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Zeitschrift für Kristallographie - New Crystal Structures

Editor-in-Chief: Huppertz, Hubert

Editorial Board: Hübschle, Christian / Janka, Oliver / Lemmerer, Andreas / Reiß, Guido / Tiekink, Edward R.T.


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Volume 232, Issue 2

Issues

Crystal structure of 2-(bis(4-methoxyphenyl)amino)-2-oxoacetic acid, C16H15NO5

Gamal A. El-Hiti
  • Corresponding author
  • Cornea Research Chair, Department of Optometry, College of Applied Medical Sciences, King Saud University, P.O. Box 10219, Riyadh 11433, Saudi Arabia
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/ Keith Smith / Mesfer Alamri
  • School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK
  • School of Biosciences, Cardiff University, Cardiff CF10 3AT, UK
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/ Ceri A. Morris
  • School of Biosciences, Cardiff University, Cardiff CF10 3AT, UK
  • School of Medicine, Cardiff University, Tenovus Building, Heath Park, Cardiff CF14 4XN, UK
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/ Benson M. Kariuki / Peter Kille
Published Online: 2017-01-20 | DOI: https://doi.org/10.1515/ncrs-2016-0325

Abstract

C16H15NO5, monoclinic, P21/n (no. 14), a = 6.7689(5) Å, b = 45.219(3) Å, c = 10.1102(6) Å, β = 101.360(7)°, V = 3033.9(4) Å3, T = 298(2) K.

This article offers supplementary material which is provided at the end of the article.

CCDC no.:: 1525292

Tables 1 and 2 contain details of the measurement method and a list of the atoms including atomic coordinates and displacement parameters.

Table 1

Data collection and handling.

Table 2

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).

Source of material

A solution of oxalyl chloride (1 mole equivalent) in dichloromethane (DCM) was added dropwise to a solution of bis(4-methoxyphenyl)amine (1 mole equivalent) in DCM in the presence of triethylamine at room temperature. The mixture was stirred for 1.5 h and water was added. The organic layer was separated, dried over anhydrous magnesium sulfate and evaporated under reduced pressure to give the title compound in 46% yield. The low yield could be a result of half of the amine acting as a base to abstract hydrogen chloride evolved from the reaction. To investigate this issue the reaction was repeated with two equivalents of bis(4-methoxyphenyl)amine and no triethylamine. Following aqueous work-up, the crude product was obtained in 75% yield based on oxalyl chloride. Crystallization using acetonitrile gave the title compound as colorless crystals, Mp. 122–123 °C. The NMR spectra recorded at room temperature showed two sets of signals for the two aryl rings, confirming restricted rotation about the C—N bond. The barriers to free rotation in such compounds are already known to be substantial [1], [2], [3]. 1H NMR (400 MHz, DMSO-d6): δ 7.04, 6.96 (2 d, J = 8.5 Hz, 4 H, H-2/H-6), 6.86, 6.69 (2 d, J = 8.5 Hz, 4 H, H-3/H-5), 3.82, 3.71 (2 s, 6 H, OMe); 13C NMR (100 MHz, DMSO-d6): δ 164.4 (s, CO2H), 159.2 (s, C = O), 158.3 (s, C-4), 134.0, 132.8 (2 s, C-1), 129.8, 127.7 (2 d, C-2/C-6), 114.8 (2 d, C-3/C-5), 56.0, 55.8 (2 q, OMe); ES+−MS: m/z (%) 302 (MH+, 100), 288 (12), 256 (21), 228 (12); HRMS (ES+): calculated for C16H16NO5 (MH+): 302.1028; found: 302.1028. IR (FT): νmax 3300, 1740, 1713, 1665, 1500, 1366, 1167 cm−1.

Experimental details

Non-hydrogen atoms were refined with anisotropic displacement parameters. All hydrogen atoms were placed in calculated positions and refined using a ring model. Methyl C—H bonds were fixed at 0.96 Å and displacement parameters were 1.5 times Ueq(C). The methyl groups were allowed to spin about the C—C bond. Aromatic C—H distances were set to 0.93 Å and their U(iso) parameters were set to 1.2 times Ueq(C). Hydroxyl O—H distances were set to 0.82 Å and their U(iso) set to 1.5 times Ueq(O). Crystal data, data collection and structure refinement details are summarized in Table 1.

