Synthesis and Study of the Crystal Structure of 2-[(Dipyrrolidin-1-yl) methylene] malononitrile
Keywords:single-crystal X-ray study, crystal structure, orthorhombic crystal system, direct displacement, R factor = 0.040, wR = 0.110
This study aims to synthesis 2-[(dipyrrolidin-1-yl)methylene] malononitrile 2 and identify its crystal structure by X-ray diffraction analysis. 2-[(dipyrrolidin-1-yl)methylene] malononitrile was prepared by a direct displacement of the methylthio group (SMe) in the 2-[bis(methylthio)methylene] malononitrile 1 with pyrrolidine as cyclic secondary amine by conjugating addition-elimination reaction under reflux conditions for two hours. The compound was obtained in high yield (80%). The structure of compound 2-[(dipyrrolidin-1-yl)methylene] malononitrile2 was identified by performing X-ray diffraction analysis. Suitable crystals of compound 2 were grown by slow evaporation of methanol solution of the compound. The compound 2 crystallized in an orthorhombic crystal system with a space group of Pbcn. In the title compound, the two cyanide groups and the two pyrrolidine rings adopted trans configurations across the C2=C3 bond. The bond lengths and angles of the two pyrrolidinyl rings in the compound are within the normal range. The maximum deviation of N5/C2/C3/C4/N5a/C4a is 0.002(1) around C4, and no deviation has been recorded for the fragment N1/N1a/C2/C3 (0.000 (1)°). The dihedral angle between the pyrrolidine ring and N1/N1a/C2/C3 is 33.06(8)°, and the dihedral angle between the pyrrolidine ring and N5/C2/C3/C4/N5a/C4a is 50.57(7)°. The crystal packing is stabilized by two intermolecular and one intramolecular C---H…N hydrogen bonds, which form a one-dimensional polymeric chain along the axis.
Al-Adiwish, W. M., Hamza, M. M., & Hamza, K. M. (2019). A Study X-ray Crystal Structure of Compound 2-[Methylthio (morpholino) methylene] malononitrile, C 9 H 11 N 3 OS. American Journal of Quantum Chemistry and Molecular Spectroscopy, 3(1), 12-16.
Al-Adiwish, W. M., Tahir, M., Siti-Noor-Adnalizawati, A., Hashim, S. F., Ibrahim, N., & Yaacob, W. (2013). Synthesis, antibacterial activity and cytotoxicity of new fused pyrazolo [1, 5-a] pyrimidine and pyrazolo [5, 1-c][1, 2, 4] triazine derivatives from new 5-aminopyrazoles. European journal of medicinal chemistry, 64, 464-476. DOI: https://doi.org/10.1016/j.ejmech.2013.04.029
Al-Afaleq, E. I. (2001). A facile method for the synthesis of novel pyridinone derivatives via ketene N, S-acetals. Synthetic communications, 31(22), 3557-3567. DOI: https://doi.org/10.1081/SCC-100106218
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G., & Taylor, R. (1987). Tables of bond lengths determined by X-ray and neutron diffraction. Part 1. Bond lengths in organic compounds. Journal of the Chemical Society, Perkin Transactions 2(12), S1-S19. DOI: https://doi.org/10.1039/p298700000s1
Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M., Polidori, G. t., & Camalli, M. (1994). SIRPOW. 92–a program for automatic solution of crystal structures by direct methods optimized for powder data. Journal of Applied Crystallography, 27(3), 435-436. DOI: https://doi.org/10.1107/S0021889894000221
Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K., & Watkin, D. J. (2003). CRYSTALS version 12: software for guided crystal structure analysis. Journal of Applied Crystallography, 36(6). DOI: https://doi.org/10.1107/S0021889803021800
El-Saghier, A. M., Matough, F. S., Farhat, M. F., Saleh, N. A., Kreddan, K. M., El-Tier, S. O., & Hussien, H. B. (2008). Synthesis and Biological Evaluation of Some New Thienopyridine and Thienopyrimidine Derivatives. Jordan Journal of Chemistry (JJC), 3(3), 223-232.
