organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

2-(4-Methyl­phen­yl)acetohydrazide

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[Narayana, B., Ashalatha, B. V., Vijayaraj, K. K., Fernandes, J. & Sarojini, B. K. (2005). Bioorg. Med. Chem. 13, 4638-4644.]). For related structures, see: Hanif et al. (2007[Hanif, M., Qadeer, G., Rama, N. H., Farman, M. & Ružička, A. (2007). Acta Cryst. E63, o4828.]); Liu & Gao (2012[Liu, G. & Gao, J. (2012). Acta Cryst. E68, o1969.]); Fun et al. (2011[Fun, H.-K., Quah, C. K., Malladi, S. M. V. A. & Isloor, A. M. (2011). Acta Cryst. E67, o165.]). For standard bond lengths, see: Allen et al. (1987)[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.].

[Scheme 1]

Experimental

Crystal data
  • C9H12N2O

  • Mr = 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[Agilent (2012). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, England.]) Tmin = 0.746, Tmax = 1.000

  • 4845 measured reflections

  • 1675 independent reflections

  • 1359 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.26 e Å−3

  • Δρmin = −0.21 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Agilent (2012). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012[Agilent (2012). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, England.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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).

Refinement top

H1A, H1B and H2 were restrained with DFIX = 0.86 (2)Å. All the H atoms were placed in their calculated positions and then refined using the riding model with Atom—H lengths of 0.93Å (CH), 0.97Å (CH2), 0.96Å (CH3) or 0.86Å (NH). Isotropic displacement parameters for these atoms were set to 1.19-1.21 (CH, CH2), 1.49 (CH3) or 1.20 (NH) times Ueq of the parent atom.

