1211-1214Single-crystal study of indolyl chalcone (E)-1-(4-bromophenyl)-3-(1-H-indol-3-yl)-prop-2-en-1-one is reported here. It has been synthesized by microwave assisted method from indole-3-carbaldehyde and 4-bromo acetophenone by Claisen-Schmidt reaction. IR,1H NMR and HRMS data is reported here. The crystalline structure of this compound is described within the sp. gr. I -4; its unit cell parameters are a = 23.9636(17)Å,b = 23.9636(17)Å,c = 5.1428(5)Å. Crystallographic study shows formation of hydrogen-bonded cyclic tetramer around a 2-fold axis and 4-fold roto-inversion axis through N1–H1···O1 interactions between the indolic NH group as a hydrogen-bond donor and the carbonyl O atom as a hydrogen-bond acceptor

Banpurkar, Anita R

Perdih, Franc

Wazalwar, Sachin S

NOPR

Indian Journal of Chemistry Vol. 60B, September 2021, pp. 1211-1214 Study of solid state structural and bonding features of (E)-1-(4-bromophenyl)-3-(1-H-indol-3-yl)-prop-2-en-1-one Anita R Banpurkara, Sachin S Wazalwar*a& Franc Perdihb a Department of Applied Chemistry, Rajiv Gandhi College of Engineering, Research and Technology, Chandrapur 442 403, India b Faculty of Chemistry and Chemical Technology,University of Ljubljana, SI-1000 Ljubljana, Slovenia E-mail: sacheein@gmail.com; franc.perdih@fkkt.uni-lj.siReceived 31 January 2020; accepted (revised) 18 August 2021 Single-crystal study of indolyl chalcone (E)-1-(4-bromophenyl)-3-(1-H-indol-3-yl)-prop-2-en-1-one is reported here. It has been synthesized by microwave assisted method from indole-3-carbaldehyde and 4-bromo acetophenone by Claisen-Schmidt reaction. IR,1H NMR and HRMS data is reported here. The crystalline structure of this compound is described within the sp. gr. I -4; its unit cell parameters are a = 23.9636(17)Å,b = 23.9636(17)Å,c = 5.1428(5)Å. Crystallographic study shows formation of hydrogen-bonded cyclic tetramer around a 2-fold axis and 4-fold roto-inversion axis through N1–H1···O1 interactions between the indolic NH group as a hydrogen-bond donor and the carbonyl O atom as a hydrogen-bond acceptor. Keywords: Indolyl chalcone, indole-3-carbaldehyde, 4-bromoacetophenone, microwave assisted, X-ray diffraction, cyclic tetramer Indolyl chalcones have been reported to possess potent biological activities like anticancer1,2 anti-inflammatory2, antioxidant2, antitumor3 and antimicrobial4 activities.Heterocyclic analogue is reported to be effective even against resistant cell lines1. Apart from biological activities it is also useful in synthesis of biologically active pyrazoles5, flavones6, pyrazolines7. Microwave assisted synthesis of chalcones is a rapid,eco-friendly and convenient method of synthesis8. As a part of study, we report here synthesis, characterization and single-crystal study of (E)-1-(4-bromophenyl)-3-(1-H-indol-3-yl)-prop-2-en-1-one. Results and Discussion The compound (E)-1-(4-bromophenyl)-3-(1-H-indol-3-yl)-prop-2-en-1-one (3a) was obtained by microwave assisted Claisen-Schmidt reaction between indol-3-carbaldehyde (1a) and 4-bromoacetophenone (2a) using NaOH as a catalyst and ethanol