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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o344.
Published online 2007 December 21. doi:  10.1107/S1600536807067268
PMCID: PMC2915385

(E)-Methyl 2-[(4-nitro­phen­yl)­hydrazono]­propanoate

Abstract

The title compound, C10H11N3O4, is a condensation product of 4-nitro­phenyl­hydrazine and methyl pyruvate. The complete mol­ecule except for the methyl groups can be considered as a conjugated π system. All non-H atoms are approximately coplanar (r.m.s. deviation 0.117 Å). The crystal packing involves an N—H(...)O hydrogen bond and a π–π inter­action between the aromatic rings, with a centroid–centroid distance of 3.617 Å.

Related literature

For related literature, see: Humphrey & Kuethe (2006 [triangle]); Tietze et al. (2003 [triangle]); Van Order & Lindwall (1942 [triangle]).

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Object name is e-64-0o344-scheme1.jpg

Experimental

Crystal data

  • C10H11N3O4
  • M r = 237.22
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o344-efi1.jpg
  • a = 12.836 (3) Å
  • b = 6.9260 (14) Å
  • c = 11.915 (2) Å
  • β = 90.11 (3)°
  • V = 1059.3 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 173 (2) K
  • 0.60 × 0.54 × 0.16 mm

Data collection

  • Rigaku R-AXIS SPIDER diffractometer
  • Absorption correction: none
  • 9730 measured reflections
  • 2416 independent reflections
  • 1997 reflections with I > 2σ(I)
  • R int = 0.021

Refinement

  • R[F 2 > 2σ(F 2)] = 0.042
  • wR(F 2) = 0.126
  • S = 1.09
  • 2416 reflections
  • 176 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.29 e Å−3
  • Δρmin = −0.29 e Å−3

Data collection: RAPID-AUTO (Rigaku, 2004 [triangle]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: ORTEX (McArdle, 1995 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807067268/bt2665sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807067268/bt2665Isup2.hkl

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

Acknowledgments

This work was supported by the Foundations of Fujian Province (No. 2006F5058) and Fuzhou University (No. XRC0527).

supplementary crystallographic information

Comment

The title compound, a phenylhydrazone derivative, is an important intermediate for the synthesis of indoles by the Fischer indole reaction (Van Order & Lindwall, 1942; Humphrey & Kuethe, 2006).

The molecular structure of the title compound is shown in Fig. 1. The complete molecule except the methyl groups can be considered as a conjugated π-system. All non-H atoms lie in a common plane (r.m.s. deviation 0.117 Å). The crystal packing shows an N—H···O hydrogen bond (Table 1) and a π-π interaction between the aromatic rings with a centroid-centroid distance of 3.617Å (symmetry operator: 1 - x, -y, 1 - z).

Experimental

A suspension of 4-nitrophenylhydrazine (7.65 g, 50 mmol) in concd. HCl (20 ml) and H2O (20 ml) was heated to reflux untill the suspension solved. The solution was cooled to room temperature. Then the precipitate was filtrated off and dried. The solid was dissolved in methanol (100 ml) and treated with NaOAc (4.92 g, 60 mmol) and methyl pyruvate (5.10 g, 50 mmol). The mixture was stirred at room temperature for 18 h. Then the yellow precipitate was filtered off, washed with methanol and dried to afford 11.13 g of the title compound (47 mmol, 94%) (Tietze et al., 2003). mp: 209.6–211.1°C. IR: (KBr, ν, cm-1): 3301 (N—H), 2962 (C—H), 1716 (C—O), 1611 (C—N), 1578, 1504, 1486, 1438, 1338, 1399, 1253, 1177, 1130, 1113, 847, 751.

Refinement

H atoms of the two methyl groups were refined using a riding model with C—H = 0.96Å and U(H)=1.5Ueq(C). These methyl groups were allowed to rotate but not to tip. All other H atoms were freely refined.

Figures

Fig. 1.
The molecular structure of the title compound with atom labels and 50% probability displacement ellipsoids for non-H atoms.