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
[Figure 1] Fig. 1. Molecular structure of the title compound showing the atom labeling scheme and 50% probability displacement ellipsoids.
[Figure 2] 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.
[Figure 3] Fig. 3. Synthesis of the title compound.
2-(4-Methylphenyl)acetohydrazide top
Crystal data top
C9H12N2OF(000) = 352
Mr = 164.21Dx = 1.280 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybcCell parameters from 1566 reflections
a = 15.4261 (16) Åθ = 3.0–72.3°
b = 6.2618 (7) ŵ = 0.69 mm1
c = 9.2073 (10) ÅT = 173 K
β = 106.651 (12)°Chunk, colorless
V = 852.09 (16) Å30.32 × 0.22 × 0.08 mm
Z = 4
Data collection top
Agilent Xcalibur (Eos, Gemini)
diffractometer
1675 independent reflections
Radiation source: Enhance (Cu) X-ray Source1359 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
Detector resolution: 16.0416 pixels mm-1θmax = 72.5°, θmin = 3.0°
ω scansh = 1819
Absorption correction: multi-scan
(CrysAlis RED; Agilent, 2012)
k = 74
Tmin = 0.746, Tmax = 1.000l = 1011
4845 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.151H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0882P)2 + 0.1271P]
where P = (Fo2 + 2Fc2)/3
1675 reflections(Δ/σ)max < 0.001
119 parametersΔρmax = 0.26 e Å3
3 restraintsΔρmin = 0.21 e Å3
Crystal data top
C9H12N2OV = 852.09 (16) Å3
Mr = 164.21Z = 4
Monoclinic, P21/cCu Kα radiation
a = 15.4261 (16) ŵ = 0.69 mm1
b = 6.2618 (7) ÅT = 173 K
c = 9.2073 (10) Å0.32 × 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)
Tmin = 0.746, Tmax = 1.000Rint = 0.028
4845 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0503 restraints
wR(F2) = 0.151H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.26 e Å3
1675 reflectionsΔρmin = 0.21 e Å3
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
xyzUiso*/Ueq
O10.08543 (9)0.1283 (2)0.28834 (14)0.0417 (4)
N10.06203 (11)0.2284 (3)0.0460 (2)0.0396 (4)
H1A0.0731 (15)0.323 (3)0.110 (2)0.048*
H1B0.0656 (15)0.105 (3)0.093 (2)0.048*
N20.03002 (10)0.2537 (2)0.05112 (18)0.0336 (4)
H20.0399 (15)0.293 (3)0.030 (2)0.040*
C10.09783 (12)0.1991 (3)0.17011 (19)0.0319 (4)
C20.19169 (12)0.2268 (3)0.1528 (2)0.0370 (4)
H2A0.18730.29170.05530.044*
H2B0.21990.08780.15510.044*
C30.25012 (11)0.3654 (3)0.27779 (19)0.0340 (4)
C40.22379 (12)0.5730 (3)0.2991 (2)0.0381 (4)
H40.17070.62790.23430.046*
C50.27565 (12)0.6990 (3)0.4157 (2)0.0394 (4)
H50.25620.83630.42920.047*
C60.35650 (12)0.6232 (3)0.5132 (2)0.0381 (4)
C70.38281 (12)0.4170 (3)0.4904 (2)0.0402 (5)
H70.43660.36300.55380.048*
C80.33043 (12)0.2894 (3)0.3747 (2)0.0373 (4)
H80.34950.15150.36210.045*
C90.41413 (15)0.7621 (4)0.6381 (2)0.0518 (6)
H9A0.37830.81250.70090.078*
H9B0.43650.88170.59440.078*
H9C0.46420.68020.69850.078*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0437 (8)0.0512 (8)0.0323 (7)0.0037 (6)0.0144 (6)0.0019 (5)
N10.0299 (8)0.0442 (9)0.0452 (10)0.0016 (6)0.0115 (7)0.0051 (7)
N20.0311 (8)0.0391 (8)0.0321 (8)0.0006 (6)0.0113 (6)0.0010 (6)
C10.0347 (9)0.0320 (8)0.0298 (9)0.0025 (6)0.0105 (7)0.0047 (6)
C20.0328 (9)0.0492 (10)0.0307 (9)0.0012 (7)0.0119 (7)0.0038 (7)
C30.0293 (8)0.0435 (10)0.0310 (9)0.0022 (7)0.0113 (7)0.0004 (7)
C40.0288 (9)0.0460 (10)0.0392 (10)0.0037 (7)0.0095 (7)0.0048 (7)
C50.0327 (9)0.0409 (10)0.0468 (11)0.0015 (7)0.0151 (8)0.0014 (8)
C60.0303 (9)0.0484 (10)0.0374 (10)0.0060 (7)0.0126 (7)0.0032 (8)
C70.0301 (9)0.0496 (11)0.0388 (10)0.0012 (7)0.0065 (7)0.0040 (8)
