Structural Characterization, Theoretical Investigation and Hirshfeld Surface Analysis of 2,6-(E,E)-bis((thiophene-2-yl)methylene)cyclohexanone

Year 2019, Volume: 3 Issue: 2, 47 - 58, 15.12.2019

Gül Yakalı , Abdullah Biçer , Günseli Turgut Cin

https://doi.org/10.33435/tcandtc.457453

Cited By: 1

Abstract

The bis(chalcone) compound, 2,6-(E,E)-bis((thiophene-2-yl)methylene)cyclohexanone,
has been synthesized and characterized by FTIR, ¹H-NMR, ¹³C-NMR
techniques, X-ray structure analysis. The optimized molecular structure of the
studied compound is calculated using DFT/B3LYP with 6-31G (d,p) level.
The calculated geometrical parameters are in good agreement with the
experimental data obtained from our reported X-ray structure. The calculated IR
fundamental bands, ¹H and ¹³C NMR chemical shifts of the
compound  were assigned and compared with
the experimental data. Additionally, frontier
molecular orbital energies (HOMO, LUMO), their energy gap (, molecular electrostatic potential analysis of the compound
have been calculated by the same method. The molecular electrostatic potential
(MEP) was used to visualize the charge distribution on the molecule. In
addition, the
intercontacts in the crystal structure are analyzed using Hirshfeld surfaces
computational method. The title compound (C₁₆H₁₄OS₂)
crystallizes in the monoclinic
chiral space group P21/c with a=15.0492(10)Å, b=12.0085(9)Å, c=7.6283(6)
Å, β=95.883(7)^o, V=1371.31(17)ų, D_calc=1.387g/cm³. The central cyclohexanone
ring has a flattened chair conformation and the
substituents at the vinyl group of each chalcone moiety exhibit a trans
(entgegen) disposition, and the two thiophene rings adopt a syn orientation and
are located on the both side of the cyclohexanone. The asymmetric unit
of the title compound, C₁₆H₁₄OS₂, contains one-half
of a molecule. The other half of the molecule is generated with (x,y,-z)  symmetry operator. In the molecule there are two weak
C-H…S and C-H…O intramolecular and only C-H…O intermolecular hydrogen bonds. In
addition, π…π interactions are found in the crystal structure between the
thiophene rings.

