Startseite Crystal structure of methyl 1-(4-fluorobenzyl)-4-methoxy-5-oxopyrrolidine-3-carboxylate, C14H16FNO4
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Crystal structure of methyl 1-(4-fluorobenzyl)-4-methoxy-5-oxopyrrolidine-3-carboxylate, C14H16FNO4

  • Hammouda Chebbi EMAIL logo , Abderrahmen Guesmi und Ahmed Driss
Veröffentlicht/Copyright: 18. August 2017

Abstract

C14H16FNO4, monoclinic, P21/n (no. 14), a = 10.189(4) Å, b = 7.742(2) Å, c = 17.240(5) Å, β = 94.50(1)°, V = 1355.8(7) Å3, Z = 4, Rgt(F) = 0.0420, wRref(F2) = 0.1183, T = 295 K.

CCDC no.:: 1514594

The crystal structure is shown in the figure. Tables 1 and 2 contain details on crystal structure and measurement conditions and a list of the atoms including atomic coordinates and displacement parameters.

Table 1

Data collection and handling.

Crystal:Colorless parallelepiped
Size:0.25 × 0.19 × 0.15 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:0.11 mm−1
Diffractometer, scan mode:Enraf-Nonius CAD-4, ω/2θ
θmax:27.0°
N(hkl)measured, N(hkl)unique, Rint:5376, 2949, 0.030
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 2172
N(param)refined:246
Programs:CAD-4 EXPRESS [11, 12] , XCAD4 [13], SHELX [2], WinGX [14]
Table 2

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

xyzUiso*/Ueq
O10.58756(12)0.28236(16)0.52385(7)0.0534(3)
O20.82705(11)0.06561(16)0.47420(7)0.0514(3)
O30.81681(14)−0.15410(17)0.31053(8)0.0619(4)
O40.76067(13)−0.31875(15)0.40865(7)0.0533(3)
F1−0.01456(12)0.24082(19)0.26308(9)0.0876(4)
N10.57842(14)0.22963(16)0.39264(7)0.0425(3)
C10.11313(19)0.2782(2)0.28724(12)0.0576(5)
C20.1443(2)0.3078(3)0.36484(13)0.0620(5)
C30.27348(19)0.3456(2)0.38948(10)0.0523(4)
C40.36927(17)0.35123(19)0.33706(9)0.0424(4)
C50.33260(19)0.3206(2)0.25889(10)0.0504(4)
C60.2037(2)0.2841(2)0.23337(12)0.0579(5)
C70.51029(18)0.3874(2)0.36463(11)0.0481(4)
C80.61154(15)0.19481(19)0.46757(8)0.0373(3)
C90.69091(15)0.0266(2)0.47100(8)0.0374(3)
C100.65125(16)−0.05534(19)0.39231(8)0.0381(3)
C110.6204(2)0.0987(2)0.33899(9)0.0468(4)
C120.8785(3)0.1309(4)0.54734(14)0.0697(6)
C130.75311(16)−0.17663(19)0.36457(9)0.0399(3)
C140.8484(3)−0.4525(3)0.38590(16)0.0660(6)
H20.077(2)0.299(3)0.4005(13)0.071(6)*
H30.2977(19)0.367(3)0.4437(11)0.057(5)*
H50.4010(19)0.328(3)0.2205(12)0.059(5)*
H60.176(2)0.263(3)0.1782(14)0.077(7)*
H7A0.5166(18)0.471(3)0.4087(11)0.055(5)*
H7B0.5597(18)0.434(3)0.3207(11)0.054(5)*
H90.6715(16)−0.038(2)0.5157(10)0.040(4)*
H100.5709(16)−0.121(2)0.3989(9)0.039(4)*
H11A0.5497(18)0.074(2)0.3000(11)0.049(5)*
H11B0.701(2)0.139(3)0.3129(11)0.058(5)*
H12A0.846(3)0.240(4)0.5558(14)0.087(8)*
H12B0.974(3)0.131(4)0.5449(15)0.097(8)*
H12C0.850(3)0.054(4)0.5921(18)0.112(10)*
H14A0.937(3)−0.409(4)0.3805(14)0.088(8)*
H14B0.848(3)−0.536(4)0.4295(16)0.106(9)*
H14C0.815(3)−0.495(4)0.3345(17)0.111(10)*

