Acta Cryst. (2008). E64, o1676 [ doi:10.1107/S1600536808024264 ]
The molecule of the title compound, C11H14N2O3, adopts a trans configuration with respect to the C=N bond. The dihedral angle between the benzene ring and the hydrazinecarboxylate plane is 12.06 (9)°. Molecules are linked into a one-dimensional network by N-H
O hydrogen bonds and C-H![[pi]](/logos/entities/pi_rmgif.gif)
interactions. The benzene rings of inversion-related molecules are stacked with their centroids separated by 3.777 (1) Å, indicating - interactions.
4-Methoxy-acetophenone (1.50 g, 0.01 mol) and methyl hydrazinecarboxylate (0.90 g, 0.01 mol) were dissolved in stirred methanol (15 ml) and left for 3.5 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 an ethanol solution at room temperature (m.p. 470–472 K).
The H atoms attached N2 were located in a difference map and its position and Uiso values were freely refined. 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 or 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]](./zl2130fig1thm.gif)
| Fig. 1. Molecular structure of (I), showing 50% probability displacement ellipsoids and the atomic numbering. |
![[Figure 2]](./zl2130fig2thm.gif)
| Fig. 2. Crystal packing of the title compound, viewed approximately down the a axis. Dashed lines indicate intermolecular hydrogen bonds. |
| C11H14N2O3 | F000 = 472 |
| Mr = 222.24 | Dx = 1.332 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 1952 reflections |
| a = 12.416 (3) Å | θ = 1.6–25.0º |
| b = 11.113 (3) Å | µ = 0.10 mm−1 |
| c = 8.073 (2) Å | T = 273 (2) K |
| β = 95.628 (3)º | Block, colourless |
| V = 1108.5 (5) Å3 | 0.30 × 0.26 × 0.25 mm |
| Z = 4 |
| Bruker SMART CCD area-detector diffractometer | 1952 independent reflections |
| Radiation source: fine-focus sealed tube | 1624 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.030 |
| T = 273(2) K | θmax = 25.0º |
| φ and ω scans | θmin = 1.7º |
| Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −14→14 |
| Tmin = 0.972, Tmax = 0.978 | k = −13→11 |
| 7124 measured reflections | l = −9→9 |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
| R[F2 > 2σ(F2)] = 0.036 | w = 1/[σ2(Fo2) + (0.0461P)2 + 0.2826P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.102 | (Δ/σ)max = 0.001 |
| S = 1.07 | Δρmax = 0.19 e Å−3 |
| 1952 reflections | Δρmin = −0.14 e Å−3 |
| 153 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: 0.042 (4) |
| Secondary atom site location: difference Fourier map |
| C11H14N2O3 | V = 1108.5 (5) Å3 |
| Mr = 222.24 | Z = 4 |
| Monoclinic, P21/c | Mo Kα |
| a = 12.416 (3) Å | µ = 0.10 mm−1 |
| b = 11.113 (3) Å | T = 273 (2) K |
| c = 8.073 (2) Å | 0.30 × 0.26 × 0.25 mm |
| β = 95.628 (3)º |
| Bruker SMART CCD area-detector diffractometer | 1952 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2002) | 1624 reflections with I > 2σ(I) |
| Tmin = 0.972, Tmax = 0.978 | Rint = 0.030 |
| 7124 measured reflections |
| R[F2 > 2σ(F2)] = 0.036 | 153 parameters |
| wR(F2) = 0.102 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.07 | Δρmax = 0.19 e Å−3 |
| 1952 reflections | Δρmin = −0.14 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | ||
| H2A | 0.6796 (14) | 0.1822 (17) | 0.308 (2) | 0.059 (5)* | |
