Acta Cryst. (2008). E64, o2071 [ doi:10.1107/S160053680803184X ]
The title molecule, C11H14N2O2, adopts a trans configuration with respect to the C=N bond. The dihedral angle between the benzene ring and the hydrazinecarboxylate plane is 7.61 (16)°. In the crystal structure, molecules are linked into centrosymmetric dimers by N-H
O hydrogen bonds and the dimers are linked together by C-H![[pi]](/logos/entities/pi_rmgif.gif)
interactions.
4-Methyl-acetophenone (1.34 g, 0.01 mol) and methyl hydrazinecarboxylate (0.90 g, 0.01 mol) were dissolved in stirred methanol (25 ml) and left for 5.5 h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound (yield 93%, m.p. 453-455 K). Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.
H atoms were positioned geometrically, with N-H = 0.86 Å and C-H = 0.93 and 0.96 Å for aromatic and methyl H, respectively, and constrained to ride on their parent atoms with Uiso(H) = xUeq(C,N), where x = 1.5 for methyl H and x = 1.2 for all other H atoms. A rotating group model was used for the methyl groups.
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]](./cv2459fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. |
![[Figure 2]](./cv2459fig2thm.gif)
| Fig. 2. A packing diagram of the title compound. Hydrogen bonds are shown as dashed lines. |
| C11H14N2O2 | F(000) = 440 |
| Mr = 206.24 | Dx = 1.235 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 1951 reflections |
| a = 11.5197 (3) Å | θ = 1.8–25.0° |
| b = 5.5734 (6) Å | µ = 0.09 mm−1 |
| c = 17.3281 (2) Å | T = 273 K |
| β = 94.193 (14)° | Block, colourless |
| V = 1109.55 (12) Å3 | 0.24 × 0.22 × 0.20 mm |
| Z = 4 |
| Bruker SMART CCD area-detector diffractometer | 1951 independent reflections |
| Radiation source: fine-focus sealed tube | 1209 reflections with I > 2σ(I) |
| graphite | Rint = 0.032 |
| φ and ω scans | θmax = 25.0°, θmin = 1.8° |
| Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −13→13 |
| Tmin = 0.978, Tmax = 0.980 | k = −6→6 |
| 5502 measured reflections | l = −19→20 |
| 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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.172 | H-atom parameters constrained |
| S = 1.03 | w = 1/[σ2(Fo2) + (0.07P)2 + 0.5722P] where P = (Fo2 + 2Fc2)/3 |
| 1951 reflections | (Δ/σ)max < 0.001 |
| 138 parameters | Δρmax = 0.28 e Å−3 |
| 3 restraints | Δρmin = −0.26 e Å−3 |
| C11H14N2O2 | V = 1109.55 (12) Å3 |
| Mr = 206.24 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 11.5197 (3) Å | µ = 0.09 mm−1 |
| b = 5.5734 (6) Å | T = 273 K |
| c = 17.3281 (2) Å | 0.24 × 0.22 × 0.20 mm |
| β = 94.193 (14)° |
| Bruker SMART CCD area-detector diffractometer | 1951 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2002) | 1209 reflections with I > 2σ(I) |
| Tmin = 0.978, Tmax = 0.980 | Rint = 0.032 |
| 5502 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.057 | H-atom parameters constrained |
| wR(F2) = 0.172 | Δρmax = 0.28 e Å−3 |
| S = 1.03 | Δρmin = −0.26 e Å−3 |
| 1951 reflections | Absolute structure: ? |
| 138 parameters | Flack parameter: ? |
| 3 restraints | Rogers parameter: ? |
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 | ||
| C6 | 0.4332 (2) | −0.0332 (5) | 0.39288 (14) | 0.0447 (6) | |
| C5 | 0.5218 (2) | −0.2016 (5) | 0.40434 (17) | 0.0571 (8) | |