as a solvent. The yellow solid obtained in good yield. The IR spectrum of compounds 3a shows characteristic υ(-C=O) absorption band in the region 1631 cm–1, and υ(-CH=CH) band in the region 3163 cm–1(Figure 1). The 1H NMR spectra of compounds 3a in DMSO exhibit characteristic singlet at 12.13 ppm attributed to indolicNH proton, doublet at 7.51 and 7.76 ppm showing one proton each is attributed to CH=CH protons representing CH=CH of chalcone moiety (Figure 2). Furthermore, the mass spectra, elemental analysis and single-crystal structure confirms the structure of compound 3a. We were able to obtain crystals suitable for X-ray structural analysis and crystal structure shows that all the bond lengths are within normal ranges9 (Table I, Figure 3). Molecule is essentially planar with the maximum deviation from planarity of –0.155(9) Å for atom O1 and torsion angle between indole and phenyl ring of 2.6(5). Figure 1 — FTIR spectra of compound 3a INDIAN J. CHEM., SEC B, SEPTEMBER 2021    1212   Figure 2 — 1HNMR spectra of compound 3a    Figure 3 — Molecular structures and atom numbering scheme  for 3a. Probability ellipsoids are drawn at the 50% level  Table I — Crystallographic data for compound 3a Compd 3a CCDC number 1893165 Mol. Formula C17H12BrNO Mol. Wt. 326.19 Crystal System Tetragonal Space group I–4 a (Å) 23.9636(17) b (Å) 23.9636(17) c (Å) 5.1428(5) α (°) 90 β (°) 90 γ (°) 90 Z 8 V (Å3) 2953.3(5) Dcalc (g cm–3) 1.467 μ (mm–1) 2.778 F(000) 1312 Reflections collected 4007 Independent reflections 2790 Rint 0.0249 Parameters 181 R1, wR2 [I> 2σ(I)]a 0.0761, 0.1938 R1, wR2 (all data)a 0.1486, 0.2457 GOFb 1.006 Δρmin, Δρmax (e Å–3) 0.880, –0.403 a R = ∑||Fo| – |Fc||/∑|Fo|; wR2 = {∑[w(Fo2 – Fc2)2]/∑[w(Fo2)2]}1/2. bS = {∑[(Fo2 – Fc2)2]/(n/p)}1/2 where n is the number of reflections and p is the total number of parameters refined. Materials and Methods The starting materials indole-3-carbaldehyde, 4-bromoacetophenone, and solvents were purchased from commercial sources and were used without further purification. Microwave oven of Samsung, 800W output with digital timer and clock was used for synthesis. Melting point was determined in open capillary using electro thermal melting point apparatus and is uncorrected. Progress of reactions was monitored by TLC. Infrared (IR) spectra (4000–600 cm–1) of the samples were recorded using a Perkin–Elmer Spectrum 100, equipped with a Specac Golden Gate Diamond ATR as a solid sample support. 1H NMR spectra were recorded with a Bruker Avance III 500 NMR spectrometer with TMS as internal reference. MS spectra were recorded with an Agilent 6624 Accurate Mass TOF LC/MS instrument (ESI ionization).  Single-crystal X-ray diffraction data was collected on an Agilent Technologies SuperNova Dual diffractometer with an Atlas detector using monochromated Mo-Kα radiation (λ = 0.71073 Å) at room temperature. The data was processed using CrysAlis Pro10. Structure was solved by direct methods and refined on F2 using full-matrix least-squares procedures using SHELX2014 11. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were readily located in a difference Fourier maps and were subsequently treated as riding atoms in geometrically idealized positions, with C–H = 0.93 (aromatic and alkenyl), N–H = 0.86 Å and with Uiso(H) = 1.2Ueq(C,N). Crystallographic data are listed in Table II.  Experimental Section  Synthesis of (E)-1-(4-bromophenyl)-3-(1-H-indol-3-yl)-prop-2-en-1-one, 3a A mixture of indol-3-carbaldehyde (1.45 g, 10 mmol), 4-bromoacetophenone (1.99 g, 10 mmol), 2-3 drops of saturated NaOH solution and ethanol  (15 mL) as a solvent was irradiated to microwave for about 3 minutes at 450 watts at an interval of 5 seconds The orange yellow product so obtained was poured in crushed ice followed by acidification with 0.1 M HCl solution(Scheme I). The product obtained was filtered, dried and recrystallized using ethanol. Table II — Hydrogen bond geometry of 3a D–H···A D–H (Å) H···A (Å) D···A (Å) D–H  (Å) Symmetry code N1–H1···O1 0.86 1.97 2.824(16) 176 y,1 – x, –z BANPURKAR et al.: (E)-1-(4-BROMOPHENYL)-3-(1-H-INDOL-3-YL)-PROP-2-EN-1-ONE   1213 The recrystallized product was allowed for crystal growth by slow evaporation of its saturated solution in ethanol and chloroform (1:1 v/v) in a dark chamber at room temperature12. Spectral data of compound 3a: Yield 87%. m.p.150°C. IR: (KBr): 3163 (CH=CH), 3046 (Ar-CH), 1631 (C=O), 1434 cm–1 (C=C); 1H NMR (500 MHz, DMSO-d6,): δ 7.20-7.27 (m, 3H, Ar-H), 7.51 (d, 1H, CH=CH), 7.76 (d, 1H, CH=CH), 78.05-8.14 (m, 3H, Ar-H), 8.28 (s, 1H,Ar-H), 9.93 (s, 1H, Ar-H), 12.13 (s, 1H, NH); MS (ESI+): m/z 326.19 (MH+); HRMS: Calcd for C17H12NO: 326.018. Found: 325.0106.   Figure 4 — (a) View along c-axis (top view) on hydrogen-bonded cyclic tetramer of 3a generated by N1–H1···O1hydrogen bonding (blue dashed lines). (b) View along a-axis (side view) on hydrogen-bonded cyclic tetramer (color code: arbitrary colors). (c) Packing of cyclic tetramers along c-axis. (d) Stacking of cyclic tetramers parallel with c-axis (color code: arbitrary colors).  Conclusion Chalcone3a was synthesized by microwave assisted Claisen-Schmidt condensation reaction with good yield. X-ray structural analysis and crystal structure shows that all the bond lengths are  within normal ranges. Molecule is planar with  the maximum deviation from planarity of –0.155(9) Å for atom O1 and torsion angle between indole  and phenyl ring of 2.6(5)°. Formation of hydrogen-bonded cyclic tetramer around a 2-fold axis and  4-fold roto-inversion axis is observed through  N1–H1···O1interactions between the indole NH group as a hydrogen-bond donor and the carbonyl O atom as a hydrogen-bond acceptor forming a R44(32) graph set motif. Hydrogen-bonded cyclic tetramer around a 2-fold axis and 4-fold roto-inversion axis is formed through N1–H1···O1 interactions between the indole NH group as a hydrogen-bond donor and the   Scheme I — Synthesis of (E)-1-(4-bromophenyl)-3-(1-H-indol-3-yl)-prop-2-en-1-one  Table III — Bond lengths d(Å) and bond angles (deg) in the structure of 3a Bond d Bond d Br1–C15 1.878(14) C6–C11 1.398(16) O1–C1 1.272(13) C7–C8 1.385(17) N1–C5 1.324(18) C8–C9 1.42(2) N1–C11 1.366(14) C9–C10 1.361(19) C1–C2 1.438(17) C10–C11 1.409(18) C1–C12 1.468(16) C12–C17 1.392(15) C2–C3 1.371(16) C12–C13 1.411(17) C3–C4 1.392(16) C13–C14 1.397(19) C4–C5 1.378(17) C14–C15 1.363(19) C4–C6 1.416(15) C15–C16 1.386(18) C6–C7 1.389(16) C16–C17 1.383(17) Atoms ω Atoms ω C5–N1–C11 108.2(11) C10–C9–C8 120.6(13) O1–C1–C2 122.3(11) C9–C10–C11 117.3(12) O1–C1–C12 117.0(11) N1–C11–C6 108.4(11) C2–C1–C12 120.8(10) N1–C11–C10 128.6(12) C3–C2–C1 122.0(10) C6–C11–C10 123.0(11) C2–C3–C4 129.7(10) C17–C12–C13 117.5(11) C5–C4–C3 122.4(11) C17–C12–C1 123.0(11) C5-C4-C6 105.3(10) C13-C12-C1 119.5(10) C3-C4-C6 132.3(10) C14-C13-C12 120.8(12) N1-C5-C4 111.5(12) C15-C14-C13 118.9(13) C7-C6-C11 118.9(11) C14-C15-C16 122.4(13) C7-C6-C4 134.6(10) C14-C15-Br1 118.6(10) C11-C6-C4 106.6(9) C16-C15-Br1 118.9(11) C8-C7-C6 118.8(12) C17-C16-C15 118.1(13) C7-C8-C9 121.4(13) C16-C17-C12 122.3(12)  INDIAN J. CHEM., SEC B, SEPTEMBER 2021    1214 carbonyl O atom as a hydrogen-bond acceptor forming a R44(32) graph set motif13(Table III, Figure 4). There are noother significant hydrogen-bonding, halogen∙halogen or π∙∙∙π interactions  present in the system. Table III shows important  bond distances and bond angles in 3a.  Supplementary Information Supplementary information is available in the website http://nopr.niscair.res.in/handle/123456789/60.  Acknowledgments Financial support from the Slovenian Research Agency (ARRS) through project P1-0175 is gratefully acknowledged. The authors thank the EN-FIST Centre of Excellence, Ljubljana, Slovenia, for providing access to the Super Nova diffractometer.  References 1 Sharma V, Kumar V & Kumar P, Anti-Cancer Agents Med Chem, 13 (2013) 422. 2 Bhale P S,Chavan H V, Dongare S B, Shingare S N, Mule Y B, Nagane S S&Bandgar B P, Bioorg Med Chem Lett, 27 (2017) 1502. 3 Kumar D, Kumar N M, Akamatsu K, Kusaka E, Harada H & Ito T, Bioorg Med Chem Lett,20 (2010) 3916. 4 Chauhan R, Dwivedi J, Anees A A S & Kishore D, Pharm Chem J,44 (2011) 542. 5 Sharath V, Kumar H V & Naik N, J Pharm Res, 6 (2013) 785. 6 Venkatesan P &Maruthavanan T, Bull Chem Soc Ethiop, 25 (2011) 419. 7 Siddiqui Z N, Farooq F & Mohammed Musthafa T N,  Green Chem Lett Rev,4 (2011) 63. 8 Kakati D, Sarma R K, Saikia R, Barua N C & Sarma J C, Steroids, 78 (2013) 321. 9 Allen F H, Kennard O, Watson D G, Brammer L, Orpen A G & Taylor R, J Chem Soc Perkin Trans II (1987) S1. 10 CrysAlis PRO, Agilent Technologies, Yarnton, England (2013). 11 Sheldrick G M, Acta Cryst, C 71 (2015) 3. 12 Wazalwar S S, Banpurkar A R &Perdih F, J Mol Struct,1150 (2017) 258. 13 Bernstein J, Davis R E, Shimoni L & Chang N L, Angew Chem Int Ed, 34 (1995) 1555.   

Study of solid state structural and bonding features of (E)-1-(4-bromophenyl)-3-(1-H-indol-3-yl)-prop-2-en-1-one

http://nopr.niscair.res.in/bitstream/123456789/58199/1/IJC%20%28Section%20B%29%2c%2060B%2c%201211-1214%20%28Sep%2c2021%29.pdf

Study of solid state structural and bonding features of (E)-1-(4-bromophenyl)-3-(1-H-indol-3-yl)-prop-2-en-1-one

Abstract

Similar works

Full text

Available Versions

NOPR