Acta Cryst. (2008). E64, o1675 [ doi:10.1107/S1600536808024227 ]
The title compound, C10H12N2O3, adopts a trans configuration with respect to the C=N bond. The dihedral angle between the benzene ring and the hydrazine carboxylic acid plane is 8.29 (7)°. Molecules are linked into a three-dimensional network by N-H
O, O-HO, O-HN hydrogen bonds and C-H![[pi]](/logos/entities/pi_rmgif.gif)
interactions.
4-Hydroxy-acetophenone (1.36 g, 0.01 mol) and methyl hydrazinecarboxylate (0.90 g, 0.01 mol) were dissolved in stirred methanol (25 ml) and left for 4 h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound in 80% yield. Crystals suitable for X-ray analysis were obtained by slow evaporation of a ethanol solution at room temperature (m.p. 483–485 K).
H atoms were included in the riding model approximation with N—H = 0.86Å and O—H =0.82 Å. C-bound H atoms were positioned geometrically (C—H = 0.93 or 0.96 Å) and refined using a riding model, with Uiso(H) = 1.2–1.5Ueq(C).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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).
![[Figure 1]](./bg2200fig1thm.gif)
| Fig. 1. Molecular structure of (I), showing 50% probability displacement ellipsoids and the atomic numbering. |
| C10H12N2O3 | F000 = 880 |
| Mr = 208.22 | Dx = 1.368 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 1794 reflections |
| a = 11.2532 (18) Å | θ = 2.4–25.0º |
| b = 10.4310 (17) Å | µ = 0.10 mm−1 |
| c = 17.226 (3) Å | T = 273 (2) K |
| V = 2022.1 (6) Å3 | Block, colourless |
| Z = 8 | 0.31 × 0.27 × 0.25 mm |
| Bruker SMART CCD area-detector diffractometer | 1794 independent reflections |
| Radiation source: fine-focus sealed tube | 1626 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.016 |
| T = 273(2) K | θmax = 25.1º |
| φ and ω scans | θmin = 2.4º |
| Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −13→10 |
| Tmin = 0.972, Tmax = 0.978 | k = −12→12 |
| 12287 measured reflections | l = −20→20 |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.033 | w = 1/[σ2(Fo2) + (0.0493P)2 + 0.6007P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.098 | (Δ/σ)max = 0.001 |
| S = 1.09 | Δρmax = 0.17 e Å−3 |
| 1794 reflections | Δρmin = −0.15 e Å−3 |
| 140 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0032 (8) |
| Secondary atom site location: difference Fourier map |
| C10H12N2O3 | V = 2022.1 (6) Å3 |
| Mr = 208.22 | Z = 8 |
| Orthorhombic, Pbca | Mo Kα |
| a = 11.2532 (18) Å | µ = 0.10 mm−1 |
| b = 10.4310 (17) Å | T = 273 (2) K |
| c = 17.226 (3) Å | 0.31 × 0.27 × 0.25 mm |