| H5 | 0.5107 | −0.3340 | 0.4357 | 0.069* | |
| C8 | 0.3200 (2) | −0.0595 (5) | 0.42808 (15) | 0.0472 (7) | |
| C7 | 0.4558 (2) | 0.1643 (5) | 0.34621 (16) | 0.0520 (7) | |
| H7 | 0.3994 | 0.2827 | 0.3379 | 0.062* | |
| C3 | 0.6471 (2) | 0.0163 (5) | 0.32361 (16) | 0.0548 (7) | |
| C2 | 0.5594 (2) | 0.1865 (5) | 0.31268 (16) | 0.0548 (7) | |
| H2 | 0.5712 | 0.3193 | 0.2817 | 0.066* | |
| C10 | 0.0517 (2) | 0.2495 (5) | 0.42066 (17) | 0.0562 (7) | |
| C4 | 0.6258 (2) | −0.1771 (5) | 0.37036 (18) | 0.0632 (8) | |
| H4 | 0.6830 | −0.2937 | 0.3792 | 0.076* | |
| C1 | 0.7601 (3) | 0.0414 (7) | 0.28540 (19) | 0.0764 (10) | |
| H1A | 0.7559 | 0.1786 | 0.2518 | 0.115* | |
| H1B | 0.7732 | −0.1002 | 0.2557 | 0.115* | |
| H1C | 0.8230 | 0.0618 | 0.3243 | 0.115* | |
| C9 | 0.3016 (2) | −0.2711 (5) | 0.47910 (17) | 0.0602 (8) | |
| H9A | 0.2698 | −0.2178 | 0.5258 | 0.063* | |
| H9C | 0.3746 | −0.3499 | 0.4916 | 0.063* | |
| H9B | 0.2484 | −0.3812 | 0.4526 | 0.063* | |
| C11 | −0.0088 (3) | 0.5827 (6) | 0.3454 (2) | 0.0789 (10) | |
| H11A | −0.0725 | 0.5048 | 0.3167 | 0.118* | |
| H11B | 0.0235 | 0.7033 | 0.3137 | 0.118* | |
| H11C | −0.0362 | 0.6564 | 0.3907 | 0.118* | |
| N2 | 0.13765 (19) | 0.0920 (4) | 0.44132 (14) | 0.0613 (7) | |
| H2A | 0.1257 | −0.0182 | 0.4746 | 0.074* | |
| N1 | 0.24476 (18) | 0.1054 (4) | 0.40979 (13) | 0.0548 (6) | |
| O2 | 0.07955 (17) | 0.4080 (4) | 0.36804 (12) | 0.0690 (7) | |
| O1 | −0.04293 (16) | 0.2424 (4) | 0.44769 (13) | 0.0733 (7) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C6 | 0.0480 (15) | 0.0439 (15) | 0.0421 (14) | 0.0020 (12) | 0.0018 (11) | −0.0030 (12) |
| C5 | 0.0586 (17) | 0.0476 (17) | 0.0660 (19) | 0.0056 (13) | 0.0102 (14) | 0.0060 (14) |
| C8 | 0.0514 (15) | 0.0426 (15) | 0.0478 (15) | 0.0001 (13) | 0.0055 (12) | 0.0006 (12) |
| C7 | 0.0509 (16) | 0.0495 (17) | 0.0559 (17) | 0.0076 (13) | 0.0054 (13) | 0.0025 (14) |
| C3 | 0.0485 (16) | 0.0588 (18) | 0.0572 (18) | −0.0005 (14) | 0.0052 (13) | −0.0077 (15) |
| C2 | 0.0564 (17) | 0.0573 (18) | 0.0515 (17) | −0.0049 (14) | 0.0089 (13) | 0.0058 (14) |
| C10 | 0.0485 (16) | 0.0579 (18) | 0.0631 (19) | −0.0015 (14) | 0.0098 (14) | 0.0062 (15) |
| C4 | 0.0537 (17) | 0.0569 (19) | 0.080 (2) | 0.0145 (14) | 0.0090 (15) | 0.0013 (16) |
| C1 | 0.0543 (18) | 0.095 (3) | 0.082 (2) | −0.0016 (18) | 0.0152 (16) | −0.004 (2) |
| C9 | 0.0566 (17) | 0.0590 (19) | 0.0662 (19) | 0.0039 (14) | 0.0116 (14) | 0.0098 (15) |
| C11 | 0.071 (2) | 0.070 (2) | 0.096 (3) | 0.0151 (18) | 0.0100 (18) | 0.0236 (19) |
| N2 | 0.0532 (14) | 0.0602 (16) | 0.0729 (16) | 0.0043 (12) | 0.0202 (12) | 0.0171 (13) |
| N1 | 0.0459 (13) | 0.0557 (15) | 0.0641 (15) | 0.0030 (11) | 0.0133 (11) | 0.0075 (12) |
| O2 | 0.0572 (12) | 0.0718 (15) | 0.0801 (15) | 0.0104 (11) | 0.0194 (11) | 0.0241 (12) |
| O1 | 0.0492 (12) | 0.0806 (16) | 0.0922 (16) | 0.0046 (11) | 0.0205 (11) | 0.0214 (13) |
| C6—C5 | 1.390 (4) | C10—N2 | 1.351 (4) |
| C6—C7 | 1.402 (4) | C4—H4 | 0.9300 |
| C6—C8 | 1.487 (3) | C1—H1A | 0.9600 |
| C5—C4 | 1.380 (4) | C1—H1B | 0.9600 |
| C5—H5 | 0.9300 | C1—H1C | 0.9600 |
| C8—N1 | 1.286 (3) | C9—H9A | 0.9600 |
| C8—C9 | 1.498 (4) | C9—H9C | 0.9600 |
| C7—C2 | 1.370 (4) | C9—H9B | 0.9600 |
| C7—H7 | 0.9300 | C11—O2 | 1.442 (3) |
| C3—C4 | 1.381 (4) | C11—H11A | 0.9600 |
