2-(4-Methyl­phen­yl)acetohydrazide

Praveen, A.S.; Jasinski, J.P.; Krauss, S.T.; Yathirajan, H.S.; Narayana, B.

doi:10.1107/S160053681204799X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3467

doi:10.1107/S160053681204799X

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2-(4-Methylphenyl)acetohydrazide

A.S. Praveen,^a Jerry P. Jasinski,^b ^* Shannon T. Krauss,^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 16 November 2012; accepted 21 November 2012; online 28 November 2012)

In the title compound, C₉H₁₂N₂O, the dihedral angle between the benzene ring and the mean plane of the acetohydrazide group is 88.2 (7)°. In the crystal, N—H⋯O hydrogen bonds and weak C—H⋯O interactions link the molecules into infinite ribbons along [001].

Related literature

For hydrazides as precursors in the synthesis of heterocyclic systems, see: Narayana et al. (2005 ). For related structures, see: Hanif et al. (2007 ); Liu & Gao (2012 ); Fun et al. (2011 ). For standard bond lengths, see: Allen et al. (1987).

Experimental

Crystal data

C₉H₁₂N₂O
M_r = 164.21
Monoclinic, P 2₁ /c
a = 15.4261 (16) Å
b = 6.2618 (7) Å
c = 9.2073 (10) Å
β = 106.651 (12)°
V = 852.09 (16) Å³
Z = 4
Cu Kα radiation
μ = 0.69 mm⁻¹
T = 173 K
0.32 × 0.22 × 0.08 mm

Data collection

Agilent Xcalibur (Eos, Gemini) diffractometer
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012 ) T_min = 0.746, T_max = 1.000
4845 measured reflections
1675 independent reflections
1359 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.151
S = 1.07
1675 reflections
119 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ⁱ	0.84 (2)	2.05 (2)	2.884 (2)	171 (2)
C2—H2A⋯O1ⁱ	0.97	2.56	3.408 (2)	146
N1—H1A⋯O1ⁱⁱ	0.89 (2)	2.16 (2)	3.007 (2)	159 (2)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012); 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/S160053681204799X/ng5307sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681204799X/ng5307Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681204799X/ng5307Isup3.cml

checkCIF report

Comment top

Hydrazides are useful precursors in the synthesis of several related heterocyclic systems (Narayana et al., 2005). The crystal structures of some similar hydrazides, viz., 2-(4-methoxyphenoxy)acetohydrazide (Liu & Gao, 2012), 2-(3-methoxyphenyl)acetohydrazide (Hanif et al., 2007) and 2-(4-methylphenoxy)acetohydrazide (Fun et al., 2011) have been reported. In view of the importance of hydrazides, the crystal structure of title compound (I) is reported.

In the title compound, C₉H₁₂N₂O, the dihedral angle between the mean planes of the benzene ring (C3–C8) and acetohydrazide group (O1/C1/N2/N1) is 88.2 (7)° (Fig. 1). Bond lengths are in normal ranges (Allen et al., 1987). In the crystal N—H···O hydrogen bonds and weak C—H···O intermolecular interactions link the molecules into infinite ribbons along [001] (Fig. 2, Table 1).

Related literature top

For hydrazides as precursors in the synthesis of heterocyclic systems, see: Narayana et al. (2005). For related structures, see: Hanif et al. (2007); Liu & Gao (2012); Fun et al. (2011). For standard bond lengths, see: Allen et al. (1987).

Experimental top

To a solution of methyl (4-methylphenyl)acetate (2 g, 12.18 mmol) in methanol (20 mL), hydrazine hydrate (2 mL) was added and the reaction mixture was stirred at room temperature for 6 hours (Fig. 3). After the completion of the reaction methanol was removed under vacuum, added water, 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 91%. (m.p.: 426-428 K).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis RED (Agilent, 2012); 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 and weak C—H···O intermolecular interactions linking molecules into infinite 1-D chains along [001]. The remaining H atoms have been removed for clarity.
	Fig. 3. Synthesis of the title compound.

