organic compounds
N′-[(E)-2-Hydroxybenzylidene]-5-methylisoxazole-4-carbohydrazide monohydrate
aSchool of Pharmaceutical and Chemical Engineering, Taizhou University, Linhai 317000, People's Republic of China, and bOffice of Assets Administration, Taizhou University, Linhai 317000, People's Republic of China
*Correspondence e-mail: snowflakej@gmail.com
In the structure of the title compound, C12H11N3O3·H2O, the dihedral angle formed by the benzene and isoxazole rings is 2.03 (8)°. The molecular conformation is stabilized by an intramolecular O—H⋯N hydrogen bond. In the molecules are linked into a three-dimesional network by intermolecular N—H⋯O, O—H⋯N and O—H⋯O hydrogen bonds, and by π–π stacking interactions involving adjacent benzene and isoxazole rings [centroid–centroid separation = 3.663 (2) Å].
Related literature
For the biological and coordination properties of hydrazine compounds, see: Molina et al. (1994); Reiter et al. (1985); Sato et al. (1998); Edwards et al. (1975). For the pharmaceutical activity of isoxazole compounds, see: Stevens & Albizati (1984); El-Gaby et al. (2002). For the synthesis of the title compound, see: Jin et al. (2008). For reference structural data, see: Allen et al. (1987).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2004); cell SAINT (Bruker, 2004); 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: SHELXL97.
Supporting information
10.1107/S1600536809048028/rz2385sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809048028/rz2385Isup2.hkl
The title compound, C12H13N3O4, was synthesized according to the literature method (Jin et al.2008). Salicylaldehyde (1.44 ml) was added into a solution of 5-methylisoxazole-4-carbonyl hydrazine (2.0 g, 0.014 mol) in anhydrous ethanol (40 ml). The mixture was refluxed for 2 h, then the precipitate was collected by filtration and washed with water, chloroform and ethanol. The product was recrystallized from ethanol, then dried under reduced pressure (yield 84.5%). Pink block-shaped crystals were obtained by slow evaporation of a dimethylformamide solution.
The water and hydroxyl H atoms were located in a difference Fourier map and isotropically refined with the O—H distance restrained to 0.86 (1) Å. All other H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93–0.96 Å, N—H = 0.86 Å, and with Uiso(H) = 1.2 Ueq(C, N) or 1.5 Ueq(C) for methyl H atoms. In the absence of significant
effects, Friedel pairs were merged in the final refinement.Data collection: APEX2 (Bruker, 2004); cell
SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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: SHELXL97 (Sheldrick, 2008).C12H11N3O3·H2O | F(000) = 552 |
Mr = 263.25 | Dx = 1.387 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 6440 reflections |
a = 12.8783 (6) Å | θ = 2.4–27.0° |
b = 11.3108 (6) Å | µ = 0.11 mm−1 |
c = 8.6535 (4) Å | T = 296 K |
V = 1260.50 (11) Å3 | Block, pink |
Z = 4 | 0.48 × 0.39 × 0.28 mm |
Bruker APEXII area-detector diffractometer | 1432 independent reflections |
Radiation source: fine-focus sealed tube | 1279 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
ω scans | θmax = 27.0°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −16→16 |
Tmin = 0.951, Tmax = 0.971 | k = −12→13 |
