Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807053160/hk2352sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807053160/hk2352Isup2.hkl |
CCDC reference: 672787
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (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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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.
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.
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).
C8H10N2O3 | Dx = 1.448 Mg m−3 |
Mr = 182.18 | Melting point: 475(2) K |
Trigonal, R3 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -R 3 | Cell parameters from 13690 reflections |
a = 19.4079 (10) Å | θ = 1.0–27.5° |
c = 11.5250 (4) Å | µ = 0.11 mm−1 |
V = 3759.5 (3) Å3 | T = 120 K |
Z = 18 | Block, colorless |
F(000) = 1728 | 0.21 × 0.20 × 0.12 mm |
Nonius KappaCCD diffractometer | 1920 independent reflections |
Radiation source: fine-focus sealed tube | 1362 reflections with I > 2σ(I) |
Horizontally mounted graphite crystal monochromator | Rint = 0.064 |
Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ϕ scans and ω scans with κ offset | h = −24→25 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −25→25 |
Tmin = 0.977, Tmax = 0.987 | l = −14→12 |
14714 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)] = 0.045 | Hydrogen site location: mixed |
wR(F2) = 0.087 | H 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 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C8H10N2O3 | Z = 18 |
Mr = 182.18 | Mo Kα radiation |
Trigonal, R3 | µ = 0.11 mm−1 |
a = 19.4079 (10) Å | T = 120 K |
c = 11.5250 (4) Å | 0.21 × 0.20 × 0.12 mm |
V = 3759.5 (3) Å3 |
Nonius KappaCCD diffractometer | 1920 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1362 reflections with I > 2σ(I) |
Tmin = 0.977, Tmax = 0.987 | Rint = 0.064 |
14714 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.24 e Å−3 |
1920 reflections | Δρmin = −0.23 e Å−3 |
135 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 | ||
O1 | 0.09395 (7) | 0.93439 (7) | −0.22631 (10) | 0.0177 (3) | |
O2 | 0.24707 (7) | 1.00363 (7) | −0.25462 (9) | 0.0166 (3) | |
H2O | 0.2983 (15) | 1.0281 (14) | −0.2516 (19) | 0.044 (7)* | |
O3 | 0.35414 (6) | 0.92873 (6) | 0.09783 (9) | 0.0144 (3) | |
N1 | 0.24700 (9) | 0.81514 (8) | 0.15538 (11) | 0.0143 (3) | |
H1N | 0.1958 (12) | 0.7796 (12) | 0.1509 (16) | 0.024 (5)* | |
N2 | 0.29078 (9) | 0.78856 (8) | 0.22064 (13) | 0.0147 (3) | |
H2N | 0.3332 (12) | 0.7967 (11) | 0.1776 (16) | 0.019 (5)* | |
H2M | 0.3109 (12) | 0.8204 (12) | 0.2860 (18) | 0.027 (5)* | |
C1 | 0.00948 (10) | 0.89463 (11) | −0.21621 (16) | 0.0229 (4) | |
H1A | −0.0118 | 0.8370 | −0.2146 | 0.034* | |
H1B | −0.0128 | 0.9083 | −0.2828 | 0.034* | |
H1C | −0.0051 | 0.9113 | −0.1444 | 0.034* | |
C2 | 0.13430 (10) | 0.91959 (10) | −0.14269 (13) | 0.0132 (4) | |
C3 | 0.21694 (10) | 0.95706 (9) | −0.15902 (13) | 0.0126 (4) | |
C4 | 0.26263 (10) | 0.94487 (9) | −0.07985 (13) | 0.0130 (4) | |
H4 | 0.3185 | 0.9699 | −0.0910 | 0.016* | |
C5 | 0.22816 (9) | 0.89622 (9) | 0.01679 (13) | 0.0123 (3) | |
C6 | 0.28099 (9) | 0.88187 (9) | 0.09396 (13) | 0.0118 (3) | |
C7 | 0.14684 (10) | 0.86073 (10) | 0.03336 (14) | 0.0157 (4) | |
H7 | 0.1229 | 0.8281 | 0.0994 | 0.019* | |
C8 | 0.10022 (10) | 0.87259 (10) | −0.04603 (14) | 0.0160 (4) | |
H8 | 0.0445 | 0.8483 | −0.0339 | 0.019* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0116 (6) | 0.0231 (7) | 0.0181 (6) | 0.0085 (5) | −0.0025 (5) | 0.0038 (5) |
O2 | 0.0117 (6) | 0.0203 (7) | 0.0145 (6) | 0.0057 (6) | 0.0019 (5) | 0.0062 (5) |
O3 | 0.0126 (6) | 0.0125 (6) | 0.0172 (6) | 0.0056 (5) | 0.0002 (5) | 0.0016 (5) |
N1 | 0.0118 (8) | 0.0130 (7) | 0.0168 (7) | 0.0051 (7) | −0.0025 (6) | 0.0022 (6) |
N2 | 0.0147 (8) | 0.0159 (8) | 0.0157 (7) | 0.0093 (7) | −0.0025 (6) | 0.0016 (6) |
