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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): o3205.
Published online 2010 November 17. doi:  10.1107/S1600536810045691
PMCID: PMC3011499

Diethyl 4-acetyl-5-(2-nitro­phen­yl)pyrrolidine-2,2-dicarboxyl­ate

Abstract

The title compound, C18H22N2O7, was synthesized by the 1,3-dipolar cyclo­addition reaction of but-3-en-2-one, diethyl 2-amino­malonate and 2-nitro­benzaldehyde. In the mol­ecule, the pyrrolidine ring possesses an envelope conformation. Inter­molecular N—H(...)O and C—H(...)O hydrogen bonds are present in the crystal structure.

Related literature

For the biological activity of pyrrolidine derivatives, see: Coldham & Hufton (2005 [triangle]); Grigg (1995 [triangle]); Kravchenko et al. (2005 [triangle]); Nair & Suja (2007 [triangle]); Pandey et al. (2006 [triangle]); Sardina & Rapoport (1996 [triangle]); Witherup et al. (1995 [triangle]). For a related structure, see: He (2009 [triangle]).

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Object name is e-66-o3205-scheme1.jpg

Experimental

Crystal data

  • C18H22N2O7
  • M r = 378.38
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3205-efi1.jpg
  • a = 10.687 (5) Å
  • b = 7.760 (5) Å
  • c = 12.030 (5) Å
  • β = 97.455 (5)°
  • V = 989.2 (9) Å3
  • Z = 2
  • Cu Kα radiation
  • μ = 0.83 mm−1
  • T = 291 K
  • 0.38 × 0.36 × 0.30 mm

Data collection

  • Oxford Diffraction Gemini S Ultra diffractometer
  • Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 [triangle]) T min = 0.743, T max = 0.789
  • 19238 measured reflections
  • 2105 independent reflections
  • 1915 reflections with I > 2σ(I)
  • R int = 0.023

Refinement

  • R[F 2 > 2σ(F 2)] = 0.081
  • wR(F 2) = 0.166
  • S = 1.04
  • 2105 reflections
  • 249 parameters
  • 42 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.33 e Å−3
  • Δρmin = −0.42 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 [triangle]); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 [triangle]); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810045691/xu5078sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810045691/xu5078Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The diffraction measurements were made at the Centre for Testing and Analysis, Chengdu Branch, Chinese Academy of Sciences. I acknowledge financial support from China West Normal University.

supplementary crystallographic information

Comment

Substituted pyrrolidine compound is an important class of heterocyclic compounds with wide spread applications to the synthesis of biologically active compounds and natural products (Coldham et al., 2005; Grigg, 1995; Kravchenko et al., 2005; Nair et al., 2007; Pandey et al., 2006; Sardina et al., 1996; Witherup et al. 1995). Its crystal structure is reported here.

The molecular structure of (I) is shown in Fig. 1. Bond lengths and angles in (I) are normal. The pyrrolidine ring possesses an envelope conformation. The crystal packing is stabilized by N—H···0 and C—H···0 hydrogen bonding (Table 1).

Experimental

2-Nitrobenzaldehyde (0.018 g, 0.12 mmol) and diethyl 2-aminomalonate (0.017 g, 0.1 mmol) were added to a solution of methyl but-3-en-2-one (0.014 g, 0.2 mmol) in dichloromethane (2 ml). To the stirred mixture, phosphenous acid (5 mg, 0.01 mmol) was added. After the mixture had been stirred at 293 K for 48 h, the reaction was quenched with a saturated solution of sodium bicarbonate (5 ml). The mixture was extracted with ethyl acetate, evaporated and separated by flash chromatograghy. A colourless powder was obtained. Single crystals suitable for X-ray diffraction were obtained by slow evaporation of an ethyl acetate solution.

Refinement

H atom on N atom was located in a difference Fourier map and refined isotropically. The carbon-bound hydrogen atoms were placed in calculated positions, with C—H = 0.93–0.98 Å, and refined using a riding model, with Uiso(H) = 1.5Ueq(C) for methyl H atoms and Uiso(H) = 1.2Ueq(C) for the others.

Figures

Fig. 1.
The molecular structure of (I) with 30% probability displacement ellipsoids (arbitrary spheres for H atoms).