Source of material

Dimethyl 2-methoxy-3-methylenesuccinate (0.3 g, 1.58 mmol) was dissolved in 6 mL of MeOH followed by dropwise addition of 4-fluorobenzylamine (1.58 mmol, 1 equiv.) under a nitrogen atmosphere at 0 °C. The mixture was then stirred vigorously at this temperature during 6 h. The solvent was concentrated under reduced pressure, and the crude product purifieded by chromatography on silica gel (Et2O/petroleum ether, 8:2) [1]. The crystallization was carried out by vapor diffusion at room temperature for 1 week to obtain colourless crystals. Yield: (0.38 g, 85%), yellow solid, mp: 89–90 °C; IR (film, cm−1): 1740 (COO), 1698 (CON); 1H NMR (300 MHz, CDCl3): δ (ppm) 7.23 (dd, 2H, 3JHH = 6.00 Hz, 3JHH = 6.00 Hz, aromatic H), 7.04(t, 1H, 3JHH = 9.00 Hz, aromatic H), 4.45 (AB, 2H, 2JAB = 15.00 Hz), 4.07 (d, 1H, 3JHH = 9.00 Hz), 3.71 (s, 3H), 3.60 (s, 3H), 3.35 (q, 1H, 3JHH = 9.00 Hz), 3.67–3.21 (m, 2H); 19F NMR (282 MHz, CDCl3): δ (ppm) −114.51 (1F); 13C NMR (75 MHz, CDCl3): δ (ppm) 170.0 (CO2), 169.6 (CON), 162.3 (d, aromatic = C–F, 1JCF = 246.8 Hz), 131.4 (aromatic = C), 129.9 (aromatic = CH), 129.8 (aromatic = CH), 115.8 (aromatic = CH), 115.5 (aromatic = CH), 78.7 (OCH), 59.3 (OCH3), 52.1 (OCH3), 45.8 (CH2N), 45.5 (CHCO2), 42.7 (CH2); MS (EI)m/z (%): 251(37), 249(40), 192(100), 190(94), 109(89), 75(14). MS (CI/NH3): M + 1 = 282. HRMS [M+Na] calcd. for C14H16NO4NaF: 304.0961, found: 304.0962.

Experimental details

The structure was solved by Direct Methods [2] and the refinement was done against F2 [2]. The reflections were corrected for Lorentz and polarization effects followed by psi-scan absorption correction [3].

Discussion

Highly functionalized pyrrolidines have gained much interest in the past years as they constitute the structural element of many natural and synthetic pharmacologically active compounds [4]. Optically active pyrrolidines have been used as intermediates, chiral ligands or auxiliaries in controlled asymmetric synthesis [5]. Pyrrolidine compounds are reported to exhibit antifungal [6] and anti-influenza virus [7]. The asymmetric unit of the title compound (cf. the figure) consists of one molecule. The title compound contains one phenyl ring (C1—C6) and one pyrrolidine ring (C8—C11/N6). The pyrrolidine ring adopts an envelope conformation with a C10 atom displaced by 0.474(3) Å from the mean plane formed by the remaining ring atoms. The puckering parameters [8] for the pyrrolidine ring, which makes an angle of 76.85(6)° with the phenyl ring, are Q = 0.3026 Å and ϕ = 282.5416°. The N—C and C—C bonds lengths, and the C—C—N and C—N—C angles in the pyrrolidine ring are comparable with those in other pyrrolidines [5], [9], [10]. The phenyl ring is planar and stacked over one another with a centroid-centroid distance of 4.432(2) Å.

Acknowledgement

Financial support from the Ministry of Higher Education and Scientific Research of Tunisia is gratefully acknowledged.

References

Arfaoui, A.; Saâdi, F.; Ben Smida, Y.; Arfaoui, Y.; Nefzi, A.; Amri, H.: A convenient synthesis of 3,4-cis-disubstituted pyrrolidin-2-ones. Tetrahedron Lett. 56 (2015) 98–100.10.1016/j.tetlet.2014.11.023Suche in Google Scholar

Sheldrick, G. M.: A short history of SHELX. Acta Crystallogr. A64 (2008) 112–122.10.1107/S0108767307043930Suche in Google Scholar PubMed

North, A. C. T.; Phillips, D. C.; Mathews, F. S.: A semi-empirical method of absorption correction. Acta Crystallogr. 24 (1968) 351–359.10.1107/S0567739468000707Suche in Google Scholar

Waldmann, H.: Amino acid esters: Versatile chiral auxiliary groups for the asymmetric synthesis of nitrogen heterocycles. Synlett 2 (1995) 133–141.10.1055/s-1995-4882Suche in Google Scholar

Savithri, M. P.; Suresh, M.; Raghunathan, R.; Vimala, G.; Raja, R.; SubbiahPandi, A.: Crystal structures of ethyl (2S*,2′R*)-1′-methyl-2′′,3-dioxo-2,3-dihydrodispiro[1-benzothiophene-2,3′-pyrrolidine-2′,3′′-indoline]-4′-carboxylate and ethyl (2S*,2′R*)-5′′-chloro-1′-methyl-2′′,3-dioxo-2,3-δihydrodispiro[1-benzothiophene-2,3′-pyrrolidine-2′,3′′-indoline]-4′-carboxylate. Acta Crystallogr. E70 (2014) 94–97.10.1107/S1600536814015426Suche in Google Scholar PubMed PubMed Central

Govind, M. M.; Selvanayagam, S.; Velmurugan, D.; Ravikumar, K.; Rathna Durga, R.; Raghunathan, R.: 1,2,3,4-Tetrahydro-4′-furfuryl-1′-methylnaphthene-2-spiro-3′-pyrrolidine-2′-spiro-1′′-acenaphthene-1,2′′-dione. Acta Crystallogr. E59 (2003) o1875–o1877.10.1107/S1600536803024711Suche in Google Scholar

Gayathri, D.; Velmurugan, D.; Ravikumar, K.; Poornachandran, M.; Raghunathan, R.: 1′-Methyl-4′,5-diphenyl-5,6,7,8,9,10-hexahydro-1,3-cycloheptapyrimidino[2,3-b]thiazole-2-spiro-3′-pyrrolidine-2′-spiro-3′-1H-indole-2′′,3(2H,3′′H)-dione. Acta Crystallogr. E61 (2005) o3556–03558.10.1107/S1600536805031272Suche in Google Scholar

Cremer, D.; Pople, J. A.: General definition of ring puckering coordinates. J. Am. Chem. Soc. 97 (1975) 1354–1358.10.1021/ja00839a011Suche in Google Scholar

Mathusalini, S.; Viswanathan, V.; Mohan, P. S.; Lin, C. H.; Velmurugan, D.: Crystal structure of 4′-(2-methoxyquinolin-3-yl)-1′-methyldispiro[indan-2,2′-pyrrolidine-3′,3′′-indoline]-1,3,2′′-trione. Acta Crystallogr. E71 (2015) o1038–o1039.10.1107/S2056989015023026Suche in Google Scholar PubMed PubMed Central

Gainsford, G. J.; Mason, J. M.: Ethyl 1-benzyl-4-hydroxy-2-methyl-5-oxopyrrolidine-3-carboxylate. Acta Crystallogr. E66 (2010) o957–o957.10.1107/S1600536810010834Suche in Google Scholar PubMed PubMed Central