Keywords

Bis(chalcone), X-ray crystallography, DFT

References

• [1] Carlo GD, Mascolo N, Izzo AA, Capasso F (1999) Life Sci. 65 337.
• [2] Romanelli G, Pasquale G, Sathicq A, Thomas H, Autino J, Vazquez P (2011) J Mol Catal A Chem. 340 24.
• [3] Eddarir S, Cotelle N, Bakkour Y, Rolando C, (2003) Tetrahedron Lett 44 5359.
• [4] Shettigar S, Chandrasekharan K, Umesh G, Sarojini BK, Narayana B (2006) Polymer 47:3565
• [5] Patil PS, Dharmaprakash SM, Fun HK, Karthikeyan MS (2006) J Cryst Growth 297:111
• [6] Fayed TA, Awad MK (2004) Chem Phys 303:317.
• [7] SensR, Drexhage K (1981) H Lumin J 24:709.
• [8] Asiri AM, Khan SA (2012) J Hetrocyl Chem 49 : 1434.
• [9] Kumar Reddya RS, Badama R, Sattibabub R, Mollib M, Muthukumarb VS, Sankara Saib SS, Raoa GN (2014) Chemical Physics Letters 616–617 142–147.
• [10] Modzelewska A, Pettit C, Achanta G, Davidson NE, Huang P, Khan SR (2006) Bioorg Med Chem Lett 14: 3491.
• [11] Bazzaro M, Anchoori RK, Mudiam MKR (2011) J Med Chem 54: 449.
• [12] Govindaraju C, et al. (2012) Med Chem Res 21 :2671.
• [13] Padmavathi BV, Jagan Mohan Reddy DRC, Subbaiah V (2004) New J Chem 28: 1479.
• [14] Dinkova-Kostova AT, Abeygunawardana C, Talalay P (1998) J Med Chem 41: 5287.
• [15] D’silva ED, Narayana Rao D, Philip R, Butcher RJ, Rajnikant, Harmaprakash SMD (2011) J Phys Chem Solids 72: 824.
• [16] Asiri AM, Khan SA (2011) Mater. Lett. 65: 1749.
• [17] Zhao B, Wu Y, Zhou ZH, Lu WQ (2000) Chen, Appl. Phys. B 70: 601.
• [18] Dimmock JR, Arora VK, Chen M, Allen TM, Kao GK (1994) Drug Des. Discovery 12: 19.
• [19]Dimmock JR, Arora VK, Duffy MJ, Reid RS, Allen TM, Kao GY (1992) Drug Des. Discovery 8 :291.
• [20]Hussein MA, Marwani HM, Alamry KA, Asiri AM, El-Daly SA (2014) J Appl Poly Sci 131: 40873.
• [21] CrysAlis PRO and CrysAlis RED. Agilent Technologies (2002) Yarnton Oxfordshire England.
• [22] Sheldrick GM (2008) Acta Cryst A 64: 112.
• [23] Dolomanov OV, Bourhis LJ, Gildea RJ, Howard JAK, Puschmann H (2009) J Appl Cryst 42: 339-341.
• [24] Hohenberg P, Kohn W (1964) Phys Rev 136: B846–B871.
• [25] Kohn W, Sham LJ (1965) Phys Rev 140:A1133–A1138.
• [26]Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JA, Vreven JT, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi Scalmani GJM, Rega N, Petersson GA,Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda, Hasegawa R, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Adamo C, Jaramillo J, Gomperts R, Stratmann RE,Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VV, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman B, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al- Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA (2003) Gaussian 03 Revision E. 01 Gaussian Inc Pittsburgh PA.
• [27]Frisch A, Dennington RD, Keith TA, Milliam J, Nielsen JA, Holder AJ, Hiscocks J (2007) GaussView Reference Version 4.0 Gaussian Inc Pittsburgh.
• [28] Aksöz BE, Ertan R (2012) J pharm Sci 37,4:205-206.
• [29] Zhang Y, Pan KL, He F, Chen LF, Liu ZG, Liang G (2015) Z Kristallogr NCS 230 :271-272.
• [30] Contreras D, Moreno Y, Soto C, Saavedra M, Brovellı F, Baggıo R (2009) J Chil Chem Soc 54: 4.
• [31] Jiang C, Feng Z, Song B, Lib X, Lia X (2010) Acta Cryst E66: o1009
• [32] Padmaja L, Ravikumar C, Sajan D, Joe IH, Jayakumar VS, Pettit GS (2009) J Raman Spectros 40:419–28.
• [33] Barakat A, Al-Majid AM, Soliman SM, Mabkhot YN, Ali M, Ghabbour HA, Fun HK, Wadood A (2015) Chemistry Central Journal .
• [34] Karabıyık H, Sevincek R, Karabıyık H (2015) J Phys Org Chem 28:490-496.
• [35] Murugavel S, Manıkandan N, Lakshmanan D, Naveen K, Perumal PT (2015) J Chil Chem Soc 60:3.
• [36] Nesterov VV, Nesterov VN, Richmond MG (2012) Polyhedron,35:24-129.
• [37] Babu NR, Subashchandrabose S, Padusha MSA, Saleem H, Erdoğdu Y (2014) Molecular and Biomolecular Spectroscopy 120 : 314–322.[38] Spackman MA, McKinnon JJ (2002) CrystEngComm 4: 378–392.[39] Wolff SK, Grimwood DJ, McKinnon JJ, Turner MJ, Jayatilaka D, Spackman MA (2012) CrystalExplorer (Version 3.0) University of Western Australia.