organic compounds
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
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); Jin et al. (2011). For the preparation of the title compound, see: Li et al. (2001). For a related structure, see: Jin (2007).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2001); cell SAINT (Bruker, 2001); data reduction: SAINT; 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/S160053681203468X/lh5501sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S160053681203468X/lh5501Isup2.hkl
Supporting information file. DOI: 10.1107/S160053681203468X/lh5501Isup3.cml
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.
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.
Data collection: SMART (Bruker, 2001); cell
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).Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids. The dashed lines indicates a hydrogen bond. | |
Fig. 2. Packing diagram for (I). The hydrogen bonds are indicated by dashed lines. |
C8H10N2O2 | F(000) = 352 |
Mr = 166.18 | Dx = 1.308 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1880 reflections |
a = 7.4863 (10) Å | θ = 2.7–26.5° |
b = 14.706 (2) Å | µ = 0.10 mm−1 |
c = 7.7232 (11) Å | T = 294 K |
β = 96.898 (2)° | Block, colorless |
V = 844.1 (2) Å3 | 0.30 × 0.20 × 0.20 mm |
Z = 4 |
Bruker SMART CCD diffractometer | 1837 independent reflections |
Radiation source: fine-focus sealed tube | 1381 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
ϕ and ω scans | θmax = 27.0°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→9 |
Tmin = 0.972, Tmax = 0.981 | k = −16→18 |
6478 measured reflections | l = −9→9 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H 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 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C8H10N2O2 | V = 844.1 (2) Å3 |
Mr = 166.18 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.4863 (10) Å | µ = 0.10 mm−1 |
b = 14.706 (2) Å | T = 294 K |
c = 7.7232 (11) Å | 0.30 × 0.20 × 0.20 mm |
β = 96.898 (2)° |
Bruker SMART CCD diffractometer | 1837 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1381 reflections with I > 2σ(I) |
Tmin = 0.972, Tmax = 0.981 | Rint = 0.045 |
6478 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.129 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.16 e Å−3 |
1837 reflections | Δρmin = −0.26 e Å−3 |
119 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.75411 (17) | 0.59342 (9) | 0.39608 (15) | 0.0389 (3) | |
C2 | 0.88807 (19) | 0.63880 (10) | 0.50734 (17) | 0.0467 (4) | |
C3 | 0.8400 (2) | 0.68846 (12) | 0.6475 (2) | 0.0593 (4) | |
H3 | 0.9278 | 0.7199 | 0.7192 | 0.071* | |
C4 | 0.6643 (2) | 0.69159 (11) | 0.68107 (19) | 0.0576 (4) | |
H4 | 0.6344 | 0.7240 | 0.7769 | 0.069* | |
C5 | 0.5313 (2) | 0.64697 (10) | 0.57369 (18) | 0.0496 (4) | |
H5 | 0.4122 | 0.6494 | 0.5965 | 0.060* | |
C6 | 0.57723 (19) | 0.59916 (9) | 0.43321 (17) | 0.0432 (4) | |
H6 | 0.4874 | 0.5697 | 0.3605 | 0.052* | |
C7 | 0.80781 (18) | 0.54385 (10) | 0.24308 (16) | 0.0423 (4) | |
C8 | 0.7418 (3) | 0.36724 (13) | 0.0064 (2) | 0.0769 (6) | |
H8A | 0.8366 | 0.3593 | 0.1005 | 0.115* | |
H8B | 0.7758 | 0.3395 | −0.0973 | 0.115* | |
H8C | 0.6338 | 0.3392 | 0.0363 | 0.115* | |
N1 | 0.67678 (17) | 0.50872 (10) | 0.13066 (14) | 0.0514 (4) | |
H1A | 0.565 (3) | 0.5176 (12) | 0.139 (2) | 0.062* | |
N2 | 0.71005 (17) | 0.46382 (10) | −0.02434 (14) | 0.0498 (4) | |
H2A | 0.805 (2) | 0.4910 (11) | −0.058 (2) | 0.060* | |
O1 | 1.06320 (14) | 0.63710 (9) | 0.48180 (15) | 0.0688 (4) | |
H1B | 1.071 (3) | 0.6000 (15) | 0.388 (3) | 0.103* | |
O2 | 0.96759 (14) | 0.53627 (8) | 0.21771 (13) | 0.0597 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0367 (8) | 0.0413 (8) | 0.0386 (7) | 0.0003 (6) | 0.0045 (5) | 0.0015 (5) |