12295 measured reflections | l = −10→11 |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.092 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.89 | w = 1/[σ2(Fo2) + (0.0725P)2 + 0.135P] where P = (Fo2 + 2Fc2)/3 |
1432 reflections | (Δ/σ)max = 0.097 |
182 parameters | Δρmax = 0.14 e Å−3 |
5 restraints | Δρmin = −0.14 e Å−3 |
C12H11N3O3·H2O | V = 1260.50 (11) Å3 |
Mr = 263.25 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 12.8783 (6) Å | µ = 0.11 mm−1 |
b = 11.3108 (6) Å | T = 296 K |
c = 8.6535 (4) Å | 0.48 × 0.39 × 0.28 mm |
Bruker APEXII area-detector diffractometer | 1432 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 1279 reflections with I > 2σ(I) |
Tmin = 0.951, Tmax = 0.971 | Rint = 0.039 |
12295 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 5 restraints |
wR(F2) = 0.092 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.89 | Δρmax = 0.14 e Å−3 |
1432 reflections | Δρmin = −0.14 e Å−3 |
182 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 | ||
N1 | 0.14390 (16) | −0.00283 (18) | 0.3335 (3) | 0.0565 (5) | |
N2 | 0.24031 (12) | 0.15708 (15) | 0.7518 (2) | 0.0421 (4) | |
H2B | 0.1744 | 0.1523 | 0.7368 | 0.051* | |
N3 | 0.27882 (14) | 0.20055 (16) | 0.8883 (2) | 0.0416 (4) | |
O1W | 0.01706 (11) | 0.16789 (14) | 0.7294 (2) | 0.0559 (4) | |
H1W1 | −0.026 (2) | 0.123 (2) | 0.776 (4) | 0.084* | |
H1W2 | −0.019 (2) | 0.2255 (19) | 0.704 (4) | 0.084* | |
O1 | 0.24526 (12) | −0.01962 (14) | 0.2774 (2) | 0.0550 (4) | |
O2 | 0.40155 (10) | 0.13200 (14) | 0.6549 (2) | 0.0517 (4) | |
O3 | 0.43156 (13) | 0.25524 (19) | 1.0747 (2) | 0.0648 (5) | |
C1 | 0.26059 (14) | 0.06858 (16) | 0.5035 (3) | 0.0373 (4) | |
C2 | 0.15530 (16) | 0.0488 (2) | 0.4659 (3) | 0.0467 (5) | |
H2A | 0.1002 | 0.0704 | 0.5294 | 0.056* | |
C3 | 0.31271 (16) | 0.02328 (18) | 0.3808 (3) | 0.0442 (5) | |
C4 | 0.42389 (18) | 0.0114 (3) | 0.3423 (4) | 0.0716 (8) | |
H4A | 0.4309 | −0.0251 | 0.2427 | 0.107* | |
H4B | 0.4575 | −0.0367 | 0.4189 | 0.107* | |
H4C | 0.4555 | 0.0882 | 0.3404 | 0.107* | |
C5 | 0.30730 (14) | 0.12213 (16) | 0.6423 (3) | 0.0376 (4) | |
C6 | 0.25002 (15) | 0.27711 (17) | 1.1395 (3) | 0.0390 (4) | |
C7 | 0.35615 (16) | 0.29084 (19) | 1.1731 (3) | 0.0443 (5) | |
C8 | 0.3861 (2) | 0.3415 (2) | 1.3120 (3) | 0.0578 (6) | |
H8A | 0.4563 | 0.3500 | 1.3347 | 0.069* | |
C9 | 0.3126 (2) | 0.3794 (2) | 1.4164 (3) | 0.0583 (6) | |
H9A | 0.3336 | 0.4143 | 1.5086 | 0.070* | |
C10 | 0.2090 (2) | 0.3664 (2) | 1.3859 (3) | 0.0568 (6) | |
H10A | 0.1598 | 0.3912 | 1.4576 | 0.068* | |
C11 | 0.17799 (17) | 0.31606 (19) | 1.2483 (3) | 0.0488 (5) | |
H11A | 0.1075 | 0.3080 | 1.2277 | 0.059* | |
C12 | 0.21445 (16) | 0.22851 (18) | 0.9941 (3) | 0.0422 (5) | |
H12A | 0.1437 | 0.2176 | 0.9776 | 0.051* | |
H3A | 0.403 (2) | 0.224 (2) | 0.994 (3) | 0.070 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0478 (11) | 0.0662 (12) | 0.0556 (12) | −0.0047 (9) | −0.0081 (9) | −0.0123 (11) |
N2 | 0.0321 (8) | 0.0543 (9) | 0.0399 (9) | −0.0018 (7) | −0.0076 (7) | −0.0024 (8) |
N3 | 0.0401 (8) | 0.0488 (9) | 0.0358 (9) | 0.0008 (7) | −0.0086 (8) | −0.0013 (7) |
O1W | 0.0322 (7) | 0.0646 (9) | 0.0708 (11) | 0.0027 (6) | 0.0057 (8) | 0.0108 (9) |
O1 | 0.0562 (9) | 0.0595 (9) | 0.0491 (9) | −0.0023 (7) | 0.0009 (8) | −0.0155 (8) |
O2 | 0.0307 (7) | 0.0630 (9) | 0.0613 (10) | 0.0010 (6) | −0.0087 (7) | −0.0070 (8) |