Comment

Aryl oxamic acid derivatives have various interesting applications [4], [5], [6], [7], [8]. In addition, aryl oxamic acids can be used as intermediates for the synthesis of various classes of compounds including heterocycles [9], [10], [11], [12]. Oxamates can be synthesized by the use of various synthetic procedures [13], [14], [15], [16], [17].

In the title crystal structure, the asymmetric unit consists of two independent molecules of C16H15NO5. The oxoacetic acid fragments of the molecule are involved in intermolecular hydrogen bonding, of the type O—H⋯O, with the following geometric parameters: O4⋯O7 = 2.673(2) Å, O—H⋯O = 171.0°; and O9⋯O2 = 2.734(2) Å, O—H⋯O = 169.9° forming chains along [101].

These hydrogen bonds can be classified as medium strong. Bond lengths and angles in both crystallographically independent molecules are in the expected ranges.

Acknowledgement

We thank the EPSRC for the grant which supplied the MS instrumentation used in this study. M. Alamri thanks the Saudi Cultural Bureau, London for a scholarship and G. A. El-Hiti extends his appreciation to the Deanship of Scientific Research at King Saud University for its funding for this research through the research group project RGP-239.

References

  • 1

    Hobson, R. F.; Reeves, L. W.: Hindered rotation about the N-C bond in some vinylogous amides. J. Magn. Reson. 10 (1973) 243–252. Google Scholar

  • 2

    Smith, B. D.; Goodenough-Lashua, D. M.; D’Souza, C. J. E.; Norton, K. J.; Schmidt, L. M.; Tung, J. C.: Substituent effects on the barrier to carbamate C–N rotation. Tetrahedron Lett. 45 (2004) 2747–2749. Google Scholar

  • 3

    Krishnan, V. V.; Thompson, W. B.; Goto, J. J.; Maitra, K.; Maitra, S.: Modulations in restricted amide rotation by steric induced conformational trapping. Chem. Phys. Lett. 523 (2012) 124–127. Google Scholar

  • 4

    Maiore, L.; Aragoni, M. C.; Carcangiu, G.; Cocco, O.; Isaia, F.; Lippolis, V.; Meloni, P.; Murru, A.; Slawin, A. M. Z.; Tuveri, E.; Woollins, J. D.; Arca, M.: Oxamate salts as novel agents for the restoration of marble and limestone substrates: case study of ammonium N-phenyloxamate. New J. Chem. 40 (2016) 2768–2774. Google Scholar

  • 5

    Miskimins, W. K.; Ahn, H. J.; Kim, J. Y.; Ryu, S.; Jung, Y.-S.; Choi, J. Y.: Synergistic anti-cancer effect of phenformin and oxamate. PLOS One 9 (2014) e85576, doi: 10.1371/journal.pone.0085576. Google Scholar

  • 6

    Choi, S.-R.; Beeler, A. B.; Pradhan, A.; Watkins, E. B.; Rimoldi, J. M.; Tekwani, B.; Avery, M. A.: Generation of oxamic acid libraries: antimalarials and inhibitors of plasmodium falciparum lactate dehydrogenase. J. Comb. Chem. 9 (2007) 292–300. Google Scholar

  • 7

    Hargrave, K. D.; Hess, F. K.; Oliver, J. T.: N-(4-Substituted-thiazolyl)oxamic acid derivatives, new series of potent, orally active antiallergy agents. J. Med. Chem. 26 (1983) 1158–1163. Google Scholar

  • 8

    Klaubert, D. H.; Sellstedt, J. H.; Guinosso, C. J.; Capetola, R. J.; Bell, S. C.: N-(Aminophenyl)oxamic acids and esters as potent, orally active antiallergy agents. J. Med. Chem. 24 (1981) 742–748. Google Scholar

