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

Yu, H.-Y.; Fang, X.; Cao, M.-L.; Zhang, Y.-J.; Wang, J.-D.

doi:10.1107/S1600536807067268

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o344

https://doi.org/10.1107/S1600536807067268

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

Hai-Yang Yu,^a Xin Fang,^a Ming-Lei Cao,^a Yan-Jun Zhang ^a and Jun-Dong Wang ^a ^*

^aDepartment of Chemistry, University of Fuzhou, Fuzhou 350002, People's Republic of China
^*Correspondence e-mail: yhyang198@yahoo.com.cn

(Received 10 December 2007; accepted 17 December 2007; online 21 December 2007)

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 ); Tietze et al. (2003 ); Van Order & Lindwall (1942 ).

Experimental

Crystal data

C₁₀H₁₁N₃O₄
M_r = 237.22
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.042
wR(F²) = 0.126
S = 1.09
2416 reflections
176 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H5⋯O3ⁱ	0.853 (18)	2.200 (18)	2.9928 (17)	154.6 (16)
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807067268/bt2665Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Structure description top

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).

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

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: SHELXL97-2 (Sheldrick, 1997).

Figures top

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

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

Crystal data top

C₁₀H₁₁N₃O₄	F(000) = 496
M_r = 237.22	D_x = 1.487 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P2ybc	Cell parameters from 7757 reflections
a = 12.836 (3) Å	θ = 6.4–55.0°
b = 6.9260 (14) Å	µ = 0.12 mm⁻¹
c = 11.915 (2) Å	T = 173 K
β = 90.11 (3)°	Chip, yellow
V = 1059.3 (4) Å³	0.60 × 0.54 × 0.16 mm
Z = 4

Data collection top

Rigaku R-AXIS Spider diffractometer	1997 reflections with I > 2σ(I)
Radiation source: Rotating Anode	R_int = 0.021
Graphite monochromator	θ_max = 27.5°, θ_min = 3.2°
Detector resolution: 10 pixels mm^-1	h = −16→16
ω oscillation scans	k = −8→7
9730 measured reflections	l = −15→15
2416 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0696P)² + 0.336P] where P = (F_o² + 2F_c²)/3
2416 reflections	(Δ/σ)_max < 0.001
176 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₀H₁₁N₃O₄	V = 1059.3 (4) Å³
M_r = 237.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.836 (3) Å	µ = 0.12 mm⁻¹
b = 6.9260 (14) Å	T = 173 K
c = 11.915 (2) Å	0.60 × 0.54 × 0.16 mm
β = 90.11 (3)°

Data collection top

Rigaku R-AXIS Spider diffractometer	1997 reflections with I > 2σ(I)
9730 measured reflections	R_int = 0.021
2416 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.29 e Å⁻³
2416 reflections	Δρ_min = −0.29 e Å⁻³
176 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
N1	0.23523 (9)	0.09076 (17)	0.62405 (10)	0.0249 (3)
N2	0.65298 (8)	0.28388 (17)	0.55245 (9)	0.0217 (3)
H5	0.6937 (13)	0.255 (3)	0.6065 (15)	0.028 (4)*
N3	0.68657 (8)	0.33719 (16)	0.44935 (9)	0.0202 (3)
O1	0.21019 (8)	0.03458 (18)	0.71835 (9)	0.0362 (3)
O2	0.17278 (8)	0.10441 (19)	0.54620 (10)	0.0381 (3)
O3	0.75514 (8)	0.43209 (18)	0.24033 (8)	0.0339 (3)
O4	0.90897 (7)	0.50736 (15)	0.31757 (8)	0.0256 (3)
C1	0.34331 (10)	0.14249 (18)	0.60429 (11)	0.0200 (3)
C2	0.37287 (10)	0.2085 (2)	0.49903 (11)	0.0219 (3)
H1	0.3235 (14)	0.217 (3)	0.4375 (16)	0.040 (5)*
C3	0.47596 (10)	0.25744 (19)	0.48098 (11)	0.0207 (3)
H2	0.4965 (13)	0.309 (2)	0.4086 (15)	0.029 (4)*
C4	0.54879 (9)	0.23761 (19)	0.56748 (10)	0.0188 (3)
C5	0.51738 (10)	0.1701 (2)	0.67302 (11)	0.0225 (3)
H3	0.5685 (14)	0.158 (3)	0.7310 (16)	0.035 (5)*
C6	0.41453 (10)	0.1227 (2)	0.69133 (11)	0.0225 (3)
H4	0.3938 (13)	0.072 (3)	0.7635 (15)	0.031 (4)*
C7	0.78391 (10)	0.37883 (19)	0.43797 (11)	0.0204 (3)
C8	0.86529 (11)	0.3763 (3)	0.52797 (12)	0.0333 (4)
H6	0.8767	0.5053	0.5548	0.050*
H7	0.9291	0.3258	0.4980	0.050*
H8	0.8423	0.2962	0.5888	0.050*
C9	0.81181 (10)	0.44003 (19)	0.32127 (11)	0.0204 (3)
C10	0.94452 (11)	0.5806 (2)	0.21009 (12)	0.0303 (3)
H9	1.0130	0.6345	0.2185	0.045*
H10	0.8975	0.6788	0.1841	0.045*
H11	0.9466	0.4770	0.1566	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0205 (6)	0.0267 (6)	0.0276 (6)	−0.0007 (5)	0.0051 (4)	−0.0034 (5)
N2	0.0181 (5)	0.0302 (6)	0.0169 (5)	−0.0020 (5)	0.0008 (4)	0.0016 (4)
N3	0.0202 (5)	0.0217 (6)	0.0188 (5)	−0.0005 (4)	0.0040 (4)	−0.0011 (4)
O1	0.0273 (5)	0.0512 (7)	0.0302 (6)	−0.0087 (5)	0.0102 (4)	0.0038 (5)
O2	0.0202 (5)	0.0564 (8)	0.0376 (6)	−0.0041 (5)	−0.0033 (4)	0.0014 (5)
O3	0.0255 (5)	0.0559 (7)	0.0202 (5)	−0.0093 (5)	−0.0011 (4)	0.0031 (5)
O4	0.0199 (5)	0.0350 (6)	0.0220 (5)	−0.0066 (4)	0.0039 (3)	0.0013 (4)
C1	0.0174 (6)	0.0199 (6)	0.0227 (6)	−0.0011 (5)	0.0036 (5)	−0.0039 (5)
C2	0.0204 (6)	0.0246 (7)	0.0208 (6)	0.0013 (5)	−0.0005 (5)	−0.0005 (5)
C3	0.0216 (6)	0.0234 (6)	0.0172 (6)	0.0006 (5)	0.0026 (5)	0.0017 (5)
C4	0.0186 (6)	0.0184 (6)	0.0193 (6)	0.0000 (5)	0.0031 (4)	−0.0022 (5)
C5	0.0210 (6)	0.0293 (7)	0.0173 (6)	−0.0004 (5)	0.0001 (5)	−0.0010 (5)
C6	0.0235 (6)	0.0266 (7)	0.0173 (6)	−0.0014 (5)	0.0045 (5)	−0.0006 (5)
C7	0.0195 (6)	0.0217 (6)	0.0199 (6)	−0.0017 (5)	0.0019 (5)	−0.0024 (5)
C8	0.0234 (6)	0.0543 (10)	0.0223 (7)	−0.0100 (7)	−0.0005 (5)	0.0040 (6)
C9	0.0191 (6)	0.0216 (6)	0.0207 (6)	−0.0007 (5)	0.0028 (5)	−0.0022 (5)
C10	0.0256 (7)	0.0384 (8)	0.0270 (7)	−0.0052 (6)	0.0085 (5)	0.0057 (6)