| C7 | 0.96977 (11) | 0.12453 (12) | 0.16378 (16) | 0.0297 (3) | |
| C8 | 0.85779 (11) | 0.12580 (12) | 0.21369 (16) | 0.0317 (3) | |
| C10 | 0.62251 (11) | 0.29834 (13) | 0.14528 (18) | 0.0348 (3) | |
| C3 | 1.18244 (11) | 0.12536 (13) | 0.07457 (18) | 0.0341 (3) | |
| C5 | 1.04408 (11) | 0.03686 (13) | 0.22113 (17) | 0.0351 (4) | |
| H5 | 1.0223 | −0.0236 | 0.2902 | 0.042* | |
| C6 | 1.00522 (11) | 0.21282 (12) | 0.05809 (17) | 0.0348 (4) | |
| H6 | 0.9574 | 0.2727 | 0.0174 | 0.042* | |
| C2 | 1.14990 (11) | 0.03671 (13) | 0.17850 (18) | 0.0375 (4) | |
| H2 | 1.1983 | −0.0225 | 0.2196 | 0.045* | |
| C4 | 1.10911 (11) | 0.21306 (13) | 0.01308 (18) | 0.0364 (4) | |
| H4 | 1.1305 | 0.2720 | −0.0587 | 0.044* | |
| C1 | 1.36336 (12) | 0.05169 (17) | 0.0921 (2) | 0.0551 (5) | |
| H1A | 1.3691 | 0.0574 | 0.2113 | 0.083* | |
| H1B | 1.4320 | 0.0704 | 0.0531 | 0.083* | |
| H1C | 1.3425 | −0.0286 | 0.0588 | 0.083* | |
| C11 | 0.44286 (12) | 0.36579 (16) | 0.1528 (2) | 0.0528 (5) | |
| H11A | 0.4628 | 0.4492 | 0.1589 | 0.079* | |
| H11B | 0.3810 | 0.3529 | 0.2132 | 0.079* | |
| H11C | 0.4254 | 0.3433 | 0.0385 | 0.079* | |
| O1 | 1.28412 (8) | 0.13431 (10) | 0.02268 (14) | 0.0460 (3) | |
| O3 | 0.53202 (8) | 0.29346 (10) | 0.22464 (14) | 0.0467 (3) | |
| O2 | 0.63408 (8) | 0.36576 (10) | 0.03058 (13) | 0.0432 (3) | |
| N1 | 0.79718 (9) | 0.21424 (11) | 0.15959 (14) | 0.0350 (3) | |
| N2 | 0.69424 (10) | 0.21707 (12) | 0.21353 (17) | 0.0391 (3) | |
| C9 | 0.82244 (12) | 0.02704 (14) | 0.3229 (2) | 0.0439 (4) | |
| H9A | 0.8329 | 0.0521 | 0.4372 | 0.066* | |
| H9B | 0.8646 | −0.0439 | 0.3082 | 0.066* | |
| H9C | 0.7472 | 0.0098 | 0.2933 | 0.066* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C7 | 0.0318 (7) | 0.0303 (7) | 0.0271 (7) | −0.0005 (5) | 0.0034 (5) | −0.0038 (5) |
| C8 | 0.0343 (7) | 0.0334 (8) | 0.0277 (7) | −0.0011 (6) | 0.0052 (5) | −0.0037 (6) |
| C10 | 0.0317 (7) | 0.0391 (8) | 0.0346 (8) | 0.0006 (6) | 0.0082 (6) | −0.0059 (7) |
| C3 | 0.0301 (7) | 0.0370 (8) | 0.0357 (8) | 0.0004 (6) | 0.0048 (6) | −0.0050 (6) |
| C5 | 0.0388 (8) | 0.0333 (8) | 0.0336 (8) | 0.0002 (6) | 0.0058 (6) | 0.0038 (6) |
| C6 | 0.0342 (7) | 0.0328 (8) | 0.0374 (8) | 0.0051 (6) | 0.0041 (6) | 0.0021 (6) |
| C2 | 0.0362 (8) | 0.0357 (8) | 0.0403 (8) | 0.0086 (6) | 0.0021 (6) | 0.0019 (6) |
| C4 | 0.0361 (8) | 0.0354 (8) | 0.0386 (8) | −0.0008 (6) | 0.0079 (6) | 0.0049 (6) |
| C1 | 0.0332 (8) | 0.0649 (12) | 0.0680 (12) | 0.0125 (8) | 0.0084 (8) | 0.0035 (9) |
| C11 | 0.0314 (8) | 0.0592 (11) | 0.0684 (12) | 0.0078 (7) | 0.0075 (7) | 0.0000 (9) |
| O1 | 0.0304 (5) | 0.0522 (7) | 0.0565 (7) | 0.0053 (5) | 0.0107 (5) | 0.0060 (5) |
| O3 | 0.0316 (5) | 0.0567 (7) | 0.0539 (7) | 0.0066 (5) | 0.0153 (5) | 0.0079 (5) |
| O2 | 0.0425 (6) | 0.0493 (7) | 0.0396 (6) | 0.0093 (5) | 0.0125 (5) | 0.0054 (5) |
| N1 | 0.0308 (6) | 0.0412 (7) | 0.0345 (7) | 0.0028 (5) | 0.0097 (5) | 0.0002 (5) |
| N2 | 0.0330 (6) | 0.0467 (8) | 0.0393 (7) | 0.0047 (5) | 0.0131 (5) | 0.0059 (6) |
| C9 | 0.0379 (8) | 0.0442 (9) | 0.0516 (9) | 0.0011 (7) | 0.0144 (7) | 0.0075 (7) |
| C7—C5 | 1.3896 (19) | C2—H2 | 0.9300 |
| C7—C6 | 1.399 (2) | C4—H4 | 0.9300 |
| C7—C8 | 1.4850 (19) | C1—O1 | 1.4201 (19) |
