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Acta Cryst. (2008). E64, o2127    [ doi:10.1107/S1600536808033461 ]

(E)-Ethyl N'-(3,4,5-trimethoxybenzylidene)hydrazinecarboxylate

L.-P. Lv, X.-M. Ding, W.-B. Yu, W.-W. Li and X.-C. Hu

Abstract top

The molecule of the title compound, C13H18N2O5, adopts a trans configuration with respect to the C=N bond. The dihedral angle between the benzene ring and the hydrazinecarboxylic acid plane is 49.75 (5)° and an intramolecular C-H...O interaction occurs. In the crystal structure, the molecules are linked into a chain along [010] by N-H...O hydrogen bonds, and a C-H...[pi] contact further stabilizes the structure.

Comment top

Benzaldehydehydrazone derivatives are of interest due to their pharmacological activity (Parashar et al., 1988) and photochromic properties (Hadjoudis et al., 1987). As part of our studies of this type of derivatives, we report herein the crystal structure of the title compound (I).

The title molecule (Fig. 1) adopts a trans configuration with respect to the C═N bond. The hydrazine carboxylic acid methyl ester group is slightly twisted away from the attached ring. The dihedral angle between the benzene ring and the C11/C12//N1/N2/O4/O5 plane is 49.75 (5)°. The bond lengths and angles agree with those observed for (E)-Methyl N'-(4-hydroxybenzylidene)hydrazinecarboxylate (Shang et al., 2007).

The molecules are linked into a chain along [010] by intermolecular and intramolecular N—H···O, C—H···O hydrogen bonds (Fig. 2, Table 1) and a C—H···π contact further stabilizes the structure.

Related literature top

For general background, see: Parashar et al. (1988); Hadjoudis et al. (1987). For a related structure, see: Shang et al. (2007).

Experimental top

3,4,5-trimethoxybenzaldehyde (1.96 g, 0.01 mol) and methyl hydrazinecarboxylate (1.04 g, 0.01 mol) were dissolved in stirred methanol (25 ml) and left for 3 h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound in 90% yield. Colourless blocks of (I) were obtained by slow evaporation of a ethanol solution at room temperature (m.p. 452–454 K).

Refinement top

The H atoms were geometrically placed (N—H = 0.86 Å, C—H = 0.93–0.96 Å) and refined as riding with Uiso(H) = 1.2Ueq(C,N) or 1.5Ueq(methyl C).

