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Acta Cryst. (2008). E64, o2062    [ doi:10.1107/S1600536808031462 ]

(E)-Ethyl N'-[1-(4-methoxyphenyl)ethylidene]hydrazinecarboxylate

L.-P. Lv, J.-W. Xie, W.-B. Yu, Y.-H. Mao and X.-C. Hu

Abstract top

The molecule of the title compound, C12H16N2O3, adopts a trans configuration with respect to the C=N bond. The dihedral angle between the benzene ring and the hydrazinecarboxylate plane is 13.82 (6)°. In the crystal structure, molecules are linked into centrosymmetric dimers by N-H...O and C-H...O hydrogen bonds, and the dimers are linked together by C-H...[pi] interactions.

Comment top

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 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). Atoms C11 and C12 deviate from the O2/O3/N1/N2/C7-C10 plane by 0.406 (2) and 0.175 (2) Å, respectively. The dihedral angle between benzene (C2-C7) and O2/O3/N1/N2/C7-C10 planes is 13.82 (6)°.

In the crystal structure, intermolecular N—H···O and C–H···O hydrogen bonds (Table 1) link the molecules into centrosymmetric dimers (Fig. 2). A C—H···π contact (Table 1) between benzene ring (centroid Cg1) and C1-methyl group further stabilizes the structure.

Related literature top

For general background, see: Parashar et al. (1988); Hadjoudis et al. (1987); Borg et al. (1999). For a related structure, see: Lv et al. (2008).

Experimental top

4-Methoxy-acetophenone (1.50 g, 0.01 mol) and ethyl hydrazinecarboxylate (1.04 g, 0.01 mol) were dissolved in stirred methanol (25 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 (yield 83%, m.p. 465-468 K). Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