Geometric parameters (Å, º) top

N1—O2	1.2284 (17)	C3—C4	1.3970 (18)
N1—O1	1.2323 (16)	C3—H2	0.970 (18)
N1—C1	1.4525 (16)	C4—C5	1.4016 (18)
N2—N3	1.3540 (15)	C5—C6	1.3783 (18)
N2—C4	1.3872 (16)	C5—H3	0.956 (18)
N2—H5	0.853 (18)	C6—H4	0.966 (18)
N3—C7	1.2897 (16)	C7—C8	1.4958 (19)
O3—C9	1.2080 (17)	C7—C9	1.4977 (18)
O4—C9	1.3323 (15)	C8—H6	0.9600
O4—C10	1.4518 (16)	C8—H7	0.9600
C1—C6	1.3880 (19)	C8—H8	0.9600
C1—C2	1.3885 (19)	C10—H9	0.9600
C2—C3	1.3831 (17)	C10—H10	0.9600
C2—H1	0.970 (19)	C10—H11	0.9600

O2—N1—O1	122.81 (12)	C4—C5—H3	118.7 (11)
O2—N1—C1	118.73 (11)	C5—C6—C1	119.20 (12)
O1—N1—C1	118.46 (12)	C5—C6—H4	119.5 (10)
N3—N2—C4	119.27 (11)	C1—C6—H4	121.3 (10)
N3—N2—H5	123.6 (11)	N3—C7—C8	126.68 (12)
C4—N2—H5	116.0 (11)	N3—C7—C9	113.23 (11)
C7—N3—N2	117.81 (11)	C8—C7—C9	120.07 (11)
C9—O4—C10	116.57 (11)	C7—C8—H6	109.5
C6—C1—C2	121.79 (12)	C7—C8—H7	109.5
C6—C1—N1	118.84 (12)	H6—C8—H7	109.5
C2—C1—N1	119.37 (12)	C7—C8—H8	109.5
C3—C2—C1	118.97 (12)	H6—C8—H8	109.5
C3—C2—H1	119.4 (11)	H7—C8—H8	109.5
C1—C2—H1	121.6 (11)	O3—C9—O4	123.49 (12)
C2—C3—C4	120.02 (12)	O3—C9—C7	125.70 (12)
C2—C3—H2	119.3 (10)	O4—C9—C7	110.81 (11)
C4—C3—H2	120.6 (10)	O4—C10—H9	109.5
N2—C4—C3	121.74 (12)	O4—C10—H10	109.5
N2—C4—C5	118.16 (12)	H9—C10—H10	109.5
C3—C4—C5	120.10 (12)	O4—C10—H11	109.5
C6—C5—C4	119.92 (12)	H9—C10—H11	109.5
C6—C5—H3	121.4 (11)	H10—C10—H11	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H5···O3ⁱ	0.853 (18)	2.200 (18)	2.9928 (17)	154.6 (16)

Symmetry code: (i) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₁N₃O₄
M_r	237.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	12.836 (3), 6.9260 (14), 11.915 (2)
β (°)	90.11 (3)
V (Å³)	1059.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.60 × 0.54 × 0.16

Data collection
Diffractometer	Rigaku R-AXIS Spider
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9730, 2416, 1997
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.126, 1.09
No. of reflections	2416
No. of parameters	176
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.29

Computer programs: RAPID-AUTO (Rigaku, 2004), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEX (McArdle, 1995), SHELXL97-2 (Sheldrick, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H5···O3ⁱ	0.853 (18)	2.200 (18)	2.9928 (17)	154.6 (16)

Symmetry code: (i) x, −y+1/2, z+1/2.

Acknowledgements

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

References

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