2-(4-Methylphenyl)acetohydrazide top

Crystal data top

C₉H₁₂N₂O	F(000) = 352
M_r = 164.21	D_x = 1.280 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 1566 reflections
a = 15.4261 (16) Å	θ = 3.0–72.3°
b = 6.2618 (7) Å	µ = 0.69 mm⁻¹
c = 9.2073 (10) Å	T = 173 K
β = 106.651 (12)°	Chunk, colorless
V = 852.09 (16) Å³	0.32 × 0.22 × 0.08 mm
Z = 4

Data collection top

Agilent Xcalibur (Eos, Gemini) diffractometer	1675 independent reflections
Radiation source: Enhance (Cu) X-ray Source	1359 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 16.0416 pixels mm^-1	θ_max = 72.5°, θ_min = 3.0°
ω scans	h = −18→19
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012)	k = −7→4
T_min = 0.746, T_max = 1.000	l = −10→11
4845 measured 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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.151	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0882P)² + 0.1271P] where P = (F_o² + 2F_c²)/3
1675 reflections	(Δ/σ)_max < 0.001
119 parameters	Δρ_max = 0.26 e Å⁻³
3 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₉H₁₂N₂O	V = 852.09 (16) Å³
M_r = 164.21	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 15.4261 (16) Å	µ = 0.69 mm⁻¹
b = 6.2618 (7) Å	T = 173 K
c = 9.2073 (10) Å	0.32 × 0.22 × 0.08 mm
β = 106.651 (12)°

Data collection top

Agilent Xcalibur (Eos, Gemini) diffractometer	1675 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012)	1359 reflections with I > 2σ(I)
T_min = 0.746, T_max = 1.000	R_int = 0.028
4845 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	3 restraints
wR(F²) = 0.151	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.26 e Å⁻³
1675 reflections	Δρ_min = −0.21 e Å⁻³
119 parameters

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	0.08543 (9)	0.1283 (2)	0.28834 (14)	0.0417 (4)
N1	−0.06203 (11)	0.2284 (3)	0.0460 (2)	0.0396 (4)
H1A	−0.0731 (15)	0.323 (3)	0.110 (2)	0.048*
H1B	−0.0656 (15)	0.105 (3)	0.093 (2)	0.048*
N2	0.03002 (10)	0.2537 (2)	0.05112 (18)	0.0336 (4)
H2	0.0399 (15)	0.293 (3)	−0.030 (2)	0.040*
C1	0.09783 (12)	0.1991 (3)	0.17011 (19)	0.0319 (4)
C2	0.19169 (12)	0.2268 (3)	0.1528 (2)	0.0370 (4)
H2A	0.1873	0.2917	0.0553	0.044*
H2B	0.2199	0.0878	0.1551	0.044*
C3	0.25012 (11)	0.3654 (3)	0.27779 (19)	0.0340 (4)
C4	0.22379 (12)	0.5730 (3)	0.2991 (2)	0.0381 (4)
H4	0.1707	0.6279	0.2343	0.046*
C5	0.27565 (12)	0.6990 (3)	0.4157 (2)	0.0394 (4)
H5	0.2562	0.8363	0.4292	0.047*
C6	0.35650 (12)	0.6232 (3)	0.5132 (2)	0.0381 (4)
C7	0.38281 (12)	0.4170 (3)	0.4904 (2)	0.0402 (5)
H7	0.4366	0.3630	0.5538	0.048*
C8	0.33043 (12)	0.2894 (3)	0.3747 (2)	0.0373 (4)
H8	0.3495	0.1515	0.3621	0.045*
C9	0.41413 (15)	0.7621 (4)	0.6381 (2)	0.0518 (6)
H9A	0.3783	0.8125	0.7009	0.078*
H9B	0.4365	0.8817	0.5944	0.078*
H9C	0.4642	0.6802	0.6985	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0437 (8)	0.0512 (8)	0.0323 (7)	−0.0037 (6)	0.0144 (6)	0.0019 (5)
N1	0.0299 (8)	0.0442 (9)	0.0452 (10)	−0.0016 (6)	0.0115 (7)	−0.0051 (7)
N2	0.0311 (8)	0.0391 (8)	0.0321 (8)	−0.0006 (6)	0.0113 (6)	0.0010 (6)
C1	0.0347 (9)	0.0320 (8)	0.0298 (9)	−0.0025 (6)	0.0105 (7)	−0.0047 (6)
C2	0.0328 (9)	0.0492 (10)	0.0307 (9)	−0.0012 (7)	0.0119 (7)	−0.0038 (7)
C3	0.0293 (8)	0.0435 (10)	0.0310 (9)	−0.0022 (7)	0.0113 (7)	0.0004 (7)
C4	0.0288 (9)	0.0460 (10)	0.0392 (10)	0.0037 (7)	0.0095 (7)	0.0048 (7)
C5	0.0327 (9)	0.0409 (10)	0.0468 (11)	−0.0015 (7)	0.0151 (8)	−0.0014 (8)
C6	0.0303 (9)	0.0484 (10)	0.0374 (10)	−0.0060 (7)	0.0126 (7)	−0.0032 (8)
C7	0.0301 (9)	0.0496 (11)	0.0388 (10)	0.0012 (7)	0.0065 (7)	0.0040 (8)
C8	0.0340 (9)	0.0386 (9)	0.0398 (10)	0.0027 (7)	0.0115 (8)	0.0021 (7)
C9	0.0403 (11)	0.0650 (14)	0.0498 (12)	−0.0083 (9)	0.0121 (10)	−0.0157 (10)