Duisenberg, A. J. M.: Indexing in single-crystal diffractometry with an obstinate list of reflections. Appl. Cryst. 25 (1992) 92–96.10.1107/S0021889891010634Suche in Google Scholar

Maciček, J.; Yordanov, A.: BLAF-a robust program for tracking out admittable Bravais lattice(s) from the experimental unit-cell data. J. Appl. Cryst. 25 (1992) 73–80.10.1107/S002188989100986XSuche in Google Scholar

Harms, K.; Wocadlo, S.: XCAD4, University of Marburg, Germany, (1995).Suche in Google Scholar

Farrugia, L. J.: WinGX and ORTEP for Windows: an update. J. Appl. Cryst. 45 (2012) 849–854.10.1107/S0021889812029111Suche in Google Scholar

Received: 2017-3-30
Accepted: 2017-7-26
Published Online: 2017-8-18
Published in Print: 2017-9-26

©2017 Hammouda Chebbi et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.

Artikel in diesem Heft

  1. Cover and Frontmatter
  2. Crystal structure of 2-(2-ethoxyphenyl)-7-propyl-5-methylimidazo[5,1-f][1,2,4]triazin-4(3H)-one, C17H20N4O2
  3. Crystal structure of catena-poly[aqua-(μ3-1,3,5-benzenetricarboxylato-κ3O:O′:O′′)-[μ3hydroxy-(1,3-di-(μ2-1,2,4-triazole-4-yl)benzoato-κ2N:N′)copper(II)], C19H16Cu2N6O9
  4. Crystal structure of poly[aqua-(μ3-3,5-di(4H-1,2,4-triazolyl-4-κ3N,N′:N′′)benzenecarboxylato)silver(I)], C11H9AgN6O3
  5. Crystal structure of tetrapropylammonium hydrogen carbonate, C13H29NO3
  6. Crystal structure of poly[μ2-acetato-κ3-O,O′:O′)diaqua(μ3-isophthalato-κ4O,O′:O′′:O′′′)yttrium(III)] monohydrate, C20H24O17Y2
  7. Crystal structure of catena-poly[dichlorido-(μ2-4-(1H-pyrazol-3-yl)-pyridine-κ2N,N′)]cadmium(II), C48H42Cd3Cl16N18
  8. Crystal structure of bis(tetraethylammonium) [1,1′-biphenyl]-2,2′-dicarboxylate trihydrate, C30H54N2O7
  9. Crystal structure of poly[(thiophene-3,4-dicarboxylato-κ1O)bis[1,2-bis(4-pyridyl)ethane-κ2N:N′]silver(I)] octahydrate, C30H42Ag2N4O12S
  10. The crystal structure of amine-(4-(1H-1,2,4-triazol-1-yl)benzoato-κN)silver(I) dihydrate, C9H13AgN4O4
  11. Crystal structure of poly[tetrakis(μ2-cyanido-κ2N:O)-cyanido-tris(pyridine)dicobalt(II/III)], C20H15Co2N8
  12. Crystal structure of bis(pyridine)-bis(2-formyl-4,6-dichlorophenolato)cobalt(II), C24H16Cl4CoN2O4
  13. Crystal structure of (E)-1-(4-(((E)-5-bromo-2-hydroxybenzylidene)amino)phenyl)ethan-1-one O-methyl oxime, C16H15BrN2O2
  14. Crystal structure of catena-poly[(μ2-3-(1H-pyrazol-4-yl)-5-(pyridin-4-yl)-1,2,4-triazole-κ N:N′)-bis(benzoato-κO)zinc(II)], C24H18N6O4Zn