C80.0340 (9)0.0386 (9)0.0398 (10)0.0027 (7)0.0115 (8)0.0021 (7)
C90.0403 (11)0.0650 (14)0.0498 (12)0.0083 (9)0.0121 (10)0.0157 (10)
Geometric parameters (Å, º) top
O1—C11.240 (2)C4—C51.387 (3)
N1—N21.416 (2)C4—H40.9300
N1—H1A0.889 (16)C5—C61.395 (3)
N1—H1B0.898 (15)C5—H50.9300
N2—C11.325 (2)C6—C71.388 (3)
N2—H20.842 (15)C6—C91.511 (3)
C1—C21.511 (2)C7—C81.390 (3)
C2—C31.515 (2)C7—H70.9300
C2—H2A0.9700C8—H80.9300
C2—H2B0.9700C9—H9A0.9600
C3—C81.387 (2)C9—H9B0.9600
C3—C41.393 (3)C9—H9C0.9600
N2—N1—H1A106.6 (15)C3—C4—H4119.5
N2—N1—H1B106.3 (15)C4—C5—C6121.05 (17)
H1A—N1—H1B102 (2)C4—C5—H5119.5
C1—N2—N1123.05 (15)C6—C5—H5119.5
C1—N2—H2120.6 (15)C7—C6—C5117.77 (17)
N1—N2—H2116.0 (15)C7—C6—C9121.12 (17)
O1—C1—N2122.32 (16)C5—C6—C9121.11 (18)
O1—C1—C2121.82 (16)C6—C7—C8121.30 (16)
N2—C1—C2115.86 (15)C6—C7—H7119.3
C1—C2—C3111.39 (14)C8—C7—H7119.3
C1—C2—H2A109.3C3—C8—C7120.79 (17)
C3—C2—H2A109.3C3—C8—H8119.6
C1—C2—H2B109.3C7—C8—H8119.6
C3—C2—H2B109.3C6—C9—H9A109.5
H2A—C2—H2B108.0C6—C9—H9B109.5
C8—C3—C4118.18 (16)H9A—C9—H9B109.5
C8—C3—C2121.29 (16)C6—C9—H9C109.5
C4—C3—C2120.52 (15)H9A—C9—H9C109.5
C5—C4—C3120.90 (16)H9B—C9—H9C109.5
C5—C4—H4119.5
N1—N2—C1—O12.6 (3)C3—C4—C5—C61.2 (3)
N1—N2—C1—C2177.00 (15)C4—C5—C6—C70.6 (3)
O1—C1—C2—C355.6 (2)C4—C5—C6—C9178.63 (17)
N2—C1—C2—C3124.79 (16)C5—C6—C7—C80.1 (3)
C1—C2—C3—C8120.96 (18)C9—C6—C7—C8179.37 (18)
C1—C2—C3—C458.4 (2)C4—C3—C8—C70.4 (3)
C8—C3—C4—C51.1 (3)C2—C3—C8—C7179.03 (16)
C2—C3—C4—C5178.30 (16)C6—C7—C8—C30.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O1i0.84 (2)2.05 (2)2.884 (2)171 (2)
C2—H2A···O1i0.972.563.408 (2)146
N1—H1A···O1ii0.89 (2)2.16 (2)3.007 (2)159 (2)
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC9H12N2O
Mr164.21
Crystal system, space groupMonoclinic, P21/c
Temperature (K)173
a, b, c (Å)15.4261 (16), 6.2618 (7), 9.2073 (10)
β (°) 106.651 (12)
V3)852.09 (16)
Z4
Radiation typeCu Kα
µ (mm1)0.69
Crystal size (mm)0.32 × 0.22 × 0.08
Data collection
DiffractometerAgilent Xcalibur (Eos, Gemini)
diffractometer
Absorption correctionMulti-scan
(CrysAlis RED; Agilent, 2012)
Tmin, Tmax0.746, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
4845, 1675, 1359
Rint0.028
(sin θ/λ)max1)0.618
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.151, 1.07
No. of reflections1675
No. of parameters119
No. of restraints3
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N2—H2···O1i0.842 (15)2.050 (16)2.884 (2)171 (2)
C2—H2A···O1i0.972.563.408 (2)146.3
N1—H1A···O1ii0.889 (16)2.158 (17)3.007 (2)159 (2)
Symmetry codes: (i) x, y+1/2, z1/2; (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

First citationAgilent (2012). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, England.
First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.  CrossRef Web of Science
First citationFun, H.-K., Quah, C. K., Malladi, S. M. V. A. & Isloor, A. M. (2011). Acta Cryst. E67, o165.  Web of Science CrossRef IUCr Journals
First citationHanif, M., Qadeer, G., Rama, N. H., Farman, M. & Ružička, A. (2007). Acta Cryst. E63, o4828.  Web of Science CSD CrossRef IUCr Journals
First citationLiu, G. & Gao, J. (2012). Acta Cryst. E68, o1969.  CSD CrossRef IUCr Journals
First citationNarayana, B., Ashalatha, B. V., Vijayaraj, K. K., Fernandes, J. & Sarojini, B. K. (2005). Bioorg. Med. Chem. 13, 4638–4644.  Web of Science CrossRef PubMed CAS
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals

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