| Bruker SMART CCD area-detector diffractometer | 1794 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2002) | 1626 reflections with I > 2σ(I) |
| Tmin = 0.972, Tmax = 0.978 | Rint = 0.016 |
| 12287 measured reflections |
| R[F2 > 2σ(F2)] = 0.033 | 140 parameters |
| wR(F2) = 0.098 | H-atom parameters constrained |
| S = 1.09 | Δρmax = 0.17 e Å−3 |
| 1794 reflections | Δρmin = −0.15 e Å−3 |
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 | 0.54458 (12) | 0.13035 (13) | 0.82724 (8) | 0.0330 (3) | |
| H3 | 0.4976 | 0.1806 | 0.8596 | 0.040* | |
| C7 | 0.47041 (11) | −0.06505 (12) | 0.89717 (7) | 0.0287 (3) | |
| C5 | 0.61590 (11) | −0.07467 (13) | 0.78629 (8) | 0.0329 (3) | |
| H5 | 0.6177 | −0.1634 | 0.7913 | 0.039* | |
| C9 | 0.22859 (11) | 0.01890 (13) | 1.01445 (7) | 0.0332 (3) | |
| C3 | 0.68423 (11) | 0.11609 (13) | 0.72183 (7) | 0.0294 (3) | |
| C2 | 0.61307 (12) | 0.18868 (13) | 0.77120 (8) | 0.0339 (3) | |
| H2 | 0.6118 | 0.2775 | 0.7663 | 0.041* | |
| C6 | 0.54416 (11) | −0.00311 (12) | 0.83650 (7) | 0.0283 (3) | |
| C4 | 0.68424 (12) | −0.01681 (13) | 0.72942 (7) | 0.0328 (3) | |
| H4 | 0.7302 | −0.0667 | 0.6963 | 0.039* | |
| C8 | 0.50358 (13) | −0.19457 (13) | 0.92764 (8) | 0.0366 (3) | |
| H8A | 0.5024 | −0.1932 | 0.9834 | 0.055* | |
| H8B | 0.5819 | −0.2166 | 0.9100 | 0.055* | |
| H8C | 0.4477 | −0.2571 | 0.9091 | 0.055* | |
| N2 | 0.30927 (11) | −0.05735 (10) | 0.97785 (7) | 0.0348 (3) | |
| H2A | 0.3164 | −0.1372 | 0.9895 | 0.042* | |
| N1 | 0.37946 (9) | −0.00106 (10) | 0.92106 (6) | 0.0299 (3) | |
| O1 | 0.74919 (9) | 0.18049 (9) | 0.66825 (5) | 0.0381 (3) | |
| H1 | 0.7828 | 0.1291 | 0.6397 | 0.057* | |
| O3 | 0.16440 (10) | −0.05274 (10) | 1.06350 (6) | 0.0471 (3) | |
| O2 | 0.21727 (9) | 0.13304 (9) | 1.00534 (6) | 0.0433 (3) | |
| C10 | 0.07785 (16) | 0.01597 (17) | 1.10905 (10) | 0.0540 (5) | |
| H10A | 0.1108 | 0.0965 | 1.1253 | 0.081* | |
| H10B | 0.0571 | −0.0339 | 1.1539 | 0.081* | |
| H10C | 0.0081 | 0.0310 | 1.0783 | 0.081* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0343 (7) | 0.0289 (7) | 0.0359 (7) | 0.0019 (6) | 0.0053 (6) | −0.0057 (5) |
| C7 | 0.0261 (6) | 0.0289 (7) | 0.0309 (7) | −0.0016 (5) | −0.0063 (5) | −0.0016 (5) |
| C5 | 0.0315 (7) | 0.0245 (7) | 0.0426 (8) | 0.0020 (5) | −0.0003 (6) | −0.0014 (5) |
| C9 | 0.0302 (7) | 0.0359 (8) | 0.0334 (7) | −0.0036 (6) | −0.0026 (5) | −0.0005 (6) |
| C3 | 0.0268 (6) | 0.0316 (7) | 0.0298 (6) | −0.0015 (5) | −0.0012 (5) | −0.0024 (5) |
| C2 | 0.0390 (8) | 0.0238 (6) | 0.0390 (7) | 0.0006 (5) | 0.0041 (6) | −0.0025 (5) |
