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The title compound, C8H10N2O3, is an important inter­mediate for the synthesis of biologically active heterocyclic compounds. The planar hydrazide group is oriented at a dihedral angle of 25.15 (3)° with respect to the benzene ring. In the crystal structure, inter­molecular N—H...N, N—H...O and O—H...O hydrogen bonds link the mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807053160/hk2352sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807053160/hk2352Isup2.hkl
Contains datablock I

CCDC reference: 672787

Key indicators

  • Single-crystal X-ray study
  • T = 120 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.045
  • wR factor = 0.087
  • Data-to-parameter ratio = 14.2

checkCIF/PLATON results

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Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Aromatic hydrazides are important intermediates in heterocyclic chemistry and have been used for the synthesis of various biologically active five-membered heterocycles such as 2,5-disubstituted-1,3,4-oxadiazoles (Zheng et al., 2003; Al-Talib et al., 1990) and 5-substituted-2-mercapto-1,3,4-oxadiazoles (Yousif et al., 1986; Al-Soud et al., 2004; El-Emam et al., 2004). In view of the versatility of these compounds, we have synthesized the title compound, (I), and reported its crystal structure.

In the molecule of (I) (Fig. 1), the bond lengths and angles are within normal ranges (Allen et al., 1987). The dihedral angle between the planar hydrazidic group (C6/O3/N1/N2) and the benzene ring (C2—C5/C7/C8) is 25.15 (3)°.

In the crystal structure, intermolecular N—H···N, N—H···O and O—H···O hydrogen bonds (Table 1, Fig. 2) link the molecules, in which they seem to be effective in the stabilization of the structure.

Related literature top

For related literature, see: Zheng et al. (2003); Al-Talib et al. (1990); Yousif et al. (1986); Al-Soud et al. (2004); El-Emam et al. (2004); Furniss et al. (1978). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I), is synthesized by the reaction of methyl ester of 3-hydroxy-4-methoxybenzoic acid with hydrazine hydrate using the reported procedure (Furniss et al., 1978). For the preparation of (I), a mixture of methyl-3-hydroxy-4-methoxybenzoate (1.82 g, 10 mmol) and hydrazine hydrate (80%, 15 ml) in absolute ethanol (50 ml) was refluxed for 5 h at 413–423 K. The excess solvent was removed by distillation. The solid residue was filtered off, washed with water and recrystallized from ethanol (30%) to give the title compound (yield; 1.5 g, 82%, m.p. 475–477 K). Colorless single crystals of (I) were obtained by slow evaporation of an ethanol solution at room temperature.

Refinement top

H atoms of OH, NH and NH2 groups were located in difference syntheses and refined isotropically [O—H = 0.086 (2) Å and Uiso(H) = 0.044 (7) Å2 (for OH); N—H = 0.88 (2) Å and Uiso(H) = 0.024 (5) Å2 (for NH); N—H = 0.91 (2) and 0.93 (2) Å, Uiso(H) = 0.019 (5) and 0.027 (5) Å2 (for NH2)]. The remaining H atoms were positioned geometrically, with C—H = 0.95 and 0.98 Å for aromatic and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.2 for aromatic H, and x = 1.5 for methyl H atoms.