Geometric parameters (Å, º) top

O1—C1	1.240 (2)	C4—C5	1.387 (3)
N1—N2	1.416 (2)	C4—H4	0.9300
N1—H1A	0.889 (16)	C5—C6	1.395 (3)
N1—H1B	0.898 (15)	C5—H5	0.9300
N2—C1	1.325 (2)	C6—C7	1.388 (3)
N2—H2	0.842 (15)	C6—C9	1.511 (3)
C1—C2	1.511 (2)	C7—C8	1.390 (3)
C2—C3	1.515 (2)	C7—H7	0.9300
C2—H2A	0.9700	C8—H8	0.9300
C2—H2B	0.9700	C9—H9A	0.9600
C3—C8	1.387 (2)	C9—H9B	0.9600
C3—C4	1.393 (3)	C9—H9C	0.9600

N2—N1—H1A	106.6 (15)	C3—C4—H4	119.5
N2—N1—H1B	106.3 (15)	C4—C5—C6	121.05 (17)
H1A—N1—H1B	102 (2)	C4—C5—H5	119.5
C1—N2—N1	123.05 (15)	C6—C5—H5	119.5
C1—N2—H2	120.6 (15)	C7—C6—C5	117.77 (17)
N1—N2—H2	116.0 (15)	C7—C6—C9	121.12 (17)
O1—C1—N2	122.32 (16)	C5—C6—C9	121.11 (18)
O1—C1—C2	121.82 (16)	C6—C7—C8	121.30 (16)
N2—C1—C2	115.86 (15)	C6—C7—H7	119.3
C1—C2—C3	111.39 (14)	C8—C7—H7	119.3
C1—C2—H2A	109.3	C3—C8—C7	120.79 (17)
C3—C2—H2A	109.3	C3—C8—H8	119.6
C1—C2—H2B	109.3	C7—C8—H8	119.6
C3—C2—H2B	109.3	C6—C9—H9A	109.5
H2A—C2—H2B	108.0	C6—C9—H9B	109.5
C8—C3—C4	118.18 (16)	H9A—C9—H9B	109.5
C8—C3—C2	121.29 (16)	C6—C9—H9C	109.5
C4—C3—C2	120.52 (15)	H9A—C9—H9C	109.5
C5—C4—C3	120.90 (16)	H9B—C9—H9C	109.5
C5—C4—H4	119.5

N1—N2—C1—O1	−2.6 (3)	C3—C4—C5—C6	1.2 (3)
N1—N2—C1—C2	177.00 (15)	C4—C5—C6—C7	−0.6 (3)
O1—C1—C2—C3	−55.6 (2)	C4—C5—C6—C9	178.63 (17)
N2—C1—C2—C3	124.79 (16)	C5—C6—C7—C8	−0.1 (3)
C1—C2—C3—C8	120.96 (18)	C9—C6—C7—C8	−179.37 (18)
C1—C2—C3—C4	−58.4 (2)	C4—C3—C8—C7	0.4 (3)
C8—C3—C4—C5	−1.1 (3)	C2—C3—C8—C7	−179.03 (16)
C2—C3—C4—C5	178.30 (16)	C6—C7—C8—C3	0.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.84 (2)	2.05 (2)	2.884 (2)	171 (2)
C2—H2A···O1ⁱ	0.97	2.56	3.408 (2)	146
N1—H1A···O1ⁱⁱ	0.89 (2)	2.16 (2)	3.007 (2)	159 (2)

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

Experimental details

Crystal data
Chemical formula	C₉H₁₂N₂O
M_r	164.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	15.4261 (16), 6.2618 (7), 9.2073 (10)
β (°)	106.651 (12)
V (Å³)	852.09 (16)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.69
Crystal size (mm)	0.32 × 0.22 × 0.08

Data collection
Diffractometer	Agilent Xcalibur (Eos, Gemini) diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Agilent, 2012)
T_min, T_max	0.746, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4845, 1675, 1359
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.151, 1.07
No. of reflections	1675
No. of parameters	119
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.21

Computer programs: CrysAlis PRO (Agilent, 2012), CrysAlis RED (Agilent, 2012), 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
N2—H2···O1ⁱ	0.842 (15)	2.050 (16)	2.884 (2)	171 (2)
C2—H2A···O1ⁱ	0.97	2.56	3.408 (2)	146.3
N1—H1A···O1ⁱⁱ	0.889 (16)	2.158 (17)	3.007 (2)	159 (2)

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

Acknowledgements

ASP thanks the 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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