C2 | 0.0368 (8) | 0.0526 (9) | 0.0497 (7) | 0.0011 (6) | 0.0014 (6) | −0.0013 (6) |
C3 | 0.0537 (10) | 0.0643 (11) | 0.0576 (9) | −0.0045 (8) | −0.0034 (7) | −0.0194 (7) |
C4 | 0.0604 (11) | 0.0587 (10) | 0.0547 (8) | 0.0022 (8) | 0.0112 (7) | −0.0166 (7) |
C5 | 0.0436 (9) | 0.0534 (9) | 0.0540 (8) | −0.0020 (7) | 0.0154 (6) | −0.0050 (7) |
C6 | 0.0397 (8) | 0.0466 (8) | 0.0438 (7) | −0.0051 (6) | 0.0064 (5) | −0.0015 (6) |
C7 | 0.0339 (8) | 0.0515 (9) | 0.0422 (7) | −0.0005 (6) | 0.0069 (5) | 0.0013 (6) |
C8 | 0.0874 (15) | 0.0714 (14) | 0.0732 (11) | 0.0043 (10) | 0.0149 (9) | −0.0133 (9) |
N1 | 0.0346 (7) | 0.0761 (9) | 0.0442 (6) | 0.0007 (6) | 0.0077 (5) | −0.0167 (6) |
N2 | 0.0402 (7) | 0.0668 (9) | 0.0438 (6) | −0.0031 (6) | 0.0113 (5) | −0.0136 (6) |
O1 | 0.0349 (7) | 0.0969 (10) | 0.0734 (7) | −0.0048 (6) | 0.0013 (5) | −0.0247 (7) |
O2 | 0.0352 (6) | 0.0868 (9) | 0.0586 (6) | −0.0012 (5) | 0.0113 (4) | −0.0172 (5) |
C1—C6 | 1.3907 (19) | C6—H6 | 0.9300 |
C1—C2 | 1.4081 (18) | C7—O2 | 1.2401 (16) |
C1—C7 | 1.4844 (18) | C7—N1 | 1.3336 (18) |
C2—O1 | 1.3493 (17) | C8—N2 | 1.455 (2) |
C2—C3 | 1.388 (2) | C8—H8A | 0.9600 |
C3—C4 | 1.372 (2) | C8—H8B | 0.9600 |
C3—H3 | 0.9300 | C8—H8C | 0.9600 |
C4—C5 | 1.383 (2) | N1—N2 | 1.4152 (16) |
C4—H4 | 0.9300 | N1—H1A | 0.859 (19) |
C5—C6 | 1.3709 (19) | N2—H2A | 0.884 (18) |
C5—H5 | 0.9300 | O1—H1B | 0.91 (2) |
C6—C1—C2 | 118.12 (12) | C1—C6—H6 | 119.0 |
C6—C1—C7 | 123.34 (11) | O2—C7—N1 | 120.69 (12) |
C2—C1—C7 | 118.52 (13) | O2—C7—C1 | 121.90 (12) |
O1—C2—C3 | 118.09 (13) | N1—C7—C1 | 117.40 (12) |
O1—C2—C1 | 122.37 (12) | N2—C8—H8A | 109.5 |
C3—C2—C1 | 119.53 (14) | N2—C8—H8B | 109.5 |
C4—C3—C2 | 120.61 (13) | H8A—C8—H8B | 109.5 |
C4—C3—H3 | 119.7 | N2—C8—H8C | 109.5 |
C2—C3—H3 | 119.7 | H8A—C8—H8C | 109.5 |
C3—C4—C5 | 120.57 (13) | H8B—C8—H8C | 109.5 |
C3—C4—H4 | 119.7 | C7—N1—N2 | 122.75 (12) |
C5—C4—H4 | 119.7 | C7—N1—H1A | 122.9 (11) |
C6—C5—C4 | 119.14 (14) | N2—N1—H1A | 113.8 (11) |
C6—C5—H5 | 120.4 | N1—N2—C8 | 111.07 (12) |
C4—C5—H5 | 120.4 | N1—N2—H2A | 105.5 (10) |
C5—C6—C1 | 122.00 (13) | C8—N2—H2A | 111.6 (11) |
C5—C6—H6 | 119.0 | C2—O1—H1B | 106.4 (14) |
C6—C1—C2—O1 | 179.99 (12) | C2—C1—C6—C5 | −0.2 (2) |
C7—C1—C2—O1 | −1.5 (2) | C7—C1—C6—C5 | −178.69 (12) |
C6—C1—C2—C3 | −1.0 (2) | C6—C1—C7—O2 | −176.57 (13) |
C7—C1—C2—C3 | 177.58 (13) | C2—C1—C7—O2 | 5.0 (2) |
O1—C2—C3—C4 | −179.12 (15) | C6—C1—C7—N1 | 4.7 (2) |
C1—C2—C3—C4 | 1.8 (2) | C2—C1—C7—N1 | −173.80 (13) |
C2—C3—C4—C5 | −1.4 (2) | O2—C7—N1—N2 | −1.9 (2) |
C3—C4—C5—C6 | 0.2 (2) | C1—C7—N1—N2 | 176.89 (12) |
C4—C5—C6—C1 | 0.6 (2) | C7—N1—N2—C8 | 88.87 (18) |
Cg is the centroid of the C1–C6 ring. |
D—H···A | D—H | H···A | D···A | 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+3/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C8H10N2O2 |
Mr | 166.18 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 7.4863 (10), 14.706 (2), 7.7232 (11) |
β (°) | 96.898 (2) |
V (Å3) | 844.1 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.972, 0.981 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6478, 1837, 1381 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.129, 1.03 |
No. of reflections | 1837 |
No. of parameters | 119 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.16, −0.26 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Cg is the centroid of the C1–C6 ring. |
D—H···A | D—H | H···A | D···A | 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+3/2, z+1/2. |
Acknowledgements
This work was supported by the Research Funds of South-Central University for Nationalities.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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].