  15. Hydrothermal synthesis and crystal structure of a poly[aqua-(μ4-4-(carboxylatomethyl)benzoato-κ4O:O′:O′′:O′′′)-(μ2-1-(4-(1H-imidazol-1-yl)benzyl)-1H-1,2,4-triazole-κ2N:N′) dimanganese(II)], [Mn2(C9H6O4)2(C12H11N5)(H2O)]
  16. Crystal structure of diaqua-catena-poly[diaqua-bis(μ2-5-(4-(1H-1,2,4-triazol-1-yl)phenyl)tetrazol-2-ido-κ2N:N′)cobalt(II)] dihydrate, C20H24CoN14O4
  17. Crystal structure of bis(μ3-2,2′-azanediylbis(ethan-1-olato)-κ5O:O,N,O′:O′)-tetrachlorido-bis(μ2-2-((2-hydroxyethyl)amino)ethan-1-olato-κ3N,O:O)dicobalt(II)dicobalt(III), C16H38Cl4Co4N4O8
  18. Crystal structure of poly[μ4-(4-(carboxylatomethyl)benzoato-κ4O:O′:O′′:O′′′)-(2-(4-(1H-imidazol-1-yl)phenyl)-1H-benzo[d]imidazole-κN)manganese(II)] [Mn(C9H6O4)(C16H12N4)]
  19. Crystal structure of 4-chloro-6-phenylpyrimidine, C10H7ClN2
  20. The crystal structure of [6-methoxy-2-(2,2,2-trifluoroacetyl)-3,4-dihydronaphthalen-1(2H)-one]difluoroborane, C13H10BF5O3
  21. Crystal structure of 3,3′-(butane-1,4-diylbis(azanylylidene))bis(1-phenylbut-1-en-1-olato)-κ4N,N′,O,O′]copper(II), C24H26N2O2Cu
  22. Crystal structure of tetraaqua-bis((E)-N′-(2-bromobenzylidene)isonicotinohydrazide-κN)zinc(II) dinitrate, C26H28N8O12Br2Zn
  23. Crystal structure of 2-amino-4-(4-bromophenyl)-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile, C16H13BrN2O2
  24. A single crystal study on tert-butyl-4-((4-(4-bromo-2-fluorophenylamino)-6-methoxyquinazolin-7-yloxy)methyl)piperidine-1-carboxylate, C26H30BrFN4O4
  25. Crystal structure of 1,1′-((1E,1′E)-(((ethane-1,2-diylbis(oxy))bis(2,1-phenylene))bis(azanylylidene))bis(methanylylidene))bis(naphthalen-2-olato-κ3O,O′,N)zinc(II), C36H26N2O4Zn
  26. Crystal structure of diaqua-bis(5′-(pyridin-1-ium-4-yl)-1H-[3,3′-bi(1,2,4-triazol)]-2′-ide-κ2N,N′)cobalt(II) — bis(5-(pyridin-4-yl-κN)-1H,1′H-3,3′-bi(1,2,4-triazole))octamolybdate – water (2/1/8), C27H33CoMo4N21O19
  27. Crystal structure of 3-cyclohexyl-2-(cyclohexylimino)-2,3-dihydro-6,8-diiodo-4H-1,3-benzoxazin-4-one, C20H24I2N2O2
  28. Crystal structure of dinitrato-κO-bis(tris((1H-benzo[d]imidazol-2-yl)methyl)amine-κ4N,N′,N′′,N′′′)-(μ2-cyclohexane-1,4-dicarboxylato-κ4O,O′:O′′,O′′′)dimanganese(II) – methanol – water (1/6/2), C62H80Mn2N16O18
  29. Crystal structure of bis(2-hydroxyethyl(phenyl)carbamodithioate)nickel(II), C18H20N2NiO2S4
  30. Crystal structure of methyl 1-(4-fluorobenzyl)-4-methoxy-5-oxopyrrolidine-3-carboxylate, C14H16FNO4
  31. Crystal structure of di-μ-iodido-bis(6-(p-tolyl)-2,2′-bipyridine-κ2N,N′)dicopper(I) — 2-(diphenylphosphoryl)benzoic acid (1/2), C36H29CuIN2O3P
