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2-Hy­dr­oxy-N′-methyl­benzohydrazide

aCollege of Chemistry and Material Science, South-Central University for Nationalities, Wuhan 430074, People's Republic of China
*Correspondence e-mail: z.xinwen@yahoo.com

(Received 2 July 2012; accepted 4 August 2012; online 11 August 2012)

In the title mol­ecule, C8H10N2O2, there is an intra­molecular hydrogen bond involving the hy­droxy group and the O atom of the carbonyl group. The dihedral angle between the benzene ring and the amide fragment is 87.16 (10)°. The C—N—N—C torsion angle is 88.87 (18)°. In the crystal, N—H⋯N and N—H⋯O hydrogen bonds connect mol­ecules into chains along [100]. In addition, there is a weak C—H⋯π inter­action.

Related literature

For applications of related materials, see: Zhang et al. (2012[Zhang, X. W., Wu, L. M., Zhang, J. & Jin, L. F. (2012). Synth. React. Inorg. Met. Org. Nano-Met. Chem. 42, 87-91.]); Jin et al. (2011[Jin, C. Z., Yang, Y., Jin, L. F., Wu, L. M. & Zhang, J. (2011). J. Coord. Chem. 64, 4098-4107.]). For the preparation of the title compound, see: Li et al. (2001[Li, Z. G., Wang, Q. M. & Huang, J. M. (2001). In Preparation of Organic Intermediate Compounds. Beijing: Chemical Industry Publishing House.]). For a related structure, see: Jin (2007[Jin, L.-F. (2007). Acta Cryst. E63, o3465.]).

[Scheme 1]

Experimental

Crystal data
  • C8H10N2O2

  • Mr = 166.18

  • Monoclinic, P 21 /c

  • a = 7.4863 (10) Å

  • b = 14.706 (2) Å

  • c = 7.7232 (11) Å

  • β = 96.898 (2)°

  • V = 844.1 (2) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 294 K

  • 0.30 × 0.20 × 0.20 mm

Data collection
  • Bruker SMART CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.972, Tmax = 0.981

  • 6478 measured reflections

  • 1837 independent reflections

  • 1381 reflections with I > 2σ(I)

  • Rint = 0.045

Refinement
  • R[F2 > 2σ(F2)] = 0.048

  • wR(F2) = 0.129

  • S = 1.03

  • 1837 reflections

  • 119 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.16 e Å−3

  • Δρmin = −0.26 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C1–C6 ring.

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1B⋯O2 0.91 (2) 1.72 (2) 2.5535 (15) 150 (2)
N1—H1A⋯N2i 0.859 (19) 2.16 (2) 2.9415 (18) 151.9 (15)
N1—H1A⋯N1i 0.859 (19) 2.619 (18) 3.1403 (18) 120.4 (13)
N2—H2A⋯O2ii 0.884 (18) 2.253 (17) 2.9866 (16) 140.3 (14)
C4—H4⋯Cgiii 0.93 2.83 3.6713 (13) 152
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+2, -y+1, -z; (iii) [x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}].

Data collection: SMART (Bruker, 2001[Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; 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

Materials such as the title compound and the recently determined crystal structure of 4-(5-bromo-2-hydroxybenzoyl)thiosemicarbazide (Jin, 2007) are potentially important ligands and intermediates (Zhang et al., 2012; Jin et al., 2011). Part of our studies is to find new methods to synthesize derivatives of saylicylic acid and study their structures and activities. In this paper, the X-ray crystal structure determination of the title compound (I) is reported.

The molecular structure of the title compound is shown in Fig. 1. The geometric parameters of (I) agree with those related in the structure published by Jin (2007). The atoms C1—C7/O1/O2 are essentially co-planar with an r.m.s deviation of 0.016Å. There is intramolecular hydrogen bond involving the hydroxy group and the O atom of the carbonyl group. In the crystal, N—H···N and N—H···O hydrogen bonds connect molecules into one-dimensional chains along [100] (see Table 1 and Fig. 2). In addition, there is a weak intermolecular C—H···π interaction. There are some intermolecular contacts which are shorter than the sums of the van der Waals radii of the atoms involved i.e. N1···N2iv [2.9415 (18) Å], O2···N2v [2.9866 (17) Å] and C6···C6vi [3.346 (2) Å] [symmetry code (iv): 1 - x,-y,1 - z; (v): -x,-y,1 - z; (vi): 1 - x,-y,-z].