C1 | 0.0138 (9) | 0.0299 (11) | 0.0250 (10) | 0.0109 (8) | −0.0036 (7) | 0.0019 (8) |
C2 | 0.0148 (9) | 0.0132 (8) | 0.0135 (8) | 0.0084 (7) | −0.0026 (7) | −0.0019 (7) |
C3 | 0.0164 (9) | 0.0098 (8) | 0.0111 (8) | 0.0061 (7) | 0.0002 (7) | −0.0009 (6) |
C4 | 0.0109 (8) | 0.0127 (8) | 0.0148 (8) | 0.0055 (7) | 0.0002 (6) | −0.0019 (7) |
C5 | 0.0151 (8) | 0.0098 (8) | 0.0128 (8) | 0.0069 (7) | −0.0013 (7) | −0.0020 (6) |
C6 | 0.0142 (9) | 0.0114 (8) | 0.0107 (8) | 0.0071 (7) | 0.0010 (6) | −0.0022 (6) |
C7 | 0.0166 (9) | 0.0150 (9) | 0.0145 (8) | 0.0072 (7) | 0.0019 (7) | 0.0024 (7) |
C8 | 0.0109 (8) | 0.0166 (9) | 0.0194 (8) | 0.0060 (7) | 0.0009 (7) | −0.0003 (7) |
O1—C2 | 1.3599 (19) | C1—H1C | 0.9800 |
O1—C1 | 1.425 (2) | C2—C8 | 1.381 (2) |
O2—C3 | 1.3580 (19) | C2—C3 | 1.404 (2) |
O2—H2O | 0.86 (2) | C3—C4 | 1.373 (2) |
O3—C6 | 1.2464 (19) | C4—C5 | 1.396 (2) |
N1—C6 | 1.326 (2) | C4—H4 | 0.9500 |
N1—N2 | 1.4114 (19) | C5—C7 | 1.384 (2) |
N1—H1N | 0.88 (2) | C5—C6 | 1.485 (2) |
N2—H2N | 0.91 (2) | C7—C8 | 1.385 (2) |
N2—H2M | 0.93 (2) | C7—H7 | 0.9500 |
C1—H1A | 0.9800 | C8—H8 | 0.9500 |
C1—H1B | 0.9800 | ||
C2—O1—C1 | 117.11 (13) | O2—C3—C2 | 116.99 (14) |
C3—O2—H2O | 109.1 (15) | C4—C3—C2 | 119.39 (14) |
C6—N1—N2 | 123.02 (14) | C3—C4—C5 | 120.97 (15) |
C6—N1—H1N | 123.1 (12) | C3—C4—H4 | 119.5 |
N2—N1—H1N | 113.2 (12) | C5—C4—H4 | 119.5 |
N1—N2—H2N | 107.8 (12) | C7—C5—C4 | 119.24 (15) |
N1—N2—H2M | 108.6 (12) | C7—C5—C6 | 123.13 (14) |
H2N—N2—H2M | 106.6 (17) | C4—C5—C6 | 117.55 (14) |
O1—C1—H1A | 109.5 | O3—C6—N1 | 121.49 (15) |
O1—C1—H1B | 109.5 | O3—C6—C5 | 121.73 (14) |
H1A—C1—H1B | 109.5 | N1—C6—C5 | 116.74 (14) |
O1—C1—H1C | 109.5 | C5—C7—C8 | 120.24 (15) |
H1A—C1—H1C | 109.5 | C5—C7—H7 | 119.9 |
H1B—C1—H1C | 109.5 | C8—C7—H7 | 119.9 |
O1—C2—C8 | 125.10 (15) | C2—C8—C7 | 120.39 (15) |
O1—C2—C3 | 115.15 (14) | C2—C8—H8 | 119.8 |
C8—C2—C3 | 119.75 (15) | C7—C8—H8 | 119.8 |
O2—C3—C4 | 123.62 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···N2i | 0.91 (2) | 2.24 (2) | 3.1274 (19) | 165.3 (16) |
N2—H2N···N1i | 0.91 (2) | 2.567 (19) | 3.266 (2) | 134.5 (15) |
N2—H2M···O2ii | 0.93 (2) | 2.15 (2) | 3.0364 (19) | 158.6 (17) |
N2—H2M···O1ii | 0.93 (2) | 2.43 (2) | 3.1335 (18) | 132.6 (15) |
N1—H1N···O3iii | 0.88 (2) | 2.15 (2) | 2.9296 (18) | 147.6 (16) |
O2—H2O···O3iv | 0.86 (2) | 1.81 (2) | 2.6635 (16) | 171 (2) |
Symmetry codes: (i) y−1/3, −x+y+1/3, −z+1/3; (ii) −y+4/3, x−y+5/3, z+2/3; (iii) x−y+2/3, x+1/3, −z+1/3; (iv) −y+4/3, x−y+5/3, z−1/3. |
Experimental details
Crystal data | |
Chemical formula | C8H10N2O3 |
Mr | 182.18 |
Crystal system, space group | Trigonal, R3 |
Temperature (K) | 120 |
a, c (Å) | 19.4079 (10), 11.5250 (4) |
V (Å3) | 3759.5 (3) |
Z | 18 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.21 × 0.20 × 0.12 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.977, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14714, 1920, 1362 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.087, 1.07 |
No. of reflections | 1920 |
No. of parameters | 135 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.23 |
Computer programs: COLLECT (Bruker AXS, 2000), EVALCCD (Duisenberg et al., 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2007).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···N2i | 0.91 (2) | 2.24 (2) | 3.1274 (19) | 165.3 (16) |
N2—H2N···N1i | 0.91 (2) | 2.567 (19) | 3.266 (2) | 134.5 (15) |
N2—H2M···O2ii | 0.93 (2) | 2.15 (2) | 3.0364 (19) | 158.6 (17) |
N2—H2M···O1ii | 0.93 (2) | 2.43 (2) | 3.1335 (18) | 132.6 (15) |
N1—H1N···O3iii | 0.88 (2) | 2.15 (2) | 2.9296 (18) | 147.6 (16) |
O2—H2O···O3iv | 0.86 (2) | 1.81 (2) | 2.6635 (16) | 171 (2) |
Symmetry codes: (i) y−1/3, −x+y+1/3, −z+1/3; (ii) −y+4/3, x−y+5/3, z+2/3; (iii) x−y+2/3, x+1/3, −z+1/3; (iv) −y+4/3, x−y+5/3, z−1/3. |
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.