  32. Crystal structure of 2-amino-4-(3-bromo-4-fluoro-phenyl)-7,7-dimethyl-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile, C18H16BrFN2O2
  33. Crystal structure of bis(μ2-2-chlorobenzoato-κ3O,O′:O′)-(2-chlorobenzoato-κO)-(2-chlorobenzoato-κO,O′)-bis(1,10-phenanthroline-κ2N,N′)-dicadmium(II) monohydrate, C52H36Cd2Cl4N4O10
  34. Crystal structure of 2-(8a-methyl-5-oxo-hexahydroimidazo [1,2-a]pyridin-1(5H)-yl)-2-oxoethyl acetate, C12H18N2O4
  35. Crystal structure of (E)-N,N-diethyl-2-(5-nitrothiazol-2-yl)-1-phenylethen-1-amine, C15H17N3O2S
  36. Crystal structure of diazido-dimethanolato-bis(μ2-2-(((3-oxidopropyl)imino)methyl)phenolato-κ4O:O,O′,N)dimanganese(III), C22H28Mn2N8O6
  37. The crystal structure of bis(2-(2,2,2-trifluoroacetyl)-3,4-dihydronaphthalen-1-olato-κ2O,O′)copper(II), C24H16CuF6O4
  38. Crystal structure of hexaaquanickel(II) bis((E)-4-((4-(dimethylamino)phenyl)diazenyl)benzenesulfonate), C28H40N6NiO12S2
  39. Crystal structure of catena-poly[aqua-(μ2-hexamethylenetetramine-κ2N:N′)-bis(2,6-difluorobenzoato-κ2O:O′)cadmium(II)]monohydrate, C20H22CdF4N4O6
  40. Crystal structure of 3-benzyl-2,3-dihydro-2-thioxoquinazolin-4(1H)-one, C15H12N2OS
  41. Crystal structure of bis(μ2-ferrocenecarboxylato-κ2O:O′)-bis(1,10-phenanthroline-κ2N,N′)-(μ2-methanolato2O,O)dicopper(II) tetrafluoroborate – acetonitrile (1/1), C49H40BCu2F4Fe2N5O5
  42. The crystal structure of tetrakis(1,3,5-triaza-7-phosphatricyclo[3.3.1.13,7]decane-κP)silver(I) chloride dihydrate, C24H60AgClN12O6P4
  43. Crystal structure of 5-ethyl-2-(p-tolyl)-1,3-dioxane-5-carboxylic acid, C14H18O4
  44. Crystal structure of 2-(4-fluorophenyl)-1,3-dimethyl-1H-perimidin-3-ium iodide, C19H16ClIN2
  45. Crystal structure of catena-poly[(μ2-hexamethylenetetramine-κ2N:N′)-tetrakis(μ2-2,6-difluorobenzoato-κ2O:O′)dicopper(II)], C34H24Cu2F8N4O8
  46. Crystal structure of ethyl 3-hydroxy-5-methyl-2-(4-(m-tolyl)-1H-1,2,3-triazol-1-yl)-[1,1′-biphenyl]-4- carboxylate, C25H24N3O3
  47. The crystal structure of carbonyl(2-oxopyridin-1(2H)-olato-κ2O,O′)-(diphenylcyclohexylphosphine-κP)rhodium(I), C24H25NO3PRh
  48. Crystal structure of bis((pyrazin-2-ylmethyl)(pyrazine-2-carbonyl)amido-κ3N,N′,N′′)copper(II), C20H16CuN10O2
  49. Crystal structure of catena-poly[tetraaqua-(μ2-succinonitrile-κ2N:N′)cobalt(II)] dinitrate, C4H12CoN4O10
  50. The crystal structure of 1,1′-bisisoquinoline, C18H12N2
  51. Crystal structure of bis(hydroxydi(pyridin-2-yl)methanolato-κ3N,N′,O)cobalt(III) perchlorate dihydrate, C22H22ClCoN4O10
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