Crystal data

C18H22N2O7F(000) = 400
Mr = 378.38Dx = 1.270 Mg m3
Monoclinic, P21Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2ybCell parameters from 11509 reflections
a = 10.687 (5) Åθ = 4.2–72.3°
b = 7.760 (5) ŵ = 0.83 mm1
c = 12.030 (5) ÅT = 291 K
β = 97.455 (5)°Block, colorless
V = 989.2 (9) Å30.38 × 0.36 × 0.30 mm
Z = 2

Data collection

Oxford Diffraction Gemini S Ultra diffractometer2105 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source1915 reflections with I > 2σ(I)
mirrorRint = 0.023
ω scansθmax = 72.6°, θmin = 4.2°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)h = −13→13
Tmin = 0.743, Tmax = 0.789k = −8→9
19238 measured reflectionsl = −14→14

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.081H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.166w = 1/[σ2(Fo2) + (0.025P)2 + 1.3702P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
2105 reflectionsΔρmax = 0.33 e Å3
249 parametersΔρmin = −0.42 e Å3
42 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.017 (3)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

xyzUiso*/Ueq
O30.0038 (5)0.2421 (8)0.5230 (4)0.0881 (16)
N20.2698 (5)0.3189 (8)0.6658 (4)0.0681 (15)
O50.1828 (5)0.4223 (10)0.8609 (6)0.117 (2)
C30.2453 (6)0.4941 (9)0.4653 (6)0.0641 (16)
H30.19410.51840.52020.077*
O10.4209 (6)0.0223 (8)0.4138 (5)0.0957 (18)
C20.3126 (5)0.3415 (9)0.4718 (5)0.0566 (14)
O60.4399 (5)0.1838 (10)0.8411 (4)0.108 (2)
O40.0249 (5)0.2457 (11)0.8118 (5)0.112 (2)
O20.5571 (5)0.1618 (10)0.3371 (5)0.120 (2)
C80.1956 (6)0.0846 (9)0.5533 (5)0.0631 (16)
H80.2247−0.01920.51800.076*
N10.4602 (6)0.1556 (10)0.3797 (5)0.0784 (17)
C70.3030 (5)0.2205 (9)0.5697 (4)0.0589 (15)
H70.38410.16240.59050.071*
C10.3875 (5)0.3157 (10)0.3870 (5)0.0605 (15)
C160.1311 (7)0.2862 (12)0.8096 (6)0.079 (2)
C40.2514 (6)0.6116 (10)0.3802 (6)0.0776 (19)
H40.20280.71130.37710.093*
C120.0663 (7)0.1228 (11)0.3583 (5)0.085 (2)
H12A−0.00970.17600.32280.128*
H12B0.06200.00070.34550.128*
H12C0.13750.16940.32740.128*
C110.0803 (6)0.1578 (9)0.4820 (5)0.0649 (16)
O70.2881 (6)0.0324 (11)0.9076 (6)0.130 (2)
C100.2269 (6)0.1943 (11)0.7453 (5)0.0721 (19)
C60.3975 (6)0.4353 (11)0.3036 (6)0.0732 (19)
H60.45110.41490.25000.088*
C130.3357 (7)0.1387 (14)0.8371 (6)0.092 (2)
C90.1723 (8)0.0442 (10)0.6740 (5)0.080 (2)