O3 | 0.0354 (8) | 0.1088 (15) | 0.0502 (9) | 0.0052 (8) | −0.0047 (7) | −0.0136 (11) |
C1 | 0.0325 (9) | 0.0358 (9) | 0.0434 (10) | 0.0001 (7) | −0.0015 (9) | 0.0017 (8) |
C2 | 0.0353 (10) | 0.0559 (12) | 0.0488 (12) | −0.0004 (8) | −0.0036 (9) | −0.0076 (10) |
C3 | 0.0431 (11) | 0.0424 (10) | 0.0471 (12) | 0.0001 (8) | 0.0011 (10) | −0.0017 (9) |
C4 | 0.0479 (13) | 0.0867 (19) | 0.080 (2) | 0.0068 (12) | 0.0167 (14) | −0.0125 (17) |
C5 | 0.0350 (9) | 0.0360 (9) | 0.0420 (11) | 0.0000 (7) | −0.0068 (8) | 0.0030 (9) |
C6 | 0.0377 (9) | 0.0405 (9) | 0.0388 (10) | 0.0009 (7) | −0.0030 (8) | 0.0058 (9) |
C7 | 0.0386 (10) | 0.0553 (11) | 0.0390 (11) | 0.0012 (8) | −0.0051 (9) | 0.0017 (10) |
C8 | 0.0486 (13) | 0.0720 (16) | 0.0528 (13) | −0.0036 (11) | −0.0138 (11) | −0.0078 (12) |
C9 | 0.0750 (17) | 0.0579 (14) | 0.0420 (13) | 0.0036 (11) | −0.0105 (12) | −0.0088 (11) |
C10 | 0.0636 (15) | 0.0623 (14) | 0.0443 (12) | 0.0138 (11) | 0.0049 (12) | −0.0057 (11) |
C11 | 0.0427 (10) | 0.0545 (12) | 0.0491 (12) | 0.0040 (9) | 0.0003 (11) | 0.0015 (11) |
C12 | 0.0355 (9) | 0.0485 (11) | 0.0426 (11) | −0.0002 (8) | −0.0068 (9) | 0.0030 (9) |
N1—C2 | 1.294 (3) | C3—C4 | 1.476 (3) |
N1—O1 | 1.405 (3) | C4—H4A | 0.9600 |
N2—C5 | 1.341 (3) | C4—H4B | 0.9600 |
N2—N3 | 1.372 (2) | C4—H4C | 0.9600 |
N2—H2B | 0.8600 | C6—C11 | 1.393 (3) |
N3—C12 | 1.274 (3) | C6—C7 | 1.406 (3) |
O1W—H1W1 | 0.851 (17) | C6—C12 | 1.448 (3) |
O1W—H1W2 | 0.831 (17) | C7—C8 | 1.386 (3) |
O1—C3 | 1.338 (3) | C8—C9 | 1.377 (4) |
O2—C5 | 1.224 (2) | C8—H8A | 0.9300 |
O3—C7 | 1.353 (3) | C9—C10 | 1.368 (4) |
O3—H3A | 0.864 (18) | C9—H9A | 0.9300 |
C1—C3 | 1.356 (3) | C10—C11 | 1.379 (4) |
C1—C2 | 1.412 (3) | C10—H10A | 0.9300 |
C1—C5 | 1.474 (3) | C11—H11A | 0.9300 |
C2—H2A | 0.9300 | C12—H12A | 0.9300 |
C2—N1—O1 | 105.15 (19) | O2—C5—C1 | 121.0 (2) |
C5—N2—N3 | 118.78 (15) | N2—C5—C1 | 115.76 (15) |
C5—N2—H2B | 120.6 | C11—C6—C7 | 118.2 (2) |
N3—N2—H2B | 120.6 | C11—C6—C12 | 119.79 (19) |
C12—N3—N2 | 118.15 (17) | C7—C6—C12 | 121.9 (2) |
H1W1—O1W—H1W2 | 103 (2) | O3—C7—C8 | 118.0 (2) |
C3—O1—N1 | 108.85 (18) | O3—C7—C6 | 122.3 (2) |
C7—O3—H3A | 109 (2) | C8—C7—C6 | 119.7 (2) |
C3—C1—C2 | 103.6 (2) | C9—C8—C7 | 120.4 (2) |
C3—C1—C5 | 126.24 (18) | C9—C8—H8A | 119.8 |
C2—C1—C5 | 130.1 (2) | C7—C8—H8A | 119.8 |
N1—C2—C1 | 112.6 (2) | C10—C9—C8 | 120.7 (2) |
N1—C2—H2A | 123.7 | C10—C9—H9A | 119.7 |
C1—C2—H2A | 123.7 | C8—C9—H9A | 119.7 |
O1—C3—C1 | 109.82 (18) | C9—C10—C11 | 119.6 (2) |
O1—C3—C4 | 116.5 (2) | C9—C10—H10A | 120.2 |
C1—C3—C4 | 133.7 (2) | C11—C10—H10A | 120.2 |
C3—C4—H4A | 109.5 | C10—C11—C6 | 121.4 (2) |
C3—C4—H4B | 109.5 | C10—C11—H11A | 119.3 |
H4A—C4—H4B | 109.5 | C6—C11—H11A | 119.3 |
C3—C4—H4C | 109.5 | N3—C12—C6 | 120.83 (18) |
H4A—C4—H4C | 109.5 | N3—C12—H12A | 119.6 |
H4B—C4—H4C | 109.5 | C6—C12—H12A | 119.6 |
O2—C5—N2 | 123.2 (2) | ||
C5—N2—N3—C12 | −176.93 (18) | C2—C1—C5—N2 | 0.6 (3) |
C2—N1—O1—C3 | 0.1 (2) | C11—C6—C7—O3 | 179.8 (2) |
O1—N1—C2—C1 | 0.2 (2) | C12—C6—C7—O3 | −2.7 (3) |
C3—C1—C2—N1 | −0.3 (2) | C11—C6—C7—C8 | 0.3 (3) |
C5—C1—C2—N1 | −178.83 (19) | C12—C6—C7—C8 | 177.8 (2) |
N1—O1—C3—C1 | −0.3 (2) | O3—C7—C8—C9 | 179.9 (2) |
N1—O1—C3—C4 | 179.0 (2) | C6—C7—C8—C9 | −0.6 (4) |
C2—C1—C3—O1 | 0.3 (2) | C7—C8—C9—C10 | 0.9 (4) |
C5—C1—C3—O1 | 178.94 (17) | C8—C9—C10—C11 | −0.8 (4) |
C2—C1—C3—C4 | −178.7 (3) | C9—C10—C11—C6 | 0.6 (4) |