Computing details top

Data collection: COLLECT (Bruker AXS, 2000); cell refinement: EVALCCD (Duisenberg et al., 2003); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2007); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.
[Figure 3] Fig. 3. The formation of the title compound.
3-Hydroxy-4-methoxybenzohydrazide top
Crystal data top
C8H10N2O3Dx = 1.448 Mg m3
Mr = 182.18Melting point: 475(2) K
Trigonal, R3Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -R 3Cell parameters from 13690 reflections
a = 19.4079 (10) Åθ = 1.0–27.5°
c = 11.5250 (4) ŵ = 0.11 mm1
V = 3759.5 (3) Å3T = 120 K
Z = 18Block, colorless
F(000) = 17280.21 × 0.20 × 0.12 mm
Data collection top
Nonius KappaCCD
diffractometer
1920 independent reflections
Radiation source: fine-focus sealed tube1362 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromatorRint = 0.064
Detector resolution: 9 pixels mm-1θmax = 27.5°, θmin = 3.0°
ϕ scans and ω scans with κ offseth = 2425
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 2525
Tmin = 0.977, Tmax = 0.987l = 1412
14714 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)] = 0.045Hydrogen site location: mixed
wR(F2) = 0.087H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0273P)2 + 5.5999P]
where P = (Fo2 + 2Fc2)/3
1920 reflections(Δ/σ)max < 0.001
135 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = 0.23 e Å3
Crystal data top
C8H10N2O3Z = 18
Mr = 182.18Mo Kα radiation
Trigonal, R3µ = 0.11 mm1
a = 19.4079 (10) ÅT = 120 K
c = 11.5250 (4) Å0.21 × 0.20 × 0.12 mm
V = 3759.5 (3) Å3
Data collection top
Nonius KappaCCD
diffractometer
1920 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1362 reflections with I > 2σ(I)
Tmin = 0.977, Tmax = 0.987Rint = 0.064
14714 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.087H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.24 e Å3
1920 reflectionsΔρmin = 0.23 e Å3
135 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
O10.09395 (7)0.93439 (7)0.22631 (10)0.0177 (3)
O20.24707 (7)1.00363 (7)0.25462 (9)0.0166 (3)
H2O0.2983 (15)1.0281 (14)0.2516 (19)0.044 (7)*
O30.35414 (6)0.92873 (6)0.09783 (9)0.0144 (3)
N10.24700 (9)0.81514 (8)0.15538 (11)0.0143 (3)
H1N0.1958 (12)0.7796 (12)0.1509 (16)0.024 (5)*
N20.29078 (9)0.78856 (8)0.22064 (13)0.0147 (3)
H2N0.3332 (12)0.7967 (11)0.1776 (16)0.019 (5)*
H2M0.3109 (12)0.8204 (12)0.2860 (18)0.027 (5)*
C10.00948 (10)0.89463 (11)0.21621 (16)0.0229 (4)
H1A0.01180.83700.21460.034*
H1B0.01280.90830.28280.034*
H1C0.00510.91130.14440.034*
C20.13430 (10)0.91959 (10)0.14269 (13)0.0132 (4)
C30.21694 (10)0.95706 (9)0.15902 (13)0.0126 (4)
C40.26263 (10)0.94487 (9)0.07985 (13)0.0130 (4)
H40.31850.96990.09100.016*
C50.22816 (9)0.89622 (9)0.01679 (13)0.0123 (3)
C60.28099 (9)0.88187 (9)0.09396 (13)0.0118 (3)
C70.14684 (10)0.86073 (10)0.03336 (14)0.0157 (4)
H70.12290.82810.09940.019*
C80.10022 (10)0.87259 (10)0.04603 (14)0.0160 (4)
H80.04450.84830.03390.019*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0116 (6)0.0231 (7)0.0181 (6)0.0085 (5)0.0025 (5)0.0038 (5)
O20.0117 (6)0.0203 (7)0.0145 (6)0.0057 (6)0.0019 (5)0.0062 (5)
O30.0126 (6)0.0125 (6)0.0172 (6)0.0056 (5)0.0002 (5)0.0016 (5)
N10.0118 (8)0.0130 (7)0.0168 (7)0.0051 (7)0.0025 (6)0.0022 (6)
N20.0147 (8)0.0159 (8)0.0157 (7)0.0093 (7)0.0025 (6)0.0016 (6)
C10.0138 (9)0.0299 (11)0.0250 (10)0.0109 (8)0.0036 (7)0.0019 (8)
C20.0148 (9)0.0132 (8)0.0135 (8)0.0084 (7)0.0026 (7)0.0019 (7)
C30.0164 (9)0.0098 (8)0.0111 (8)0.0061 (7)0.0002 (7)0.0009 (6)
C40.0109 (8)0.0127 (8)0.0148 (8)0.0055 (7)0.0002 (6)0.0019 (7)
C50.0151 (8)0.0098 (8)0.0128 (8)0.0069 (7)0.0013 (7)0.0020 (6)
C60.0142 (9)0.0114 (8)0.0107 (8)0.0071 (7)0.0010 (6)0.0022 (6)
C70.0166 (9)0.0150 (9)0.0145 (8)0.0072 (7)0.0019 (7)0.0024 (7)
C80.0109 (8)0.0166 (9)0.0194 (8)0.0060 (7)0.0009 (7)0.0003 (7)
Geometric parameters (Å, º) top
O1—C21.3599 (19)C1—H1C0.9800
O1—C11.425 (2)C2—C81.381 (2)
O2—C31.3580 (19)C2—C31.404 (2)
O2—H2O0.86 (2)C3—C41.373 (2)
O3—C61.2464 (19)C4—C51.396 (2)
N1—C61.326 (2)C4—H40.9500
N1—N21.4114 (19)C5—C71.384 (2)
N1—H1N0.88 (2)C5—C61.485 (2)
N2—H2N0.91 (2)C7—C81.385 (2)
N2—H2M0.93 (2)C7—H70.9500
C1—H1A0.9800C8—H80.9500
C1—H1B0.9800
C2—O1—C1117.11 (13)O2—C3—C2116.99 (14)
C3—O2—H2O109.1 (15)C4—C3—C2119.39 (14)
C6—N1—N2123.02 (14)C3—C4—C5120.97 (15)
C6—N1—H1N123.1 (12)C3—C4—H4119.5
N2—N1—H1N113.2 (12)C5—C4—H4119.5
N1—N2—H2N107.8 (12)C7—C5—C4119.24 (15)
N1—N2—H2M108.6 (12)C7—C5—C6123.13 (14)
H2N—N2—H2M106.6 (17)C4—C5—C6117.55 (14)
O1—C1—H1A109.5O3—C6—N1121.49 (15)
O1—C1—H1B109.5O3—C6—C5121.73 (14)
H1A—C1—H1B109.5N1—C6—C5116.74 (14)
O1—C1—H1C109.5C5—C7—C8120.24 (15)
H1A—C1—H1C109.5C5—C7—H7119.9
H1B—C1—H1C109.5C8—C7—H7119.9
O1—C2—C8125.10 (15)C2—C8—C7120.39 (15)
O1—C2—C3115.15 (14)C2—C8—H8119.8
C8—C2—C3119.75 (15)C7—C8—H8119.8
O2—C3—C4123.62 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···N2i0.91 (2)2.24 (2)3.1274 (19)165.3 (16)
N2—H2N···N1i0.91 (2)2.567 (19)3.266 (2)134.5 (15)
N2—H2M···O2ii0.93 (2)2.15 (2)3.0364 (19)158.6 (17)
N2—H2M···O1ii0.93 (2)2.43 (2)3.1335 (18)132.6 (15)
N1—H1N···O3iii0.88 (2)2.15 (2)2.9296 (18)147.6 (16)
O2—H2O···O3iv0.86 (2)1.81 (2)2.6635 (16)171 (2)
Symmetry codes: (i) y1/3, x+y+1/3, z+1/3; (ii) y+4/3, xy+5/3, z+2/3; (iii) xy+2/3, x+1/3, z+1/3; (iv) y+4/3, xy+5/3, z1/3.