| C3—C2 | 1.389 (4) | C11—H11B | 0.9600 |
| C3—C1 | 1.509 (4) | C11—H11C | 0.9600 |
| C2—H2 | 0.9300 | N2—N1 | 1.388 (3) |
| C10—O1 | 1.218 (3) | N2—H2A | 0.8600 |
| C10—O2 | 1.326 (3) | ||
| C5—C6—C7 | 116.5 (2) | C3—C1—H1A | 109.5 |
| C5—C6—C8 | 122.1 (2) | C3—C1—H1B | 109.5 |
| C7—C6—C8 | 121.3 (2) | H1A—C1—H1B | 109.5 |
| C4—C5—C6 | 121.6 (3) | C3—C1—H1C | 109.5 |
| C4—C5—H5 | 119.2 | H1A—C1—H1C | 109.5 |
| C6—C5—H5 | 119.2 | H1B—C1—H1C | 109.5 |
| N1—C8—C6 | 115.1 (2) | C8—C9—H9A | 109.5 |
| N1—C8—C9 | 125.8 (2) | C8—C9—H9C | 109.5 |
| C6—C8—C9 | 119.1 (2) | H9A—C9—H9C | 109.5 |
| C2—C7—C6 | 121.3 (3) | C8—C9—H9B | 109.5 |
| C2—C7—H7 | 119.3 | H9A—C9—H9B | 109.5 |
| C6—C7—H7 | 119.3 | H9C—C9—H9B | 109.5 |
| C4—C3—C2 | 117.0 (3) | O2—C11—H11A | 109.5 |
| C4—C3—C1 | 121.7 (3) | O2—C11—H11B | 109.5 |
| C2—C3—C1 | 121.3 (3) | H11A—C11—H11B | 109.5 |
| C7—C2—C3 | 121.9 (3) | O2—C11—H11C | 109.5 |
| C7—C2—H2 | 119.1 | H11A—C11—H11C | 109.5 |
| C3—C2—H2 | 119.1 | H11B—C11—H11C | 109.5 |
| O1—C10—O2 | 123.7 (3) | C10—N2—N1 | 121.1 (2) |
| O1—C10—N2 | 122.4 (3) | C10—N2—H2A | 119.5 |
| O2—C10—N2 | 113.9 (2) | N1—N2—H2A | 119.5 |
| C5—C4—C3 | 121.6 (3) | C8—N1—N2 | 117.8 (2) |
| C5—C4—H4 | 119.2 | C10—O2—C11 | 115.8 (2) |
| C3—C4—H4 | 119.2 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···O1i | 0.86 | 2.12 | 2.944 (3) | 162 |
| C2—H2···Cg1ii | 0.93 | 2.83 | 3.538 (3) | 134 |
| Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, y+1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···O1i | 0.86 | 2.12 | 2.944 (3) | 162 |
| C2—H2···Cg1ii | 0.93 | 2.83 | 3.538 (3) | 134 |
| Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, y+1/2, −z+1/2. |
The authors thank Hangzhou Vocational and Technical College, China, for financial support.
Borg, S., Vollinga, R. C., Labarre, M., Payza, K., Terenius, L. & Luthman, K. (1999). J. Med. Chem. 42, 4331–4342.
Bruker (2002). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Hadjoudis, E., Vittorakis, M. & Moustakali-Mavridis, J. (1987). Tetrahedron, 43, 1345–1360.
Lv, L.-P., Yu, W.-P., Yu, W.-B., Zhou, X.-F. & Hu, X.-C. (2008). Acta Cryst. E64, o1676.
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 attention for a long time, due to their pharmacological activities (Parashar et al., 1988) and their photochromic properties (Hadjoudis et al., 1987). They are important intermidiates for 1,3,4-oxadiazoles, which have been reported to be versatile compounds with many useful properties (Borg et al., 1999). As a further investigation of this type of derivatives, we report herein the crystal structure of the title compound.
The title molecule (Fig. 1) adopts a trans configuration with respect to the C═N double bond. The bond lengths and angles are comparable to those observed for (E)-methyl N'-[1-(4-methoxyphenyl)ethylidene]hydrazinecarboxylate (Lv et al., 2008). All atoms of O1/O2/N1/N2/C8-C11 are coplanar within ±-0.093 (2)Å. The dihedral angle between the benzene (C2-C7) and O1/O2/N1/N2/C8-C11 planes is 7.61 (16)°.
In the crystal structure, intermolecular N—H···O hydrogen bonds (Table 1) link the molecules into centrosymmetric dimers (Fig. 2). A C—H···π contact (Table 1) between the benzene ring (centroid Cg1) and H atom of aromatic C2 further stabilizes the structure.