| C6 | 0.0249 (6) | 0.0286 (7) | 0.0315 (7) | −0.0005 (5) | −0.0036 (5) | −0.0013 (5) |
| C4 | 0.0309 (7) | 0.0300 (7) | 0.0374 (7) | 0.0043 (6) | 0.0039 (5) | −0.0051 (5) |
| C8 | 0.0345 (7) | 0.0321 (7) | 0.0432 (8) | −0.0003 (6) | 0.0006 (6) | 0.0048 (6) |
| N2 | 0.0366 (7) | 0.0293 (6) | 0.0383 (6) | −0.0002 (5) | 0.0056 (5) | 0.0042 (5) |
| N1 | 0.0290 (6) | 0.0319 (6) | 0.0289 (6) | −0.0010 (5) | 0.0005 (4) | 0.0029 (4) |
| O1 | 0.0434 (6) | 0.0314 (5) | 0.0396 (5) | 0.0003 (4) | 0.0132 (4) | −0.0021 (4) |
| O3 | 0.0500 (7) | 0.0373 (6) | 0.0541 (6) | −0.0066 (5) | 0.0232 (5) | −0.0039 (5) |
| O2 | 0.0437 (6) | 0.0358 (6) | 0.0505 (6) | 0.0056 (5) | 0.0053 (5) | 0.0056 (5) |
| C10 | 0.0557 (10) | 0.0507 (10) | 0.0558 (10) | −0.0061 (8) | 0.0227 (8) | −0.0134 (8) |
| C1—C2 | 1.3770 (19) | C3—C4 | 1.3924 (19) |
| C1—C6 | 1.4012 (19) | C2—H2 | 0.9300 |
| C1—H3 | 0.9300 | C4—H4 | 0.9300 |
| C7—N1 | 1.2894 (17) | C8—H8A | 0.9600 |
| C7—C6 | 1.4827 (18) | C8—H8B | 0.9600 |
| C7—C8 | 1.4967 (18) | C8—H8C | 0.9600 |
| C5—C4 | 1.3840 (19) | N2—N1 | 1.3877 (15) |
| C5—C6 | 1.3990 (18) | N2—H2A | 0.8600 |
| C5—H5 | 0.9300 | O1—H1 | 0.8200 |
| C9—O2 | 1.2076 (17) | O3—C10 | 1.4416 (18) |
| C9—O3 | 1.3394 (16) | C10—H10A | 0.9600 |
| C9—N2 | 1.3618 (18) | C10—H10B | 0.9600 |
| C3—O1 | 1.3556 (16) | C10—H10C | 0.9600 |
| C3—C2 | 1.3920 (18) | ||
| C2—C1—C6 | 121.38 (12) | C5—C4—C3 | 120.04 (12) |
| C2—C1—H3 | 119.3 | C5—C4—H4 | 120.0 |
| C6—C1—H3 | 119.3 | C3—C4—H4 | 120.0 |
| N1—C7—C6 | 116.34 (11) | C7—C8—H8A | 109.5 |
| N1—C7—C8 | 123.60 (12) | C7—C8—H8B | 109.5 |
| C6—C7—C8 | 120.07 (11) | H8A—C8—H8B | 109.5 |
| C4—C5—C6 | 121.71 (12) | C7—C8—H8C | 109.5 |
| C4—C5—H5 | 119.1 | H8A—C8—H8C | 109.5 |
| C6—C5—H5 | 119.1 | H8B—C8—H8C | 109.5 |
| O2—C9—O3 | 125.11 (12) | C9—N2—N1 | 117.31 (11) |
| O2—C9—N2 | 125.88 (12) | C9—N2—H2A | 121.3 |
| O3—C9—N2 | 109.01 (12) | N1—N2—H2A | 121.3 |
| O1—C3—C2 | 117.17 (12) | C7—N1—N2 | 117.25 (11) |
| O1—C3—C4 | 123.86 (11) | C3—O1—H1 | 109.5 |
| C2—C3—C4 | 118.96 (12) | C9—O3—C10 | 115.49 (12) |
| C1—C2—C3 | 120.66 (12) | O3—C10—H10A | 109.5 |
| C1—C2—H2 | 119.7 | O3—C10—H10B | 109.5 |
| C3—C2—H2 | 119.7 | H10A—C10—H10B | 109.5 |
| C5—C6—C1 | 117.25 (12) | O3—C10—H10C | 109.5 |
| C5—C6—C7 | 121.75 (12) | H10A—C10—H10C | 109.5 |
| C1—C6—C7 | 121.01 (11) | H10B—C10—H10C | 109.5 |
| C6—C1—C2—C3 | 0.0 (2) | C6—C5—C4—C3 | 1.0 (2) |
| O1—C3—C2—C1 | −179.91 (12) | O1—C3—C4—C5 | 179.43 (12) |
| C4—C3—C2—C1 | 0.66 (19) | C2—C3—C4—C5 | −1.17 (19) |