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 (I), showing 40% probability displacement ellipsoids for the non-hydrogen atoms. The C—H···O interaction is shown as a dashed line.
[Figure 2] Fig. 2. Crystal packing of the title compound, viewed approximately down the a axis. Dashed lines indicate intermolecular hydrogen bonds.
(E)-Ethyl N'-(3,4,5-trimethoxybenzylidene)hydrazinecarboxylate top
Crystal data top
C13H18N2O5F(000) = 600
Mr = 282.29Dx = 1.310 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2520 reflections
a = 22.037 (2) Åθ = 1.0–25.0°
b = 4.8782 (5) ŵ = 0.10 mm−1
c = 14.0212 (15) ÅT = 273 K
β = 108.239 (4)°Block, colourless
V = 1431.5 (3) Å30.26 × 0.24 × 0.22 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer		2520 independent reflections
Radiation source: fine-focus sealed tube2108 reflections with I > 2σ(I)
graphiteRint = 0.029
ω scansθmax = 25.1°, θmin = 1.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		h = −24→25
Tmin = 0.965, Tmax = 0.968k = −5→5
14449 measured reflectionsl = −16→16
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)] = 0.035H-atom parameters constrained
wR(F2) = 0.094 w = 1/[σ2(Fo2) + (0.0431P)2 + 0.3563P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
2520 reflectionsΔρmax = 0.17 e Å−3
186 parametersΔρmin = −0.13 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: 0.0159 (15)
Crystal data top
C13H18N2O5V = 1431.5 (3) Å3
Mr = 282.29Z = 4
Monoclinic, P21/cMo Kα radiation
a = 22.037 (2) ŵ = 0.10 mm−1
b = 4.8782 (5) ÅT = 273 K
c = 14.0212 (15) Å0.26 × 0.24 × 0.22 mm
β = 108.239 (4)°
Data collection top
Bruker SMART CCD
diffractometer		2520 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		2108 reflections with I > 2σ(I)
Tmin = 0.965, Tmax = 0.968Rint = 0.029
14449 measured reflectionsθmax = 25.1°
Refinement top
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.094Δρmax = 0.17 e Å−3
S = 1.03Δρmin = −0.13 e Å−3
2520 reflectionsAbsolute structure: ?
186 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
C70.19238 (7)0.8025 (3)0.61046 (10)0.0417 (3)
H70.19610.92060.66410.050*
C90.24447 (7)0.6457 (3)0.60759 (10)0.0399 (3)
C40.13069 (7)0.6200 (3)0.44959 (10)0.0407 (3)
C80.23981 (7)0.4730 (3)0.52645 (10)0.0446 (4)
H80.27430.36430.52550.054*
C60.13492 (7)0.7831 (3)0.53350 (10)0.0400 (3)
C110.44480 (7)0.3407 (3)0.82320 (10)0.0423 (3)
C50.18340 (7)0.4648 (3)0.44715 (10)0.0439 (4)
C100.30489 (7)0.6728 (3)0.68892 (10)0.0424 (3)
H100.31410.83650.72450.051*
C30.08165 (8)1.0795 (4)0.61651 (12)0.0587 (4)
H3A0.09580.97060.67640.088*
H3B0.03961.14880.60860.088*
H3C0.11051.23000.62150.088*
C120.55019 (7)0.2692 (4)0.93180 (12)0.0548 (4)
H12A0.55540.12640.88690.066*
H12B0.54090.18380.98810.066*
C20.03622 (8)0.3905 (3)0.35788 (13)0.0584 (4)
H2A0.06030.22980.35350.088*
H2B0.00040.40720.29790.088*
H2C0.02120.37550.41500.088*
C10.22489 (9)0.1433 (4)0.35569 (13)0.0716 (6)
H1A0.26180.25200.35880.107*
H1B0.21170.04320.29360.107*
H1C0.23530.01710.41100.107*
C130.60936 (8)0.4386 (4)0.96774 (14)0.0681 (5)
H13A0.61850.51830.91120.102*
H13B0.64450.32481.00440.102*
H13C0.60310.58161.01080.102*
O50.49926 (5)0.4522 (2)0.87979 (8)0.0497 (3)
O20.07592 (5)0.6268 (2)0.36863 (7)0.0485 (3)
O30.08020 (5)0.9148 (2)0.53188 (7)0.0511 (3)
O10.17482 (5)0.3161 (3)0.36105 (8)0.0617 (3)
O40.43507 (6)0.0998 (2)0.81180 (10)0.0752 (4)