H9A0.08260.03300.67820.096*
H9B0.2137−0.06250.69950.096*
C50.3294 (7)0.5809 (11)0.3001 (6)0.084 (2)
H50.33500.66110.24350.101*
C170.1066 (10)0.5318 (17)0.9259 (8)0.128 (3)
H17A0.01740.52310.89850.154*
H17B0.13250.65150.92460.154*
C140.3850 (10)−0.0385 (18)1.0007 (8)0.137 (3)
H14A0.3874−0.16340.99940.165*
H14B0.46870.00640.99540.165*
C150.3341 (11)0.0277 (19)1.1036 (8)0.153 (3)
H15A0.3856−0.01411.16940.229*
H15B0.2490−0.01211.10360.229*
H15C0.33520.15141.10340.229*
C180.1366 (11)0.455 (2)1.0415 (9)0.158 (3)
H18A0.08960.51411.09250.237*
H18B0.22530.46641.06630.237*
H18C0.11410.33501.03910.237*
H100.342 (4)0.377 (8)0.693 (5)0.07 (2)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O30.066 (2)0.101 (4)0.099 (4)−0.003 (3)0.016 (3)−0.005 (3)
N20.073 (3)0.076 (4)0.056 (3)−0.017 (3)0.011 (2)−0.010 (3)
O50.081 (3)0.119 (5)0.154 (4)−0.015 (4)0.020 (3)−0.040 (5)
C30.059 (3)0.062 (4)0.073 (4)−0.001 (3)0.015 (3)−0.002 (3)
O10.105 (4)0.091 (4)0.092 (4)0.024 (4)0.015 (3)0.000 (4)
C20.048 (3)0.065 (4)0.057 (3)−0.007 (3)0.004 (2)−0.003 (3)
O60.075 (3)0.172 (7)0.075 (3)0.018 (4)0.004 (2)−0.009 (4)
O40.080 (3)0.162 (7)0.097 (4)−0.018 (4)0.025 (3)0.000 (4)
O20.090 (3)0.153 (6)0.126 (4)0.051 (4)0.051 (3)0.031 (5)
C80.072 (4)0.058 (4)0.059 (3)−0.007 (3)0.003 (3)0.000 (3)
N10.076 (4)0.093 (5)0.067 (3)0.020 (4)0.011 (3)−0.001 (4)
C70.058 (3)0.066 (4)0.051 (3)−0.007 (3)0.003 (2)0.000 (3)
C10.053 (3)0.070 (4)0.058 (3)0.005 (3)0.007 (2)0.000 (3)
C160.068 (4)0.106 (7)0.067 (4)0.001 (5)0.018 (3)0.010 (4)
C40.076 (4)0.066 (5)0.091 (5)0.002 (4)0.014 (4)0.005 (4)
C120.090 (5)0.086 (6)0.073 (4)−0.010 (5)−0.018 (3)−0.001 (4)
C110.062 (3)0.062 (4)0.070 (4)−0.014 (3)0.006 (3)−0.002 (3)
O70.124 (3)0.135 (4)0.131 (3)−0.003 (3)0.011 (2)0.020 (3)
C100.071 (4)0.092 (5)0.053 (3)−0.014 (4)0.005 (3)0.002 (4)
C60.072 (4)0.084 (5)0.065 (4)0.002 (4)0.019 (3)0.001 (4)
C130.070 (4)0.127 (7)0.078 (4)0.001 (4)0.010 (3)−0.023 (3)
C90.104 (5)0.076 (5)0.060 (4)−0.021 (4)0.008 (4)0.006 (4)
C50.090 (5)0.077 (5)0.086 (5)−0.005 (5)0.018 (4)0.015 (5)
C170.126 (4)0.131 (4)0.132 (3)0.013 (3)0.031 (3)−0.018 (3)
C140.139 (4)0.140 (4)0.130 (3)0.006 (3)0.007 (2)0.017 (3)
C150.165 (4)0.155 (5)0.134 (3)0.009 (3)0.004 (3)−0.002 (3)
C180.168 (5)0.165 (5)0.142 (3)0.009 (3)0.026 (3)−0.001 (3)

