2-(2-Nitro­phen­yl)acetohydrazide

Praveen, A.S.; Jasinski, J.P.; Keeley, A.C.; Yathirajan, H.S.; Narayana, B.

doi:10.1107/S1600536812047381

organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3436

doi:10.1107/S1600536812047381

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2-(2-Nitrophenyl)acetohydrazide

A. S. Praveen,^a Jerry P. Jasinski,^b ^* Amanda C. Keeley,^b H. S. Yathirajan ^a and B. Narayana ^c

^aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, ^bDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, and ^cDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri 574 199, India
^*Correspondence e-mail: jjasinski@keene.edu

(Received 12 November 2012; accepted 18 November 2012; online 24 November 2012)

In the title compound, C₈H₉N₃O₃, the dihedral angle between the benzene ring and the acetohydrazide C—C(=O)—N—N plane [maximum deviation = 0.0471 (13) Å] is 87.62 (8)°. The nitro group is twisted by 19.3 (2)° with respect to the benzene ring. In the crystal, N—H⋯O hydrogen bonds link the molecules into a double-column structure along the b axis.

Related literature

For the chemistry of hydrazides, ses: Domiano et al. (1984 ). For the biological properties of hydrazides, see: Kalsi et al. (2006 ); Masunari & Tavares (2007 ); Singh et al. (1992 ). For related structures, see: Ahmad et al. (2012 ); Dutkiewicz et al. (2009 ); Liu & Gao (2012 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₉N₃O₃
M_r = 195.18
Monoclinic, P 2₁
a = 6.6962 (5) Å
b = 4.9388 (4) Å
c = 13.3593 (12) Å
β = 92.361 (8)°
V = 441.43 (6) Å³
Z = 2
Cu Kα radiation
μ = 0.98 mm⁻¹
T = 173 K
0.36 × 0.28 × 0.08 mm

Data collection

Oxford Diffraction Xcalibur (Eos, Gemini) diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) T_min = 0.667, T_max = 0.925
3829 measured reflections
1967 independent reflections
1824 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.096
S = 1.05
1967 reflections
136 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ), 836 Friedel pairs
Flack parameter: 0.3 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O1ⁱ	0.90 (1)	2.21 (2)	3.0752 (19)	163 (2)
N2—H2⋯O1ⁱⁱ	0.85 (2)	2.03 (2)	2.8531 (18)	165 (2)
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+1]$ ; (ii) x, y-1, z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812047381/is5219sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812047381/is5219Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812047381/is5219Isup3.cml

checkCIF report

Comment top

The chemistry of hydrazides has been intensely investigated in recent years due to their excellent coordinating capability (Domiano et al., 1984). Hydrazides and their condensation products have displayed diverse range of biological properties such as anti-helmintic (Kalsi et al., 2006), anti-leprotic (Masunari & Tavares, 2007) and anti-depressant (Singh et al., 1992). The crystal structures of some hydrazides, viz., 2-(4-bromophenyl)acetohydrazide (Ahmad et al., 2012), 2-(4-chlorophenoxy)acetohydrazide (Dutkiewicz et al., 2009) and 2-(4-methoxyphenoxy)acetohydrazide (Liu & Gao, 2012) have been reported. In view of the importance of hydrazides, the crystal structure of title compound (I) is reported.

In the title compound, the dihedral angle between the benzene ring and acetohydrazide C2/C1/O1/N2/N1 plane is 87.62 (8)° (Fig. 1). The nitro group is twisted by 19.3 (2)° with the benzene ring. Bond lengths are in normal ranges (Allen et al., 1987). In the crystal, N—H···O hydrogen bonds (Table 1) link the molecules into a double-column structure along the b axis (Fig. 2).

Related literature top

For the chemistry of hydrazides, ses: Domiano et al. (1984). For the biological properties of hydrazides, see: Kalsi et al. (2006); Masunari & Tavares (2007); Singh et al. (1992). For related structures, see: Ahmad et al. (2012); Dutkiewicz et al. (2009); Liu & Gao (2012). For bond-length data, see: Allen et al. (1987).