Crystal data

C10H11N3O4F000 = 496
Mr = 237.22Dx = 1.487 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71069 Å
Hall symbol: -P2ybcCell parameters from 7757 reflections
a = 12.836 (3) Åθ = 6.4–55.0º
b = 6.9260 (14) ŵ = 0.12 mm1
c = 11.915 (2) ÅT = 173 (2) K
β = 90.11 (3)ºChip, yellow
V = 1059.3 (4) Å30.60 × 0.54 × 0.16 mm
Z = 4

Data collection

Rigaku R-AXIS Spider diffractometer2416 independent reflections
Radiation source: Rotating Anode1997 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.021
Detector resolution: 10 pixels mm-1θmax = 27.5º
T = 173(2) Kθmin = 3.2º
ω oscillation scansh = −16→16
Absorption correction: nonek = −8→7
9730 measured reflectionsl = −15→15

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.126  w = 1/[σ2(Fo2) + (0.0696P)2 + 0.336P] where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
2416 reflectionsΔρmax = 0.29 e Å3
176 parametersΔρmin = −0.29 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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
N10.23523 (9)0.09076 (17)0.62405 (10)0.0249 (3)
N20.65298 (8)0.28388 (17)0.55245 (9)0.0217 (3)
H50.6937 (13)0.255 (3)0.6065 (15)0.028 (4)*
N30.68657 (8)0.33719 (16)0.44935 (9)0.0202 (3)
O10.21019 (8)0.03458 (18)0.71835 (9)0.0362 (3)
O20.17278 (8)0.10441 (19)0.54620 (10)0.0381 (3)
O30.75514 (8)0.43209 (18)0.24033 (8)0.0339 (3)
O40.90897 (7)0.50736 (15)0.31757 (8)0.0256 (3)
C10.34331 (10)0.14249 (18)0.60429 (11)0.0200 (3)
C20.37287 (10)0.2085 (2)0.49903 (11)0.0219 (3)
H10.3235 (14)0.217 (3)0.4375 (16)0.040 (5)*
C30.47596 (10)0.25744 (19)0.48098 (11)0.0207 (3)
H20.4965 (13)0.309 (2)0.4086 (15)0.029 (4)*
C40.54879 (9)0.23761 (19)0.56748 (10)0.0188 (3)
C50.51738 (10)0.1701 (2)0.67302 (11)0.0225 (3)
H30.5685 (14)0.158 (3)0.7310 (16)0.035 (5)*
C60.41453 (10)0.1227 (2)0.69133 (11)0.0225 (3)
H40.3938 (13)0.072 (3)0.7635 (15)0.031 (4)*
C70.78391 (10)0.37883 (19)0.43797 (11)0.0204 (3)
C80.86529 (11)0.3763 (3)0.52797 (12)0.0333 (4)
H60.87670.50530.55480.050*
H70.92910.32580.49800.050*
H80.84230.29620.58880.050*
C90.81181 (10)0.44003 (19)0.32127 (11)0.0204 (3)
C100.94452 (11)0.5806 (2)0.21009 (12)0.0303 (3)
H91.01300.63450.21850.045*
H100.89750.67880.18410.045*
H110.94660.47700.15660.045*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0205 (6)0.0267 (6)0.0276 (6)−0.0007 (5)0.0051 (4)−0.0034 (5)
N20.0181 (5)0.0302 (6)0.0169 (5)−0.0020 (5)0.0008 (4)0.0016 (4)
N30.0202 (5)0.0217 (6)0.0188 (5)−0.0005 (4)0.0040 (4)−0.0011 (4)
O10.0273 (5)0.0512 (7)0.0302 (6)−0.0087 (5)0.0102 (4)0.0038 (5)
O20.0202 (5)0.0564 (8)0.0376 (6)−0.0041 (5)−0.0033 (4)0.0014 (5)
O30.0255 (5)0.0559 (7)0.0202 (5)−0.0093 (5)−0.0011 (4)0.0031 (5)
O40.0199 (5)0.0350 (6)0.0220 (5)−0.0066 (4)0.0039 (3)0.0013 (4)
C10.0174 (6)0.0199 (6)0.0227 (6)−0.0011 (5)0.0036 (5)−0.0039 (5)
C20.0204 (6)0.0246 (7)0.0208 (6)0.0013 (5)−0.0005 (5)−0.0005 (5)
C30.0216 (6)0.0234 (6)0.0172 (6)0.0006 (5)0.0026 (5)0.0017 (5)
C40.0186 (6)0.0184 (6)0.0193 (6)0.0000 (5)0.0031 (4)−0.0022 (5)
C50.0210 (6)0.0293 (7)0.0173 (6)−0.0004 (5)0.0001 (5)−0.0010 (5)
C60.0235 (6)0.0266 (7)0.0173 (6)−0.0014 (5)0.0045 (5)−0.0006 (5)
C70.0195 (6)0.0217 (6)0.0199 (6)−0.0017 (5)0.0019 (5)−0.0024 (5)
C80.0234 (6)0.0543 (10)0.0223 (7)−0.0100 (7)−0.0005 (5)0.0040 (6)
C90.0191 (6)0.0216 (6)0.0207 (6)−0.0007 (5)0.0028 (5)−0.0022 (5)
C100.0256 (7)0.0384 (8)0.0270 (7)−0.0052 (6)0.0085 (5)0.0057 (6)