Related literature top

For applications of related materials, see: Zhang et al. (2012); Jin et al. (2011). For the preparation of the title compound, see: Li et al. (2001). For a related structure, see: Jin (2007).

Experimental top

Methyl salicylate (15.2 g, 0.10 mol) and methylhydrazine in aqueous solution (23.0 g, 0.20 mol) were mixed at 273 K and stirred for 1 h. The reaction mixture was slowly warmed to 338 K and refluxed for a further 12 h. After the resulting mixture was concentrated under reduced pressure, the residue was adjusted to pH 8 with acetic acid. After staying for 1 h in a refrigerator, the resulting precipitate was filtered and rinsed with ethyl ether. A white solid formed was recrystallized to give 7.0 g (42% yield) of N-methyl-salicylhydrazide. A block-like crystal suitable for X-ray analysis was grown from a solution of the title compound in methanol at room temperature by slow evaporation.

Refinement top

The hydroxy H atom was located in a difference Fourier map and refined isotropically [O—H = 0.91 (2) Å] with Uiso(H) = 1.5Ueq(O). The H atoms bonded to N atoms were located in a difference Fourier map and refined isotropically (N—H = 0.859 (19) and 0.884 (18) Å) with Uiso(H) = 1.2Ueq(N). All other H atoms were included in a riding-model approximation, with C—H distances of 0.93 (aromatic H atoms) and 0.96 Å (methyl atoms). The isotropic displacement parameters were set to 1.2Ueq(C) for the aromatic H atoms and to 1.5Ueq(C) for the methyl H atoms.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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. The molecular structure of (I), showing 30% probability displacement ellipsoids. The dashed lines indicates a hydrogen bond.
[Figure 2] Fig. 2. Packing diagram for (I). The hydrogen bonds are indicated by dashed lines.
2-Hydroxy-N'-methylbenzohydrazide top
Crystal data top
C8H10N2O2F(000) = 352
Mr = 166.18Dx = 1.308 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1880 reflections
a = 7.4863 (10) Åθ = 2.7–26.5°
b = 14.706 (2) ŵ = 0.10 mm1
c = 7.7232 (11) ÅT = 294 K
β = 96.898 (2)°Block, colorless
V = 844.1 (2) Å30.30 × 0.20 × 0.20 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer
1837 independent reflections
Radiation source: fine-focus sealed tube1381 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.045
ϕ and ω scansθmax = 27.0°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 79
Tmin = 0.972, Tmax = 0.981k = 1618
6478 measured reflectionsl = 99
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)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0724P)2]
where P = (Fo2 + 2Fc2)/3
1837 reflections(Δ/σ)max = 0.001
119 parametersΔρmax = 0.16 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C8H10N2O2V = 844.1 (2) Å3
Mr = 166.18Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.4863 (10) ŵ = 0.10 mm1
b = 14.706 (2) ÅT = 294 K
c = 7.7232 (11) Å0.30 × 0.20 × 0.20 mm
β = 96.898 (2)°
Data collection top
Bruker SMART CCD
diffractometer
1837 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1381 reflections with I > 2σ(I)
Tmin = 0.972, Tmax = 0.981Rint = 0.045
6478 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.129H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.16 e Å3
1837 reflectionsΔρmin = 0.26 e Å3
119 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
xyzUiso*/Ueq
C10.75411 (17)0.59342 (9)0.39608 (15)0.0389 (3)
C20.88807 (19)0.63880 (10)0.50734 (17)0.0467 (4)
C30.8400 (2)0.68846 (12)0.6475 (2)0.0593 (4)
H30.92780.71990.71920.071*
C40.6643 (2)0.69159 (11)0.68107 (19)0.0576 (4)
H40.63440.72400.77690.069*
C50.5313 (2)0.64697 (10)0.57369 (18)0.0496 (4)
H50.41220.64940.59650.060*
C60.57723 (19)0.59916 (9)0.43321 (17)0.0432 (4)