Experimental top

To a solution of methyl 2-(2-nitrophenyl)acetate (2 g, 10.14 mmol) in methanol (20 mL), hydrazine hydrate (2 mL) was added and the reaction mixture was stirred at room temperature for 8 hours (Fig. 3). After the completion of the reaction, methanol was removed under vacuum, water was added, precipitated solid was filtered and dried. The single crystal was grown from mixture methanol: water (2:1) by slow evaporation method and yield of the compound was 95%. (m.p.: 422-424 K).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis RED (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound showing the atom labeling scheme and 50% probability displacement ellipsoids.
	Fig. 2. Packing diagram of the title compound viewed along the b axis. Dashed lines indicate N—H···O hydrogen bonds. H atoms not involved in the hydrogen bonds have been removed for clarity.
	Fig. 3. Synthesis of the title compound.

2-(2-Nitrophenyl)acetohydrazide top

Crystal data top

C₈H₉N₃O₃	F(000) = 204
M_r = 195.18	D_x = 1.468 Mg m⁻³
Monoclinic, P2₁	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2yb	Cell parameters from 1694 reflections
a = 6.6962 (5) Å	θ = 3.3–32.5°
b = 4.9388 (4) Å	µ = 0.98 mm⁻¹
c = 13.3593 (12) Å	T = 173 K
β = 92.361 (8)°	Chunk, colorless
V = 441.43 (6) Å³	0.36 × 0.28 × 0.08 mm
Z = 2

Data collection top

Oxford Diffraction Xcalibur (Eos, Gemini) diffractometer	1967 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1824 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
Detector resolution: 16.0416 pixels mm^-1	θ_max = 89.1°, θ_min = 7.3°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	k = −6→6
T_min = 0.667, T_max = 0.925	l = −17→17
3829 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.096	w = 1/[σ²(F_o²) + (0.0517P)² + 0.016P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1967 reflections	Δρ_max = 0.19 e Å⁻³
136 parameters	Δρ_min = −0.17 e Å⁻³
4 restraints	Absolute structure: Flack (1983), 836 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.3 (3)

Crystal data top

C₈H₉N₃O₃	V = 441.43 (6) Å³
M_r = 195.18	Z = 2
Monoclinic, P2₁	Cu Kα radiation
a = 6.6962 (5) Å	µ = 0.98 mm⁻¹
b = 4.9388 (4) Å	T = 173 K
c = 13.3593 (12) Å	0.36 × 0.28 × 0.08 mm
β = 92.361 (8)°