| C8—N1 | 1.2878 (18) | C1—H1A | 0.9600 |
| C8—C9 | 1.500 (2) | C1—H1B | 0.9600 |
| C10—O2 | 1.2105 (17) | C1—H1C | 0.9600 |
| C10—N2 | 1.3476 (19) | C11—O3 | 1.4429 (19) |
| C10—O3 | 1.3479 (17) | C11—H11A | 0.9600 |
| C3—O1 | 1.3722 (17) | C11—H11B | 0.9600 |
| C3—C2 | 1.380 (2) | C11—H11C | 0.9600 |
| C3—C4 | 1.392 (2) | N1—N2 | 1.3905 (16) |
| C5—C2 | 1.390 (2) | N2—H2A | 0.891 (19) |
| C5—H5 | 0.9300 | C9—H9A | 0.9600 |
| C6—C4 | 1.3740 (19) | C9—H9B | 0.9600 |
| C6—H6 | 0.9300 | C9—H9C | 0.9600 |
| C5—C7—C6 | 117.16 (13) | O1—C1—H1A | 109.5 |
| C5—C7—C8 | 121.66 (12) | O1—C1—H1B | 109.5 |
| C6—C7—C8 | 121.18 (12) | H1A—C1—H1B | 109.5 |
| N1—C8—C7 | 116.53 (12) | O1—C1—H1C | 109.5 |
| N1—C8—C9 | 124.24 (13) | H1A—C1—H1C | 109.5 |
| C7—C8—C9 | 119.23 (12) | H1B—C1—H1C | 109.5 |
| O2—C10—N2 | 127.18 (13) | O3—C11—H11A | 109.5 |
| O2—C10—O3 | 123.74 (13) | O3—C11—H11B | 109.5 |
| N2—C10—O3 | 109.08 (13) | H11A—C11—H11B | 109.5 |
| O1—C3—C2 | 124.78 (13) | O3—C11—H11C | 109.5 |
| O1—C3—C4 | 115.44 (13) | H11A—C11—H11C | 109.5 |
| C2—C3—C4 | 119.78 (13) | H11B—C11—H11C | 109.5 |
| C7—C5—C2 | 122.07 (13) | C3—O1—C1 | 117.08 (12) |
| C7—C5—H5 | 119.0 | C10—O3—C11 | 115.40 (12) |
| C2—C5—H5 | 119.0 | C8—N1—N2 | 115.82 (12) |
| C4—C6—C7 | 121.48 (13) | C10—N2—N1 | 118.55 (13) |
| C4—C6—H6 | 119.3 | C10—N2—H2A | 117.4 (12) |
| C7—C6—H6 | 119.3 | N1—N2—H2A | 122.0 (11) |
| C3—C2—C5 | 119.33 (13) | C8—C9—H9A | 109.5 |
| C3—C2—H2 | 120.3 | C8—C9—H9B | 109.5 |
| C5—C2—H2 | 120.3 | H9A—C9—H9B | 109.5 |
| C6—C4—C3 | 120.17 (13) | C8—C9—H9C | 109.5 |
| C6—C4—H4 | 119.9 | H9A—C9—H9C | 109.5 |
| C3—C4—H4 | 119.9 | H9B—C9—H9C | 109.5 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···O2i | 0.89 (2) | 2.01 (2) | 2.8864 (17) | 169.0 |
| C4—H4···Cg1ii | 0.93 | 2.87 | 3.6488 (19) | 142 |
| Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···O2i | 0.89 (2) | 2.01 (2) | 2.8864 (17) | 169.0 |
| C4—H4···Cg1ii | 0.93 | 2.87 | 3.6488 (19) | 142 |
| Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2. |
The authors acknowledge financial support from Hangzhou Vocational and Technical College, China.
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Benzaldehydehydrazone derivatives have received considerable attention for a long time due to their pharmacological activity (Parashar et al., 1988) and their photochromic properties (Hadjoudis et al., 1987). Meanwhile, it's an important intermidiate of 1,3,4-oxadiazoles, which have been reported to be versatile compounds with many interesting properties (Borg et al., 1999). As a further investigation of this type of derivatives, the crystal structure of the title compound, C11H14N2O3 (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/C10/C11 plane of the hydrazine carboxylic acid methyl ester group is slightly twisted away from the attached ring. The dihedral angle between the C2—C7 ring and the N1/N2/O2/O3/C10/C11 plane is 12.06 (9)°. The 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 one-dimensional network by N–H···O hydrogen bonds and C–H···π interactions (Table 1, Fig.2). The benzene rings of the inversion-related molecules are stacked with their centroids separated by a distance of 3.777 (1) Å, indicating π-π interactions.