H60.48740.56970.36050.052*
C70.80781 (18)0.54385 (10)0.24308 (16)0.0423 (4)
C80.7418 (3)0.36724 (13)0.0064 (2)0.0769 (6)
H8A0.83660.35930.10050.115*
H8B0.77580.33950.09730.115*
H8C0.63380.33920.03630.115*
N10.67678 (17)0.50872 (10)0.13066 (14)0.0514 (4)
H1A0.565 (3)0.5176 (12)0.139 (2)0.062*
N20.71005 (17)0.46382 (10)0.02434 (14)0.0498 (4)
H2A0.805 (2)0.4910 (11)0.058 (2)0.060*
O11.06320 (14)0.63710 (9)0.48180 (15)0.0688 (4)
H1B1.071 (3)0.6000 (15)0.388 (3)0.103*
O20.96759 (14)0.53627 (8)0.21771 (13)0.0597 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0367 (8)0.0413 (8)0.0386 (7)0.0003 (6)0.0045 (5)0.0015 (5)
C20.0368 (8)0.0526 (9)0.0497 (7)0.0011 (6)0.0014 (6)0.0013 (6)
C30.0537 (10)0.0643 (11)0.0576 (9)0.0045 (8)0.0034 (7)0.0194 (7)
C40.0604 (11)0.0587 (10)0.0547 (8)0.0022 (8)0.0112 (7)0.0166 (7)
C50.0436 (9)0.0534 (9)0.0540 (8)0.0020 (7)0.0154 (6)0.0050 (7)
C60.0397 (8)0.0466 (8)0.0438 (7)0.0051 (6)0.0064 (5)0.0015 (6)
C70.0339 (8)0.0515 (9)0.0422 (7)0.0005 (6)0.0069 (5)0.0013 (6)
C80.0874 (15)0.0714 (14)0.0732 (11)0.0043 (10)0.0149 (9)0.0133 (9)
N10.0346 (7)0.0761 (9)0.0442 (6)0.0007 (6)0.0077 (5)0.0167 (6)
N20.0402 (7)0.0668 (9)0.0438 (6)0.0031 (6)0.0113 (5)0.0136 (6)
O10.0349 (7)0.0969 (10)0.0734 (7)0.0048 (6)0.0013 (5)0.0247 (7)
O20.0352 (6)0.0868 (9)0.0586 (6)0.0012 (5)0.0113 (4)0.0172 (5)
Geometric parameters (Å, º) top
C1—C61.3907 (19)C6—H60.9300
C1—C21.4081 (18)C7—O21.2401 (16)
C1—C71.4844 (18)C7—N11.3336 (18)
C2—O11.3493 (17)C8—N21.455 (2)
C2—C31.388 (2)C8—H8A0.9600
C3—C41.372 (2)C8—H8B0.9600
C3—H30.9300C8—H8C0.9600
C4—C51.383 (2)N1—N21.4152 (16)
C4—H40.9300N1—H1A0.859 (19)
C5—C61.3709 (19)N2—H2A0.884 (18)
C5—H50.9300O1—H1B0.91 (2)
C6—C1—C2118.12 (12)C1—C6—H6119.0
C6—C1—C7123.34 (11)O2—C7—N1120.69 (12)
C2—C1—C7118.52 (13)O2—C7—C1121.90 (12)
O1—C2—C3118.09 (13)N1—C7—C1117.40 (12)
O1—C2—C1122.37 (12)N2—C8—H8A109.5
C3—C2—C1119.53 (14)N2—C8—H8B109.5
C4—C3—C2120.61 (13)H8A—C8—H8B109.5
C4—C3—H3119.7N2—C8—H8C109.5
C2—C3—H3119.7H8A—C8—H8C109.5
C3—C4—C5120.57 (13)H8B—C8—H8C109.5
C3—C4—H4119.7C7—N1—N2122.75 (12)
C5—C4—H4119.7C7—N1—H1A122.9 (11)
C6—C5—C4119.14 (14)N2—N1—H1A113.8 (11)
C6—C5—H5120.4N1—N2—C8111.07 (12)
C4—C5—H5120.4N1—N2—H2A105.5 (10)
C5—C6—C1122.00 (13)C8—N2—H2A111.6 (11)
C5—C6—H6119.0C2—O1—H1B106.4 (14)
C6—C1—C2—O1179.99 (12)C2—C1—C6—C50.2 (2)
C7—C1—C2—O11.5 (2)C7—C1—C6—C5178.69 (12)
C6—C1—C2—C31.0 (2)C6—C1—C7—O2176.57 (13)
C7—C1—C2—C3177.58 (13)C2—C1—C7—O25.0 (2)
O1—C2—C3—C4179.12 (15)C6—C1—C7—N14.7 (2)
C1—C2—C3—C41.8 (2)C2—C1—C7—N1173.80 (13)
C2—C3—C4—C51.4 (2)O2—C7—N1—N21.9 (2)
C3—C4—C5—C60.2 (2)C1—C7—N1—N2176.89 (12)
C4—C5—C6—C10.6 (2)C7—N1—N2—C888.87 (18)
Hydrogen-bond geometry (Å, º) top
Cg is the centroid of the C1–C6 ring.
D—H···AD—HH···AD···AD—H···A
O1—H1B···O20.91 (2)1.72 (2)2.5535 (15)150 (2)
N1—H1A···N2i0.859 (19)2.16 (2)2.9415 (18)151.9 (15)
N1—H1A···N1i0.859 (19)2.619 (18)3.1403 (18)120.4 (13)
N2—H2A···O2ii0.884 (18)2.253 (17)2.9866 (16)140.3 (14)
C4—H4···Cgiii0.932.833.6713 (13)152
Symmetry codes: (i) x+1, y+1, z; (ii) x+2, y+1, z; (iii) x, y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC8H10N2O2
Mr166.18
Crystal system, space groupMonoclinic, P21/c
Temperature (K)294
a, b, c (Å)7.4863 (10), 14.706 (2), 7.7232 (11)
β (°) 96.898 (2)
V3)844.1 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.30 × 0.20 × 0.20
Data collection
DiffractometerBruker SMART CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.972, 0.981
No. of measured, independent and
observed [I > 2σ(I)] reflections
6478, 1837, 1381
Rint0.045
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.129, 1.03
No. of reflections1837
No. of parameters119
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.16, 0.26

