organic compounds
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
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 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).
as precursors in the synthesis of heterocyclic systems, see: NarayanaExperimental
Crystal data
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Refinement
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Data collection: CrysAlis PRO (Agilent, 2012); cell 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
10.1107/S160053681204799X/ng5307sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S160053681204799X/ng5307Isup2.hkl
Supporting information file. DOI: 10.1107/S160053681204799X/ng5307Isup3.cml
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).
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.
Data collection: CrysAlis PRO (Agilent, 2012); cell
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).C9H12N2O | F(000) = 352 |
Mr = 164.21 | Dx = 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 |
Agilent Xcalibur (Eos, Gemini) diffractometer | 1675 independent reflections |
Radiation source: Enhance (Cu) X-ray Source | 1359 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
Detector resolution: 16.0416 pixels mm-1 | θmax = 72.5°, θmin = 3.0° |
ω scans | h = −18→19 |
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012) | k = −7→4 |
Tmin = 0.746, Tmax = 1.000 | l = −10→11 |
4845 measured reflections |
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(Fo2) + (0.0882P)2 + 0.1271P] where P = (Fo2 + 2Fc2)/3 |
1675 reflections | (Δ/σ)max < 0.001 |
119 parameters | Δρmax = 0.26 e Å−3 |
3 restraints | Δρmin = −0.21 e Å−3 |
C9H12N2O | V = 852.09 (16) Å3 |
Mr = 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)° |
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 = 1.000 | Rint = 0.028 |
4845 measured reflections |
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 | Δρmax = 0.26 e Å−3 |
1675 reflections | Δρmin = −0.21 e Å−3 |
119 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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) |
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 |
Mr | 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) |
Tmin, Tmax | 0.746, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4845, 1675, 1359 |
Rint | 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 |
Δρmax, Δρmin (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).
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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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).