| C4—C5—C6—C1 | −0.33 (18) | O2—C9—N2—N1 | −4.8 (2) |
| C4—C5—C6—C7 | 179.66 (12) | O3—C9—N2—N1 | 176.23 (11) |
| C2—C1—C6—C5 | −0.20 (19) | C6—C7—N1—N2 | −179.99 (10) |
| C2—C1—C6—C7 | 179.81 (12) | C8—C7—N1—N2 | −0.36 (18) |
| N1—C7—C6—C5 | −156.37 (12) | C9—N2—N1—C7 | 166.88 (11) |
| C8—C7—C6—C5 | 23.98 (18) | O2—C9—O3—C10 | −1.4 (2) |
| N1—C7—C6—C1 | 23.61 (17) | N2—C9—O3—C10 | 177.62 (12) |
| C8—C7—C6—C1 | −156.03 (12) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···O2i | 0.82 | 2.61 | 3.0523 (14) | 116 |
| O1—H1···N1i | 0.82 | 2.03 | 2.8464 (14) | 174 |
| N2—H2A···O2ii | 0.86 | 2.44 | 3.2777 (16) | 164 |
| C10—H10B···Cg1iii | 0.96 | 2.90 | 3.7169 (19) | 144 |
| Symmetry codes: (i) x+1/2, y, −z+3/2; (ii) −x+1/2, y−1/2, z; (iii) −x+3/2, −y, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···O2i | 0.82 | 2.61 | 3.0523 (14) | 116 |
| O1—H1···N1i | 0.82 | 2.03 | 2.8464 (14) | 174 |
| N2—H2A···O2ii | 0.86 | 2.44 | 3.2777 (16) | 164 |
| C10—H10B···Cg1iii | 0.96 | 2.90 | 3.7169 (19) | 144 |
| Symmetry codes: (i) x+1/2, y, −z+3/2; (ii) −x+1/2, y−1/2, z; (iii) −x+3/2, −y, z−1/2. |
The authors acknowledge financial support from Hangzhou Vocational and Technical College, China.
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Hadjoudis, E., Vittorakis, M. & Moustakali-Mavridis, J. (1987). Tetrahedron, 43, 1345–1360.
Parashar, R. K., Sharma, R. C., Kumar, A. & Mohanm, G. (1988). Inorg. Chim. Acta, 151, 201–208.
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Benzaldehydehydrazone derivatives have received considerable attentions for a long time due to their pharmacological activity (Parashar et al., 1988) and their photochromic properties(Hadjoudis et al., 1987). Meanwhile, it is an important intermediate of 1,3,4-oxadiazoles, which have been reported to be versatile compounds with interesting properties (Borg et al., 1999). As a further investigation of this type of derivatives, the crystal structure of the title compound, C10H12N2O3(Fig.1), is described here.
The title molecule (Fig.1) adopts a trans configuration with respect to the C═N bond. The N1/N2/O2/O3/C9/C10 plane of the hydrazine carboxylic acid methyl ester group is slightly twisted away from the attached ring, to which it subtends a dihedral angle of 8.29 (7)°. Bond lengths and angles agree with those observed for methyl N'-[(E)-4-methoxybenzylidene] hydrazinecarboxylate (Shang et al., 2007).
The molecules are linked into a three-dimensional network by N–H···O, O–H···O, O–H···N hydrogen bonds and C–H···π interactions. (Table 1).