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
Cg is the centroid of the C1–C6 ring.
D—H···AD—HH···AD···AD—H···A
O1—H1B···O20.91 (2)1.72 (2)2.5535 (15)150 (2)
N1—H1A···N2i0.859 (19)2.16 (2)2.9415 (18)151.9 (15)
N1—H1A···N1i0.859 (19)2.619 (18)3.1403 (18)120.4 (13)
N2—H2A···O2ii0.884 (18)2.253 (17)2.9866 (16)140.3 (14)
C4—H4···Cgiii0.932.833.6713 (13)152
Symmetry codes: (i) x+1, y+1, z; (ii) x+2, y+1, z; (iii) x, y+3/2, z+1/2.
 

Acknowledgements

This work was supported by the Research Funds of South-Central University for Nationalities.

References

First citationBruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationJin, L.-F. (2007). Acta Cryst. E63, o3465.  Web of Science CSD CrossRef IUCr Journals
First citationJin, C. Z., Yang, Y., Jin, L. F., Wu, L. M. & Zhang, J. (2011). J. Coord. Chem. 64, 4098–4107.  Web of Science CSD CrossRef CAS
First citationLi, Z. G., Wang, Q. M. & Huang, J. M. (2001). In Preparation of Organic Intermediate Compounds. Beijing: Chemical Industry Publishing House.
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationZhang, X. W., Wu, L. M., Zhang, J. & Jin, L. F. (2012). Synth. React. Inorg. Met. Org. Nano-Met. Chem. 42, 87–91.

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