Geometric parameters (Å, °)

O3—C111.202 (8)C12—C111.501 (9)
N2—C71.467 (8)C12—H12A0.9600
N2—C101.474 (9)C12—H12B0.9600
N2—H100.92 (5)C12—H12C0.9600
O5—C161.308 (10)O7—C131.330 (11)
O5—C171.470 (11)O7—C141.525 (11)
C3—C41.378 (9)C10—C91.518 (10)
C3—C21.383 (9)C10—C131.557 (10)
C3—H30.9300C6—C51.342 (11)
O1—N11.208 (9)C6—H60.9300
C2—C11.390 (8)C9—H9A0.9700
C2—C71.521 (8)C9—H9B0.9700
O6—C131.162 (9)C5—H50.9300
O4—C161.181 (8)C17—C181.509 (9)
O2—N11.214 (7)C17—H17A0.9700
C8—C111.517 (8)C17—H17B0.9700
C8—C91.537 (8)C14—C151.506 (9)
C8—C71.552 (8)C14—H14A0.9700
C8—H80.9800C14—H14B0.9700
N1—C11.474 (9)C15—H15A0.9600
C7—H70.9800C15—H15B0.9600
C1—C61.382 (9)C15—H15C0.9600
C16—C101.536 (10)C18—H18A0.9600
C4—C51.375 (9)C18—H18B0.9600
C4—H40.9300C18—H18C0.9600
C7—N2—C10107.3 (6)N2—C10—C16107.8 (6)
C7—N2—H10105 (4)C9—C10—C16114.1 (6)
C10—N2—H10114 (4)N2—C10—C13112.0 (6)
C16—O5—C17119.2 (7)C9—C10—C13112.7 (7)
C4—C3—C2122.3 (6)C16—C10—C13104.9 (5)
C4—C3—H3118.9C5—C6—C1119.7 (6)
C2—C3—H3118.9C5—C6—H6120.1
C3—C2—C1115.3 (6)C1—C6—H6120.1
C3—C2—C7119.1 (5)O6—C13—O7127.1 (9)
C1—C2—C7125.6 (6)O6—C13—C10124.7 (9)
C11—C8—C9113.0 (5)O7—C13—C10108.2 (7)
C11—C8—C7110.5 (5)C10—C9—C8106.3 (6)
C9—C8—C7103.1 (5)C10—C9—H9A110.5
C11—C8—H8110.0C8—C9—H9A110.5
C9—C8—H8110.0C10—C9—H9B110.5
C7—C8—H8110.0C8—C9—H9B110.5
O1—N1—O2122.1 (8)H9A—C9—H9B108.7
O1—N1—C1119.4 (6)C6—C5—C4120.0 (7)
O2—N1—C1118.5 (8)C6—C5—H5120.0
N2—C7—C2109.7 (6)C4—C5—H5120.0
N2—C7—C8101.8 (5)O5—C17—C18101.2 (9)
C2—C7—C8116.4 (4)O5—C17—H17A111.5
N2—C7—H7109.6C18—C17—H17A111.5
C2—C7—H7109.6O5—C17—H17B111.5
C8—C7—H7109.6C18—C17—H17B111.5
C6—C1—C2122.8 (7)H17A—C17—H17B109.3
C6—C1—N1115.6 (6)C15—C14—O7101.4 (8)
C2—C1—N1121.6 (6)C15—C14—H14A111.5
O4—C16—O5123.5 (8)O7—C14—H14A111.5
O4—C16—C10126.3 (8)C15—C14—H14B111.5
O5—C16—C10110.1 (6)O7—C14—H14B111.5
C5—C4—C3119.8 (7)H14A—C14—H14B109.3
C5—C4—H4120.1C14—C15—H15A109.5
C3—C4—H4120.1C14—C15—H15B109.5
C11—C12—H12A109.5H15A—C15—H15B109.5
C11—C12—H12B109.5C14—C15—H15C109.5
H12A—C12—H12B109.5H15A—C15—H15C109.5
C11—C12—H12C109.5H15B—C15—H15C109.5
H12A—C12—H12C109.5C17—C18—H18A109.5
H12B—C12—H12C109.5C17—C18—H18B109.5
O3—C11—C12121.3 (7)H18A—C18—H18B109.5
O3—C11—C8121.1 (6)C17—C18—H18C109.5
C12—C11—C8117.6 (6)H18A—C18—H18C109.5
C13—O7—C14114.4 (7)H18B—C18—H18C109.5
N2—C10—C9105.4 (5)
C4—C3—C2—C10.5 (9)C7—N2—C10—C16−150.7 (5)
C4—C3—C2—C7178.7 (6)C7—N2—C10—C1394.5 (7)
C10—N2—C7—C2164.3 (5)O4—C16—C10—N2120.5 (8)
C10—N2—C7—C840.5 (6)O5—C16—C10—N2−57.8 (8)
C3—C2—C7—N2−25.6 (7)O4—C16—C10—C93.7 (11)
C1—C2—C7—N2152.3 (6)O5—C16—C10—C9−174.5 (7)
C3—C2—C7—C889.2 (7)O4—C16—C10—C13−120.0 (9)
C1—C2—C7—C8−92.9 (7)O5—C16—C10—C1361.8 (9)
C11—C8—C7—N284.9 (6)C2—C1—C6—C5−2.4 (10)
C9—C8—C7—N2−36.2 (6)N1—C1—C6—C5176.5 (7)
C11—C8—C7—C2−34.3 (8)C14—O7—C13—O6−1.7 (14)
C9—C8—C7—C2−155.3 (6)C14—O7—C13—C10178.0 (8)
C3—C2—C1—C61.7 (9)N2—C10—C13—O6−2.8 (12)
C7—C2—C1—C6−176.3 (6)C9—C10—C13—O6115.9 (10)
C3—C2—C1—N1−177.2 (6)C16—C10—C13—O6−119.5 (10)
C7—C2—C1—N14.8 (9)N2—C10—C13—O7177.5 (7)
O1—N1—C1—C6−148.9 (7)C9—C10—C13—O7−63.8 (8)
O2—N1—C1—C629.6 (9)C16—C10—C13—O760.8 (9)
O1—N1—C1—C230.0 (10)N2—C10—C9—C84.1 (8)
O2—N1—C1—C2−151.4 (6)C16—C10—C9—C8122.2 (6)
C17—O5—C16—O40.4 (13)C13—C10—C9—C8−118.4 (6)
C17—O5—C16—C10178.7 (7)C11—C8—C9—C10−99.6 (7)
C2—C3—C4—C5−2.0 (11)C7—C8—C9—C1019.7 (7)
C9—C8—C11—O330.1 (9)C1—C6—C5—C40.8 (11)
C7—C8—C11—O3−84.8 (8)C3—C4—C5—C61.3 (11)
C9—C8—C11—C12−150.7 (6)C16—O5—C17—C1893.1 (11)
C7—C8—C11—C1294.4 (7)C13—O7—C14—C15119.5 (10)
C7—N2—C10—C9−28.4 (7)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H10···O2i0.92 (5)2.51 (6)3.244 (9)138 (5)
C18—H18A···O4ii0.962.533.460 (15)162 (6)

Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) −x, y+1/2, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU5078).

References

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