Experimental details

Crystal data
Chemical formulaC8H10N2O3
Mr182.18
Crystal system, space groupTrigonal, R3
Temperature (K)120
a, c (Å)19.4079 (10), 11.5250 (4)
V3)3759.5 (3)
Z18
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.21 × 0.20 × 0.12
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.977, 0.987
No. of measured, independent and
observed [I > 2σ(I)] reflections
14714, 1920, 1362
Rint0.064
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.087, 1.07
No. of reflections1920
No. of parameters135
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.24, 0.23

Computer programs: COLLECT (Bruker AXS, 2000), EVALCCD (Duisenberg et al., 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2007).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···N2i0.91 (2)2.24 (2)3.1274 (19)165.3 (16)
N2—H2N···N1i0.91 (2)2.567 (19)3.266 (2)134.5 (15)
N2—H2M···O2ii0.93 (2)2.15 (2)3.0364 (19)158.6 (17)
N2—H2M···O1ii0.93 (2)2.43 (2)3.1335 (18)132.6 (15)
N1—H1N···O3iii0.88 (2)2.15 (2)2.9296 (18)147.6 (16)
O2—H2O···O3iv0.86 (2)1.81 (2)2.6635 (16)171 (2)
Symmetry codes: (i) y1/3, x+y+1/3, z+1/3; (ii) y+4/3, xy+5/3, z+2/3; (iii) xy+2/3, x+1/3, z+1/3; (iv) y+4/3, xy+5/3, z1/3.
 

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