Data collection top

Oxford Diffraction Xcalibur (Eos, Gemini) diffractometer	1967 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	1824 reflections with I > 2σ(I)
T_min = 0.667, T_max = 0.925	R_int = 0.025
3829 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.096	Δρ_max = 0.19 e Å⁻³
S = 1.05	Δρ_min = −0.17 e Å⁻³
1967 reflections	Absolute structure: Flack (1983), 836 Friedel pairs
136 parameters	Absolute structure parameter: 0.3 (3)
4 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
O1	0.27090 (17)	0.8745 (2)	0.55928 (9)	0.0360 (3)
O2	0.0246 (2)	0.4300 (4)	0.71073 (10)	0.0632 (5)
O3	−0.0790 (2)	0.4790 (4)	0.85895 (11)	0.0576 (4)
N1	0.1751 (2)	0.4904 (3)	0.41437 (10)	0.0360 (3)
H1A	0.202 (3)	0.660 (4)	0.4013 (15)	0.043*
H1B	0.042 (2)	0.494 (5)	0.4186 (13)	0.043*
N2	0.2580 (2)	0.4374 (3)	0.51138 (10)	0.0318 (3)
H2	0.286 (3)	0.275 (4)	0.5269 (13)	0.038*
N3	0.0398 (2)	0.5265 (3)	0.79401 (10)	0.0358 (4)
C1	0.3052 (2)	0.6316 (3)	0.57676 (12)	0.0274 (3)
C2	0.4158 (2)	0.5384 (4)	0.67189 (12)	0.0338 (4)
H2A	0.3753	0.3547	0.6868	0.041*
H2B	0.5580	0.5363	0.6609	0.041*
C3	0.3777 (2)	0.7162 (3)	0.76100 (11)	0.0290 (3)
C4	0.2066 (2)	0.7141 (3)	0.81839 (11)	0.0293 (3)
C5	0.1834 (2)	0.8801 (4)	0.90089 (12)	0.0358 (4)
H5	0.0682	0.8696	0.9372	0.043*
C6	0.3327 (3)	1.0607 (4)	0.92857 (13)	0.0391 (4)
H6	0.3182	1.1750	0.9831	0.047*
C7	0.5050 (3)	1.0703 (4)	0.87408 (13)	0.0392 (4)
H7	0.6064	1.1916	0.8922	0.047*
C8	0.5260 (2)	0.9000 (4)	0.79295 (12)	0.0338 (4)
H8	0.6435	0.9080	0.7583	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0441 (6)	0.0188 (6)	0.0449 (7)	0.0021 (5)	−0.0010 (5)	0.0046 (5)
O2	0.0697 (9)	0.0736 (12)	0.0466 (8)	−0.0375 (9)	0.0085 (6)	−0.0133 (8)
O3	0.0440 (7)	0.0653 (11)	0.0651 (9)	−0.0193 (7)	0.0216 (6)	−0.0069 (8)
N1	0.0431 (7)	0.0306 (8)	0.0346 (7)	−0.0004 (7)	0.0062 (6)	0.0013 (6)
N2	0.0423 (7)	0.0197 (7)	0.0337 (7)	0.0046 (6)	0.0070 (5)	0.0036 (6)
N3	0.0339 (7)	0.0332 (9)	0.0405 (8)	−0.0061 (6)	0.0037 (6)	0.0013 (6)
C1	0.0296 (7)	0.0197 (8)	0.0336 (8)	0.0031 (6)	0.0087 (6)	0.0028 (6)
C2	0.0387 (8)	0.0261 (9)	0.0369 (9)	0.0096 (7)	0.0048 (6)	0.0034 (7)
C3	0.0314 (7)	0.0254 (8)	0.0303 (7)	0.0034 (6)	0.0006 (6)	0.0079 (7)
C4	0.0288 (7)	0.0242 (8)	0.0347 (8)	−0.0011 (6)	0.0007 (6)	0.0043 (7)
C5	0.0385 (8)	0.0353 (10)	0.0338 (8)	−0.0005 (8)	0.0048 (6)	0.0011 (7)
C6	0.0509 (10)	0.0333 (10)	0.0330 (9)	−0.0026 (8)	−0.0003 (7)	−0.0012 (7)
C7	0.0432 (9)	0.0332 (10)	0.0404 (9)	−0.0089 (8)	−0.0076 (7)	0.0077 (8)
C8	0.0300 (7)	0.0351 (10)	0.0362 (8)	−0.0023 (7)	0.0003 (6)	0.0095 (7)

Geometric parameters (Å, º) top

O1—C1	1.242 (2)	C2—H2B	0.9700
O2—N3	1.2107 (19)	C3—C8	1.399 (2)
O3—N3	1.2236 (18)	C3—C4	1.405 (2)
N1—N2	1.413 (2)	C4—C5	1.387 (2)
N1—H1A	0.877 (16)	C5—C6	1.379 (3)
N1—H1B	0.898 (14)	C5—H5	0.9300
N2—C1	1.327 (2)	C6—C7	1.390 (3)
N2—H2	0.845 (16)	C6—H6	0.9300
N3—C4	1.477 (2)	C7—C8	1.384 (3)
C1—C2	1.516 (2)	C7—H7	0.9300
C2—C3	1.509 (2)	C8—H8	0.9300
C2—H2A	0.9700