Refinement top

H atoms were positioned geometrically, with N-H = 0.86 Å and C-H = 0.93, 0.97 and 0.96 Å for aromatic, methylene 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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The crystal packing of the title compound, viewed approximately down the c axis. Hydrogen bonds are shown as dashed lines.
(E)-Ethyl N'-[1-(4-methoxyphenyl)ethylidene]hydrazinecarboxylate top
Crystal data top
C12H16N2O3F(000) = 1008
Mr = 236.27Dx = 1.246 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 2222 reflections
a = 12.1020 (11) Åθ = 1.6–25.0°
b = 8.1727 (7) ŵ = 0.09 mm−1
c = 25.476 (2) ÅT = 123 K
V = 2519.8 (4) Å3Block, colourless
Z = 80.27 × 0.23 × 0.22 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		2222 independent reflections
Radiation source: fine-focus sealed tube1845 reflections with I > 2σ(I)
graphiteRint = 0.026
φ and ω scansθmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS, Bruker, 2002)		h = −12→14
Tmin = 0.973, Tmax = 0.981k = −9→9
12848 measured reflectionsl = −30→30
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.127 w = 1/[σ2(Fo2) + (0.0637P)2 + 0.6384P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.002
2222 reflectionsΔρmax = 0.19 e Å−3
158 parametersΔρmin = −0.14 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0115 (13)
Crystal data top
C12H16N2O3V = 2519.8 (4) Å3
Mr = 236.27Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 12.1020 (11) ŵ = 0.09 mm−1
b = 8.1727 (7) ÅT = 123 K
c = 25.476 (2) Å0.27 × 0.23 × 0.22 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		2222 independent reflections
Absorption correction: multi-scan
(SADABS, Bruker, 2002)		1845 reflections with I > 2σ(I)
Tmin = 0.973, Tmax = 0.981Rint = 0.026
12848 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.127Δρmax = 0.19 e Å−3
S = 1.07Δρmin = −0.14 e Å−3
2222 reflectionsAbsolute structure: ?
158 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C70.42346 (13)0.5640 (2)0.60487 (6)0.0490 (4)
C80.43416 (13)0.4210 (2)0.56947 (6)0.0501 (4)
C30.40760 (13)0.8369 (2)0.67166 (6)0.0525 (4)
C20.37209 (14)0.8477 (2)0.62024 (7)0.0570 (4)
H20.34300.94530.60750.068*
C90.59258 (14)0.0586 (2)0.56465 (7)0.0542 (4)
C50.45905 (15)0.5568 (2)0.65717 (7)0.0580 (5)
H50.48900.46000.67000.070*
C60.38006 (15)0.7122 (2)0.58781 (6)0.0561 (4)
H60.35550.72070.55330.067*
C40.45058 (16)0.6900 (2)0.68974 (7)0.0613 (5)
H40.47400.68160.72440.074*
C10.35816 (19)1.1125 (2)0.69025 (8)0.0733 (6)
H1A0.40391.15770.66310.110*
H1B0.35501.18720.71930.110*
H1C0.28501.09480.67690.110*
C110.7327 (2)−0.0352 (3)0.68377 (9)0.0932 (7)
H11A0.76560.06940.69080.140*
H11B0.7815−0.12040.69540.140*
H11C0.6637−0.04350.70210.140*
C100.7136 (2)−0.0522 (3)0.62760 (9)0.0894 (8)
H10A0.6803−0.15760.62010.107*
H10B0.7831−0.04510.60870.107*
O30.63987 (11)0.07917 (16)0.61102 (5)0.0677 (4)
O20.61004 (11)−0.05717 (16)0.53593 (5)0.0701 (4)
O10.40315 (12)0.96202 (16)0.70721 (5)0.0673 (4)
N20.52061 (12)0.17888 (17)0.55187 (5)0.0571 (4)
H2A0.48350.17130.52320.068*
N10.50534 (12)0.31305 (17)0.58366 (5)0.0532 (4)
C120.36482 (15)0.4117 (2)0.52056 (7)0.0621 (5)
H12A0.40980.43610.49050.093*
H12B0.30560.48960.52280.093*
H12C0.33470.30360.51710.093*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C70.0429 (8)0.0533 (9)0.0509 (9)−0.0002 (7)0.0003 (7)0.0052 (7)
C80.0451 (9)0.0546 (10)0.0505 (9)−0.0011 (7)0.0025 (7)0.0067 (7)
C30.0468 (9)0.0571 (10)0.0536 (9)−0.0019 (8)0.0000 (7)−0.0028 (7)
C20.0595 (10)0.0542 (10)0.0572 (9)0.0087 (8)−0.0028 (8)0.0067 (8)
C90.0501 (9)0.0571 (10)0.0555 (9)0.0012 (8)−0.0014 (7)−0.0050 (8)
C50.0597 (10)0.0560 (10)0.0584 (10)0.0046 (8)−0.0103 (8)0.0079 (8)
C60.0606 (10)0.0615 (11)0.0461 (8)0.0065 (8)−0.0038 (7)0.0049 (8)
C40.0642 (11)0.0664 (11)0.0532 (9)0.0029 (9)−0.0134 (8)0.0029 (8)
C10.0867 (14)0.0597 (12)0.0736 (12)0.0091 (10)−0.0031 (10)−0.0111 (10)
C110.1006 (18)0.0890 (16)0.0900 (15)0.0101 (14)−0.0275 (13)0.0137 (13)
C100.0913 (17)0.0877 (16)0.0894 (15)0.0396 (13)−0.0261 (12)−0.0145 (12)
O30.0734 (9)0.0651 (8)0.0646 (8)0.0184 (6)−0.0172 (6)−0.0106 (6)
O20.0664 (8)0.0722 (9)0.0715 (8)0.0159 (7)−0.0101 (6)−0.0200 (7)
O10.0760 (9)0.0648 (8)0.0611 (7)0.0067 (6)−0.0071 (6)−0.0088 (6)
N20.0598 (8)0.0592 (9)0.0522 (8)0.0075 (7)−0.0079 (6)−0.0035 (6)
N10.0563 (8)0.0512 (8)0.0520 (8)0.0021 (6)−0.0004 (6)−0.0005 (6)
C120.0575 (10)0.0676 (12)0.0613 (10)0.0027 (9)−0.0066 (8)−0.0046 (9)
Geometric parameters (Å, °) top
C7—C61.390 (2)C1—O11.412 (2)
C7—C51.401 (2)C1—H1A0.96
C7—C81.482 (2)C1—H1B0.96
C8—N11.285 (2)C1—H1C0.96
C8—C121.504 (2)C11—C101.456 (3)
C3—O11.367 (2)C11—H11A0.96
C3—C21.382 (2)C11—H11B0.96
C3—C41.387 (2)C11—H11C0.96
C2—C61.385 (2)C10—O31.458 (2)
C2—H20.93C10—H10A0.97
C9—O21.215 (2)C10—H10B0.97
C9—O31.323 (2)N2—N11.376 (2)
C9—N21.353 (2)N2—H2A0.86
C5—C41.372 (2)C12—H12A0.96
C5—H50.93C12—H12B0.96
C6—H60.93C12—H12C0.96
C4—H40.93
C6—C7—C5116.71 (15)O1—C1—H1C109.5
C6—C7—C8122.01 (14)H1A—C1—H1C109.5
C5—C7—C8121.27 (15)H1B—C1—H1C109.5
N1—C8—C7115.38 (14)C10—C11—H11A109.5
N1—C8—C12124.94 (15)C10—C11—H11B109.5
C7—C8—C12119.67 (14)H11A—C11—H11B109.5
O1—C3—C2124.64 (16)C10—C11—H11C109.5
O1—C3—C4116.25 (15)H11A—C11—H11C109.5
C2—C3—C4119.11 (16)H11B—C11—H11C109.5
C3—C2—C6119.53 (16)C11—C10—O3108.19 (18)
C3—C2—H2120.2C11—C10—H10A110.1
C6—C2—H2120.2O3—C10—H10A110.1
O2—C9—O3124.14 (16)C11—C10—H10B110.1
O2—C9—N2122.21 (16)O3—C10—H10B110.1
O3—C9—N2113.64 (14)H10A—C10—H10B108.4
C4—C5—C7121.26 (16)C9—O3—C10115.45 (14)
C4—C5—H5119.4C3—O1—C1117.62 (14)
C7—C5—H5119.4C9—N2—N1121.58 (14)
C2—C6—C7122.46 (15)C9—N2—H2A119.2
C2—C6—H6118.8N1—N2—H2A119.2
C7—C6—H6118.8C8—N1—N2118.13 (14)
C5—C4—C3120.91 (16)C8—C12—H12A109.5
C5—C4—H4119.5C8—C12—H12B109.5
C3—C4—H4119.5H12A—C12—H12B109.5
O1—C1—H1A109.5C8—C12—H12C109.5
O1—C1—H1B109.5H12A—C12—H12C109.5
H1A—C1—H1B109.5H12B—C12—H12C109.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O2i0.862.102.914 (2)157
C12—H12C···O2i0.962.523.250 (2)133
C1—H1C···Cg1ii0.962.763.637 (2)153
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, −y−3/2, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O2i0.862.102.914 (2)157
C12—H12C···O2i0.962.523.250 (2)133
C1—H1C···Cg1ii0.962.763.637 (2)153
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, −y−3/2, z−1/2.
Acknowledgements top

The authors thank Hangzhou Vocational and Technical College, China, for financial support.

references
References top

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Lv, L.-P., Yu, W.-P., Yu, W.-B., Zhou, X.-F. & Hu, X.-C. (2008). Acta Cryst. E64, o1676.

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