Elgemeie, G., Elghandour, A., Elzanate, A., & Ahmed, S. (1997). Synthesis of some novel α-cyanoketene S, S-acetals and their use in heterocyclic synthesis. Journal of the Chemical Society, Perkin Transactions 1(21), 3285-3290. DOI: https://doi.org/10.1039/a702343j
Elgemeie, G. H., Ali, H. A., Elghandour, A. H., & Hussein, A. M. (2003). Synthesis of benzimidazole ketene N, S-acetals and their reactions with nucleophiles. Synthetic communications, 33(4), 555-562. DOI: https://doi.org/10.1081/SCC-120015809
Elgemeie, G. H., Elghandour, A. H., & Abd Elaziz, G. W. (2003). Novel synthesis of heterocyclic ketene N, N-, N, O-, and N, S-acetals using cyanoketene dithioacetals. Synthetic communications, 33(10), 1659-1664. DOI: https://doi.org/10.1081/SCC-120018927
Elgemeie, G. H., Elghandour, A. H., & Abd Elaziz, G. W. (2004). Potassium 2‐Cyanoethylene‐1‐thiolate Derivatives: A New Preparative Route to 2‐Cyanoketene S, N‐Acetals and Pyrazole Derivatives. Synthetic communications, 34(18), 3281-3291. DOI: https://doi.org/10.1081/SCC-200030549
Elgemeie, G. H., Elghandour, A. H., & Elaziz, G. W. A. (2007). Novel Cyanoketene N, S‐Acetals and Pyrazole Derivatives using Potassium 2‐Cyanoethylene‐1‐thiolates. Synthetic communications, 37(17), 2827-2834. DOI: https://doi.org/10.1080/00397910701473317
Gouda, M., Berghot, M., Shoeib, A., & Khalil, A. (2010). Synthesis and antimicrobial of new anthraquinone derivatives incorporating pyrazole moiety. European journal of medicinal chemistry, 45(5), 1843-1848. DOI: https://doi.org/10.1016/j.ejmech.2010.01.021
Khalil, A., Berghot, M., & Gouda, M. (2009). Synthesis and antibacterial activity of some new heterocycles incorporating phthalazine. European journal of medicinal chemistry, 44(11), 4448-4454. DOI: https://doi.org/10.1016/j.ejmech.2009.06.003
Ma, Y., Wang, M., Li, D., Bekturhun, B., Liu, J., & Liu, Q. (2009). α-Alkenoyl ketene S, S-acetal-based multicomponent reaction: an efficient approach for the selective construction of polyfunctionalized cyclohexanones. The Journal of Organic Chemistry, 74(8), 3116-3121. DOI: https://doi.org/10.1021/jo900217g
Misra, N., Panda, K., Ila, H., & Junjappa, H. (2007). An efficient highly regioselective synthesis of 2, 3, 4-trisubstituted pyrroles by cycloaddition of polarized ketene S, S-and N, S-acetals with activated methylene isocyanides. The Journal of Organic Chemistry, 72(4), 1246-1251. DOI: https://doi.org/10.1021/jo062139j
Paris, T. J., Schwartz, C., Sundall, E., & Willand-Charnley, R. (2021). Rapid, One-Step Synthesis of α-Ketoacetals via Electrophilic Etherification. The Journal of Organic Chemistry, 86(21), 14797-14811. DOI: https://doi.org/10.1021/acs.joc.1c01588
Paris, T. J., Schwartz, C., & Willand-Charnley, R. (2021). Electrophilic Etherification of α-Heteroaryl Carbanions with Monoperoxyacetals as a Route to Ketene O, O-and N, O-Acetals. The Journal of Organic Chemistry, 86(3), 2369-2384. DOI: https://doi.org/10.1021/acs.joc.0c02506
Pro, C. (2010). Data Collection and Processing Software for Agilent X-Ray Diffractometers. Aglient Technologies: Yarnton, UK.
Sommen, G., Comel, A., & Kirsch, G. (2003). Preparation of thieno [2, 3-b] pyrroles starting from ketene-N, S-acetals. Tetrahedron, 59(9), 1557-1564. DOI: https://doi.org/10.1016/S0040-4020(03)00054-1
Suryawanshi, S., Pandey, S., Bhatt, B., & Gupta, S. (2007). Chemotherapy of leishmaniasis Part VI: Synthesis and bioevaluation of some novel terpenyl S, N-and N, N-acetals. European journal of medicinal chemistry, 42(4), 511-516. DOI: https://doi.org/10.1016/j.ejmech.2006.09.016
Watkin, D., Prout, C., & Pearce, L. (1996). CAMERON, Chemical Crystallography Laboratory, University of Oxford: Oxford.
Zhang, L., Dong, J., Xu, X., & Liu, Q. (2016). Chemistry of ketene N, S-acetals: an overview. Chemical Reviews, 116(2), 287-322. DOI: https://doi.org/10.1021/acs.chemrev.5b00360
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