N2—N1—H1A	106.5 (14)	C8—C3—C4	115.04 (15)
N2—N1—H1B	107.5 (12)	C8—C3—C2	118.50 (14)
H1A—N1—H1B	102 (2)	C4—C3—C2	126.45 (15)
C1—N2—N1	122.93 (15)	C5—C4—C3	123.33 (15)
C1—N2—H2	118.6 (13)	C5—C4—N3	115.94 (13)
N1—N2—H2	118.3 (13)	C3—C4—N3	120.72 (14)
O2—N3—O3	122.93 (16)	C6—C5—C4	119.47 (15)
O2—N3—C4	118.92 (13)	C6—C5—H5	120.3
O3—N3—C4	118.13 (14)	C4—C5—H5	120.3
O1—C1—N2	122.50 (16)	C5—C6—C7	119.32 (16)
O1—C1—C2	122.07 (16)	C5—C6—H6	120.3
N2—C1—C2	115.32 (15)	C7—C6—H6	120.3
C3—C2—C1	113.10 (14)	C8—C7—C6	120.18 (17)
C3—C2—H2A	109.0	C8—C7—H7	119.9
C1—C2—H2A	109.0	C6—C7—H7	119.9
C3—C2—H2B	109.0	C7—C8—C3	122.65 (15)
C1—C2—H2B	109.0	C7—C8—H8	118.7
H2A—C2—H2B	107.8	C3—C8—H8	118.7

N1—N2—C1—O1	3.6 (2)	O3—N3—C4—C5	−18.1 (2)
N1—N2—C1—C2	−172.72 (13)	O2—N3—C4—C3	−20.3 (2)
O1—C1—C2—C3	32.4 (2)	O3—N3—C4—C3	160.87 (17)
N2—C1—C2—C3	−151.21 (14)	C3—C4—C5—C6	1.0 (2)
C1—C2—C3—C8	−103.44 (17)	N3—C4—C5—C6	179.95 (15)
C1—C2—C3—C4	77.9 (2)	C4—C5—C6—C7	−0.9 (3)
C8—C3—C4—C5	0.0 (2)	C5—C6—C7—C8	0.0 (3)
C2—C3—C4—C5	178.63 (16)	C6—C7—C8—C3	1.0 (3)
C8—C3—C4—N3	−178.96 (14)	C4—C3—C8—C7	−1.0 (2)
C2—C3—C4—N3	−0.3 (2)	C2—C3—C8—C7	−179.73 (16)
O2—N3—C4—C5	160.74 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1ⁱ	0.90 (1)	2.21 (2)	3.0752 (19)	163 (2)
N2—H2···O1ⁱⁱ	0.85 (2)	2.03 (2)	2.8531 (18)	165 (2)

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

Experimental details

Crystal data
Chemical formula	C₈H₉N₃O₃
M_r	195.18
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	173
a, b, c (Å)	6.6962 (5), 4.9388 (4), 13.3593 (12)
β (°)	92.361 (8)
V (Å³)	441.43 (6)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	0.98
Crystal size (mm)	0.36 × 0.28 × 0.08

Data collection
Diffractometer	Oxford Diffraction Xcalibur (Eos, Gemini) diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2010)
T_min, T_max	0.667, 0.925
No. of measured, independent and observed [I > 2σ(I)] reflections	3829, 1967, 1824
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.096, 1.05
No. of reflections	1967
No. of parameters	136
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.17
Absolute structure	Flack (1983), 836 Friedel pairs
Absolute structure parameter	0.3 (3)

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), CrysAlis RED (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1ⁱ	0.898 (14)	2.207 (16)	3.0752 (19)	163 (2)
N2—H2···O1ⁱⁱ	0.845 (16)	2.030 (18)	2.8531 (18)	164.6 (19)

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

Acknowledgements

ASP thanks UOM for research facilities. JPJ acknowledges the NSF–MRI program (grant No. CHE1039027) for funds to purchase the X-ray diffractometer.

References

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