Geometric parameters (Å, °)

N1—O21.2284 (17)C3—C41.3970 (18)
N1—O11.2323 (16)C3—H20.970 (18)
N1—C11.4525 (16)C4—C51.4016 (18)
N2—N31.3540 (15)C5—C61.3783 (18)
N2—C41.3872 (16)C5—H30.956 (18)
N2—H50.853 (18)C6—H40.966 (18)
N3—C71.2897 (16)C7—C81.4958 (19)
O3—C91.2080 (17)C7—C91.4977 (18)
O4—C91.3323 (15)C8—H60.9600
O4—C101.4518 (16)C8—H70.9600
C1—C61.3880 (19)C8—H80.9600
C1—C21.3885 (19)C10—H90.9600
C2—C31.3831 (17)C10—H100.9600
C2—H10.970 (19)C10—H110.9600
O2—N1—O1122.81 (12)C4—C5—H3118.7 (11)
O2—N1—C1118.73 (11)C5—C6—C1119.20 (12)
O1—N1—C1118.46 (12)C5—C6—H4119.5 (10)
N3—N2—C4119.27 (11)C1—C6—H4121.3 (10)
N3—N2—H5123.6 (11)N3—C7—C8126.68 (12)
C4—N2—H5116.0 (11)N3—C7—C9113.23 (11)
C7—N3—N2117.81 (11)C8—C7—C9120.07 (11)
C9—O4—C10116.57 (11)C7—C8—H6109.5
C6—C1—C2121.79 (12)C7—C8—H7109.5
C6—C1—N1118.84 (12)H6—C8—H7109.5
C2—C1—N1119.37 (12)C7—C8—H8109.5
C3—C2—C1118.97 (12)H6—C8—H8109.5
C3—C2—H1119.4 (11)H7—C8—H8109.5
C1—C2—H1121.6 (11)O3—C9—O4123.49 (12)
C2—C3—C4120.02 (12)O3—C9—C7125.70 (12)
C2—C3—H2119.3 (10)O4—C9—C7110.81 (11)
C4—C3—H2120.6 (10)O4—C10—H9109.5
N2—C4—C3121.74 (12)O4—C10—H10109.5
N2—C4—C5118.16 (12)H9—C10—H10109.5
C3—C4—C5120.10 (12)O4—C10—H11109.5
C6—C5—C4119.92 (12)H9—C10—H11109.5
C6—C5—H3121.4 (11)H10—C10—H11109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H5···O3i0.853 (18)2.200 (18)2.9928 (17)154.6 (16)

Symmetry codes: (i) x, −y+1/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2665).

References

  • Humphrey, G. R. & Kuethe, J. T. (2006). Chem. Rev.106, 2875–2911. [PubMed]
  • McArdle, P. (1995). J. Appl. Cryst.28, 65.
  • Rigaku (2004). RAPID-AUTO Version 3.0. Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (1990). Acta Cryst. A46, 467–473.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
  • Tietze, L. F., Haunert, F., Feuerstein, T. & Herzig, T. (2003). Eur. J. Org. Chem. pp. 562–566.
  • Van Order, R. B. & Lindwall, H. G. (1942). Chem. Rev.30, 69–96.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography