 European Journal of Chemistry ISSN 2153‐2249 (Print) / ISSN 2153‐2257 (Online)  2014 Eurjchem Publishing ‐ Printed in the USA http://dx.doi.org/10.5155/eurjchem.5.3.394‐396.1043 European Journal of Chemistry Journal homepage: www.eurjchem.com Synthesis, characterization and crystal structure of N'‐[(E)‐furan‐2‐ylmethylidene]furan‐2‐carbohydrazide Riya Datta a,*, Ramya Vittalacharya a and Bubbly Shivappa Gudennavar b a Department of Chemistry, Christ University, Bangalore‐560029, India b Department of Physics, Christ University, Bangalore‐560029, India *Corresponding author at: Department of Chemistry, Christ University, Bangalore‐560029, India. Tel.: +91.080.40129313. Fax: +91.080.40129000. E‐mail address: riya.datta@christuniversity.in (R. Datta). ARTICLE INFORMATION ABSTRACT DOI: 10.5155/eurjchem.5.3.394‐396.1043 Received: 06 March 2014 Received in revised form: 07 March 2014 Accepted: 07 March 2014 Online: 30 September 2014 KEYWORDS A new compound, N'‐[(E)‐furan‐2‐ylmethylidene]furan‐2‐carbohydrazide was synthesized. Elemental analysis, IR spectrum, 1H NMR and X‐ray crystal structure studies were carried out to determine the compositions and molecular structure of the compound. It crystallizes in the orthorhombic space group Pbca with unit cell parameters a = 11.3142(4) Å, b = 7.5526(2) Å and c = 22.9030(9) Å. The crystal structure studies reveal intermolecular N‐H···O hydrogen bonding interactions in the solid state. IR NMR Furfural Crystal structure Acylhydrazone p‐Chlorobenzhydrazide 1. Introduction Acyl hydrazones have stimulated lot of interest as anti‐ inflammatory agents, antimalarial agents and as antimicrobials due to their diverse pharmacological properties [1‐7]. These compounds are undoubtedly versatile ligands for complexation to transition metals [8,9]. Availability of various substituents encourages synthesizing and characterizing new hydrazones. Structure of the compound is of great importance when structure‐activity related studies (SAR) are undertaken. Due to the crystalline nature of majority of acyl hydrazones, their crystal structures are widely studied [10‐12]. In this manuscript, we have discussed a simple procedure to synthesize the title compound and characterized it by elemental analysis, various spectroscopic methods and single crystal X‐ray diffraction. 2. Experimental 2.1. Instrumentation All chemicals used in our present study were of analytical grade and procured from Sigma‐Aldrich and used without any further purification. TLC was run on silica (60 F254 coated aluminum sheets) using ethyl acetate:petroleum ether (1:1, v:v) as mobile phase and visualized in UV light. IR spectrum was recorded using FT‐ IR Perkin Elmer spectrometer. 1H NMR spectrum was obtained using Bruker NMR instrument 400MHz at room temperature. Elemental analysis was done using Elementar Vario EL III system. Needle shaped, colorless single crystals of the title compound, suitable for X‐ray analysis were obtained by slow evaporation at room temperature. X‐ray intensity data were collected at 25 C up to a 2max of 25  on a Bruker Kappa APEX2 detector with graphite monochromatic Mo‐K radiation (0.71070 Å). The intensities were corrected for Lorentz, polarization and absorption effects. The