  • 9

    Wang, H.; Guo, L.-N.; Wang, S.; Duan, X.-H.: Decarboxylative alkynylation of a-keto acids and oxamic acids in aqueous media. Org. Lett. 17 (2015) 3054–3057. Google Scholar

  • 10

    Loloiu, G.; Maior, O.: Isatin chemistry. Synthesis of N-methyl-2, 3-dioxo-2,3-dihydropyrrolo(2, 3-b) phenoxathiin. Rev. Roum. Chim. 42 (1997) 67–69. Google Scholar

  • 11

    Molina, P.; Vilaplana, M. J.; Andreu, P. L.; Moller, J.: Oxamic acid derivatives in heterocyclic synthesis: preparation of 1,2,4-triazolo[1,5-a]pyrazine derivatives. J. Heterocycl. Chem. 24 (1984) 1281–1284. Google Scholar

  • 12

    Downs, J. R.; Pastine, S. J.; Schady, D. A.; Greer, H. A.; Kelley, W.; Embree, M. C.; Townsend, J. D.; Beam, C. F.: Preparation of 1H-pyrazole-5-carboxamides from dilithiated C(α),N-phenylhydrazones and lithiated ethyl oxanilates or lithiated ethyl oxamate. J. Heterocycl. Chem. 38 (2001) 691–694. Google Scholar

  • 13

    Gadge, S. T.; Kusumawati, E. N.; Harada, K.; Sasaki, T.; Nishio-Hamane, D.; Bhanage, B. M.: Synthesis of oxamate and urea by oxidative single and double carbonylation of amines using immobilized palladium metal-containing ionic liquid@SBA-15. J. Mol. Catal. A: Chem. 400 (2015) 170–178. Web of ScienceGoogle Scholar

  • 14

    Gadge, S. T.; Bhanage, B. M.: Pd/C-Catalyzed synthesis of oxamates by oxidative cross double carbonylation of amines and alcohols under Co-catalyst, base, dehydrating agent, and ligand-free conditions. J. Org. Chem. 78 (2013) 6793–6797. Google Scholar

  • 15

    Lisnard, L.; Chamoreau, L.-M.; Li, Y.; Journaux, Y.: Solvothermal synthesis of oxamate-based helicate: temperature dependence of the hydrogen bond structuring in the solid. Cryst. Growth Des. 12 (2012) 4955–4962. Google Scholar

  • 16

    Yang, G.; Zhang, H.; Huang, Y.; Chen, Z.: Synthesis of methyl N-aryl oxamate using soluble polymer support. Synth. Commun. 36 (2006) 611–619. Google Scholar

  • 17

    Lesimple, P.; Bigg, D. C. H.: An improved procedure for the preparation of alkyl N-(4-aryl-2-thiazolyl)oxamates. Synthesis 1991(9) (1991) 763–764. Google Scholar

  • 18

    Agilent. CrysAlisPRO. Agilent Technologies, Yarnton, England, 2014. Google Scholar

  • 19

    Sheldrick, G. M.: A short history of SHELX. Acta Crystallogr. A64 (2008) 112–122. Google Scholar

  • 20

    Farrugia, L. J.: WinGX and ORTEP for Windows: an update. J. Appl. Crystallogr. 45 (2012) 849–854. Google Scholar

  • 21

    Cambridge Soft. CHEMDRAW Ultra. Cambridge Soft Corporation, Cambridge, MA, USA, 2001. Google Scholar

About the article

Received: 2016-10-17

Accepted: 2017-01-03

Published Online: 2017-01-20

Published in Print: 2017-03-01


Citation Information: Zeitschrift für Kristallographie - New Crystal Structures, Volume 232, Issue 2, Pages 333–335, ISSN (Online) 2197-4578, ISSN (Print) 1433-7266, DOI: https://doi.org/10.1515/ncrs-2016-0325.

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©2017 Gamal A. El-Hiti et al., published by De Gruyter.. This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License. BY-NC-ND 3.0

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