C5—C1—C3—C4 | −0.1 (4) | C7—C6—C11—C10 | −0.3 (3) |
N3—N2—C5—O2 | −3.5 (3) | C12—C6—C11—C10 | −177.9 (2) |
N3—N2—C5—C1 | 175.77 (16) | N2—N3—C12—C6 | −178.73 (16) |
C3—C1—C5—O2 | 1.7 (3) | C11—C6—C12—N3 | 174.73 (19) |
C2—C1—C5—O2 | 179.9 (2) | C7—C6—C12—N3 | −2.7 (3) |
C3—C1—C5—N2 | −177.57 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···N3 | 0.87 (3) | 1.89 (2) | 2.617 (2) | 145 (2) |
N2—H2B···O1W | 0.86 | 2.04 | 2.8847 (17) | 169 |
O1W—H1W1···N1i | 0.85 (3) | 2.10 (2) | 2.9304 (19) | 166 (2) |
O1W—H1W2···O2ii | 0.83 (2) | 1.96 (2) | 2.7850 (17) | 176 (2) |
Symmetry codes: (i) −x, −y, z+1/2; (ii) x−1/2, −y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C12H11N3O3·H2O |
Mr | 263.25 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 296 |
a, b, c (Å) | 12.8783 (6), 11.3108 (6), 8.6535 (4) |
V (Å3) | 1260.50 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.48 × 0.39 × 0.28 |
Data collection | |
Diffractometer | Bruker APEXII area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.951, 0.971 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12295, 1432, 1279 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.092, 0.89 |
No. of reflections | 1432 |
No. of parameters | 182 |
No. of restraints | 5 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.14, −0.14 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···N3 | 0.87 (3) | 1.890 (18) | 2.617 (2) | 145 (2) |
N2—H2B···O1W | 0.86 | 2.04 | 2.8847 (17) | 169.1 |
O1W—H1W1···N1i | 0.85 (3) | 2.097 (15) | 2.9304 (19) | 166 (2) |
O1W—H1W2···O2ii | 0.831 (15) | 1.955 (15) | 2.7850 (17) | 176 (2) |
Symmetry codes: (i) −x, −y, z+1/2; (ii) x−1/2, −y+1/2, z. |
Acknowledgements
The authors acknowledge financial support by the Zhejiang Provincial Natural Science Foundation of China (No.Y406049).
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.
The interest in the study of hydrazine compounds has recently grown due to their biological activities (Molina et al.1994; Sato et al.1998) and coordination ability (Reiter et al.1985; Edwards et al.1975). Isoxazole compounds have been widely studied because they exhibit some fungicidal activity, plant-growth regulating activity and antibacterial activity (Stevens et al.1984). Some isoxazole derivatives (El-Gaby et al.2002) are widely used as insecticides, herbicides and bactericides. However, compounds containing both the hydrazine and isoxazole groups has scarcely been reported. In order to search for more effective antibacterial medicines, we synthesized the title compound and report here its crystal structure.
The molecular structure of the title compounds is shown in Fig. 1. The molecule is almost planar, the dihedral angle between the benzene and the isoxazole rings being 2.03 (8)°. Bond lengths (Allen et al., 1987) and angles in the molecule are within normal ranges. The molecular conformation is enforced by an intramolecular O—H···N hydrogen bond (Table 1). In the crystal packing (Fig. 2), molecules are linked into supramolecular layers by intermolecular O—H···N and N—H···O hydrogen bonds, and by π–π stacking interactions involving adjacent benzene and isoxazole rings, with a centroid-to-centroid separation of 3.663 (2) Å. The layers are further linked by intermolecular O—H···O hydrogen bonds to form a three-dimensional network.