structure was solved by direct methods and refined by full matrix least‐squares method using SHELX‐97 [13]. All non‐hydrogen atoms were refined anisotropically and the hydrogen atoms isotropically. The hydrogen atom bonded to nitrogen atom was located in a difference map and refined freely. The remaining hydrogen atoms were positioned geometrically (C‐H=0.93 Å) and refined using a riding model, with Uiso(H)=1.2 Ueq (C). The refinement was continued until the maximum shift/e.s.d was zero. The crystal data and structure refinement details are given in Table 1. Datta et al. / European Journal of Chemistry 5 (3) (2014) 394‐396 395 Figure 1. ORTEP view of the molecular structure with 50% probability ellipsoids. Scheme 1 Table 1. Crystal data and structure refinement details of the title compound. Empirical formula C10H8N2O3 Formula weight 204.18 Crystal system Orthorhombic Space group Pbca Unit cell dimensions a = 11.3142(4) Å b = 7.5526(2) Å c = 22.9030(9) Å Volume 1957.10(12) Å3 Z Calculated density 8 1.386 g/cm3 F(000) 848 Crystal size 0.35 × 0.20 × 0.15 mm Absorption coefficient 0.105 mm‐1 No. of observations ( I > 2 (I)) 1646 Absorption correction Psi‐scan Max. and min. transmission 0.964 and 0.984 Refinement method Full‐matrix least‐squares on F2 Goodness‐of‐fit indicator 1.049 Index ranges ‐12 h 13 ‐6 k 8 ‐27 l 13  range for data collection 2.53 to 25.00  R ( I > 2 (I)) 0.0411 Rw ( I > 2 (I) ) 0.1091 Largest diff. peak and hole 0.223 and ‐0.185 e.Å‐3 CCDC no. 953906 2.2. Synthesis Synthesis procedure for the title compound is depicted in Scheme 1. Furfuraldehye (0.8 mL, 10 mmol) and furoic hydrazide (1.2 g, 10 mmol) were refluxed in methanol for three hours. TLC was checked for completion of the reaction. Upon evaporation of the solvent, product crystallized out. Single crystals suitable for X‐ray diffraction were obtained by recrystallization from methanol solution. N'‐[(E)‐furan‐2‐ylmethylidene]furan‐2‐carbohydrazide : Color: White. Yield: 78%. M.p.: 164‐167 oC. FT‐IR (KBr, ν, cm‐1): 3191 (m, NH), 1641 (s, C=O), 1618 (s, C=N), 1089 (s, C‐O). 1H NMR (400 MHz, DMSO‐d6, δ, ppm): 11.77 (s, 1H, NH, D2O exchangeable), 8.33 (s, 1H, CH=N), 7.92 (s, 1H, Ar‐H), 7.83 (d, 1H, J = 1.6 MHz, Ar‐H), 7.26 (s, 1H, Ar‐H), 6.91 (d, 1H, J = 3.2 MHz, Ar‐H), 6.69 (dd,1H, J = 1.6, 3.2 MHz, Ar‐H), 6.62 (dd, 1H, J = 1.6, 3.2 MHz, Ar‐H). Anal. calcd. for C10H8N2O3; C, 58.82; H, 3.95; N, 13.72. Found: C, 59.12; H, 4.10; N, 13.98%. 3. Results and discussion The IR spectrum of the title compound showed two strong bands at 1652 and 1604 cm‐1, which hints the presence of amide C=O and C=N, respectively. A medium intensity band at 3278 and 3227 cm‐1 confirm the presence of NH group. Strong band at 1100 cm‐1 was assigned to C=O stretch. These characteristic IR bands of acyl hydrazones confirmed formation of the product. However 1H NMR data of the compound further helped in elucidation of the structure. The 1H NMR spectrum of the compound exhibited resonance peak of NH group at 11.1 ppm, as a singlet and the assignment was confirmed by D2O exchange. A singlet for azomethine proton (CH=N) appeared at 8.5 ppm, whereas peaks for furyl protons showed between 8‐6 ppm. Chemical shifts, splitting patterns and coupling constants matched perfectly with the structure of the title compound. The molecular structure of the title compound is given in Figure 1. The X‐ray crystallographic study of the title compound showed that C5‐N1 bond length (1.276(2) Å) conforms to the value for a double bond (Table 2). The bond length of 1.346(2) Å between N2 and C6 which is greater than the value for a double bond and less than that for a single bond indicates conjugation in the molecule. The bond lengths and angles are similar to those found in related compounds [14‐17]. The E– configuration of the molecule is established by the torsion angle N2‐N1‐C5‐C4 which assumes a value of 178.9(2) (Table 2). The compound is found to exist in the syn‐periplanar form. The two furyl rings are planar with a dihedral angle of 14.7 between them. Packing of molecules down c‐axis in the unit cell is shown in Figure 2. The packing of molecules in the unit cell is through intermolecular N‐H···O and C‐H···O interactions (Table 3). Figure 2. Packing of molecules in the unit cell. 396 Datta et al. / European Journal of Chemistry 5 (3) (2014) 394‐396 Table 2. Selected geometric parameters for the title compound. Bond lengths, Å C1‐C4 1.341(3) C4‐C5 1.437(3) C7‐C8 1.339(3) C1‐C2 1.435(3) C5‐N1 1.276(2) C7‐O3 1.367(2) C2‐C3 1.306(4) C6‐O2 1.230(2) C8‐C9 1.409(3) C3‐O1 1.365(3) C6‐N2 1.346(2) C9‐C10 1.327(3) C4‐O1 1.358(2) C6‐C7 1.463(2) C10‐O3 1.357(2) N1‐N2 1.380(2) Bond angles, ° C4‐C1‐C2 105.8(2) O2‐C6‐N2 123.2(2) C10‐C9‐C8 106.5(2) C3‐C2‐C1 106.8(2) O2‐C6‐C7 120.4(2) C9‐C10‐O3 110.9(2) C2‐C3‐O1 111.0(2) N2‐C6‐C7 116.5(2) C5‐N1‐N2 115.5(2) C1‐C4‐O1 110.1(2) C8‐C7‐O3 109.8(2) C6‐N2‐N1 118.0(1) C1‐C4‐C5 131.0(2) C8‐C7‐C6 131.2(2) C4‐O1‐C3 106.3(2) O1‐C4‐C5 118.9(2) O3‐C7‐C6 119.0(2) C10‐O3‐C7 105.9(2) Torsion angles, ° C4‐C1‐C2‐C3 1.6(3) C8‐C9‐C10‐O3 0.2(3) C1‐C2‐C3‐O1 ‐0.9(3) C4‐C5‐N1‐N2 178.9(2) C2‐C1‐C4‐O1 ‐1.7(2) O2‐C6‐N2‐N1 ‐1.6(2) C2‐C1‐C4‐C5 178.3(2) C7‐C6‐N2‐N1 178.7(1) C1‐C4‐C5‐N1 173.6(2) C5‐N1‐N2‐C6 177.5(2) O1‐C4‐C5‐N1 ‐6.4(3) C1‐C4‐O1‐C3 1.2(3) O2‐C6‐C7‐C8 ‐4.1(3) C5‐C4‐O1‐C3 ‐178.8(2) N2‐C6‐C7‐C8 175.6(2) C2‐C3‐O1‐C4 ‐0.1(3) O2‐C6‐C7‐O3 175.9(2) C9‐C10‐O3‐C7 ‐0.3(3) N2‐C6‐C7‐O3 ‐4.4(2) C8‐C7‐O3‐C10 0.2(2) O3‐C7‐C8‐C9 0.0(2) C6‐C7‐O3‐C10 ‐179.8(2) C6‐C7‐C8‐C9 180.0(2) C7‐C8‐C9‐C10 ‐0.1(3) Table 3. Hydrogen bond geometry (Å, ) for the title compound (D‐Donor; A‐Acceptor; H‐ Hydrogen). D‐H···A d (D‐H) d (H···A) d (D···A) ∠ DHA N2‐H2A···O2 i 0.860 2.119 2.949 161.99 C2‐H2···O2 ii 0.930 2.468 3.384 168.54 C8‐H8···O2 iii 0.930 2.430 3.360 178.87 Symmetry codes: (i) ½‐x, ½+y, z; (ii) ‐½+x, y, ½‐z ; (iii) 1‐x, ‐y, ‐z. 4. Conclusion This work describes the synthesis of an acyl hydrazone of furfuraldehyde by a convenient procedure which affords good yield. The IR and 1H NMR analysis elucidate the structure of compound. Crystal structure of the compound was determined by single crystal X‐ray diffraction at room temperature. Structure analysis of the compound indicated N‐H···O hydrogen bonding in the solid state. The E‐geometry of the C=N bond was also established by this study. Acknowledgements This work was supported by Centre for Research, Christ University, Bangalore, India (Project No: MRPDSC 1105). 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