N20.40242 (6)0.5408 (2)0.78322 (9)0.0447 (3)
H20.41110.70790.80210.054*
N10.34512 (6)0.4774 (2)0.71207 (8)0.0425 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C70.0445 (8)0.0412 (8)0.0355 (7)−0.0013 (6)0.0070 (6)−0.0019 (6)
C90.0396 (8)0.0395 (8)0.0365 (7)−0.0036 (6)0.0062 (6)0.0028 (6)
C40.0411 (8)0.0409 (8)0.0333 (7)0.0000 (6)0.0020 (6)0.0044 (6)
C80.0439 (8)0.0452 (8)0.0416 (8)0.0037 (7)0.0087 (7)0.0005 (6)
C60.0402 (8)0.0389 (8)0.0390 (7)0.0016 (6)0.0093 (6)0.0043 (6)
C110.0454 (9)0.0363 (8)0.0398 (7)−0.0023 (6)0.0055 (6)−0.0018 (6)
C50.0495 (9)0.0442 (8)0.0338 (7)0.0021 (7)0.0071 (6)−0.0012 (6)
C100.0418 (8)0.0418 (8)0.0402 (7)−0.0041 (7)0.0077 (6)−0.0022 (6)
C30.0558 (10)0.0653 (11)0.0527 (9)0.0110 (8)0.0137 (8)−0.0094 (8)
C120.0469 (9)0.0577 (10)0.0524 (9)0.0147 (8)0.0048 (7)0.0007 (8)
C20.0537 (10)0.0530 (10)0.0546 (9)−0.0050 (8)−0.0031 (8)0.0000 (8)
C10.0766 (13)0.0769 (13)0.0560 (10)0.0208 (10)0.0130 (9)−0.0177 (9)
C130.0409 (9)0.0941 (14)0.0626 (10)0.0069 (9)0.0064 (8)−0.0054 (10)
O50.0398 (6)0.0418 (6)0.0562 (6)0.0018 (4)−0.0014 (5)−0.0038 (5)
O20.0477 (6)0.0469 (6)0.0386 (5)0.0012 (5)−0.0043 (4)0.0037 (4)
O30.0443 (6)0.0595 (7)0.0434 (5)0.0111 (5)0.0048 (5)−0.0053 (5)
O10.0615 (7)0.0723 (8)0.0408 (6)0.0176 (6)0.0010 (5)−0.0162 (5)
O40.0734 (8)0.0320 (6)0.0930 (9)−0.0032 (6)−0.0131 (7)−0.0022 (6)
N20.0404 (7)0.0334 (6)0.0491 (7)−0.0041 (5)−0.0020 (6)−0.0040 (5)
N10.0397 (7)0.0410 (7)0.0396 (6)−0.0060 (5)0.0019 (5)−0.0008 (5)
Geometric parameters (Å, °) top
C7—C61.3862 (19)C3—H3B0.9600
C7—C91.391 (2)C3—H3C0.9600
C7—H70.9300C12—O51.4409 (17)
C9—C81.393 (2)C12—C131.492 (2)
C9—C101.4630 (19)C12—H12A0.9700
C4—O21.3744 (16)C12—H12B0.9700
C4—C51.396 (2)C2—O21.4264 (19)
C4—C61.399 (2)C2—H2A0.9600
C8—C51.385 (2)C2—H2B0.9600
C8—H80.9300C2—H2C0.9600
C6—O31.3602 (17)C1—O11.409 (2)
C11—O41.1965 (18)C1—H1A0.9600
C11—O51.3303 (17)C1—H1B0.9600
C11—N21.3457 (18)C1—H1C0.9600
C5—O11.3697 (17)C13—H13A0.9600
C10—N11.2726 (18)C13—H13B0.9600
C10—H100.9300C13—H13C0.9600
C3—O31.4250 (18)N2—N11.3772 (16)
C3—H3A0.9600N2—H20.8600
C6—C7—C9120.07 (13)O5—C12—H12A110.4
C6—C7—H7120.0C13—C12—H12A110.4
C9—C7—H7120.0O5—C12—H12B110.4
C7—C9—C8120.37 (13)C13—C12—H12B110.4
C7—C9—C10119.07 (13)H12A—C12—H12B108.6
C8—C9—C10120.51 (13)O2—C2—H2A109.5
O2—C4—C5121.02 (12)O2—C2—H2B109.5
O2—C4—C6119.39 (13)H2A—C2—H2B109.5
C5—C4—C6119.49 (12)O2—C2—H2C109.5
C5—C8—C9119.44 (14)H2A—C2—H2C109.5
C5—C8—H8120.3H2B—C2—H2C109.5
C9—C8—H8120.3O1—C1—H1A109.5
O3—C6—C7124.73 (13)O1—C1—H1B109.5
O3—C6—C4115.43 (12)H1A—C1—H1B109.5
C7—C6—C4119.84 (13)O1—C1—H1C109.5
O4—C11—O5124.87 (14)H1A—C1—H1C109.5
O4—C11—N2125.79 (14)H1B—C1—H1C109.5
O5—C11—N2109.33 (12)C12—C13—H13A109.5
O1—C5—C8124.38 (14)C12—C13—H13B109.5
O1—C5—C4114.98 (12)H13A—C13—H13B109.5
C8—C5—C4120.61 (13)C12—C13—H13C109.5
N1—C10—C9121.50 (13)H13A—C13—H13C109.5
N1—C10—H10119.2H13B—C13—H13C109.5
C9—C10—H10119.2C11—O5—C12117.58 (12)
O3—C3—H3A109.5C4—O2—C2114.74 (11)
O3—C3—H3B109.5C6—O3—C3117.63 (11)
H3A—C3—H3B109.5C5—O1—C1117.99 (12)
O3—C3—H3C109.5C11—N2—N1119.88 (12)
H3A—C3—H3C109.5C11—N2—H2120.1
H3B—C3—H3C109.5N1—N2—H2120.1
O5—C12—C13106.72 (14)C10—N1—N2115.09 (12)
C6—C7—C9—C81.5 (2)C7—C9—C10—N1153.39 (14)
C6—C7—C9—C10179.09 (13)C8—C9—C10—N1−29.0 (2)
C7—C9—C8—C51.9 (2)O4—C11—O5—C12−0.4 (2)
C10—C9—C8—C5−175.66 (13)N2—C11—O5—C12178.13 (13)
C9—C7—C6—O3175.98 (13)C13—C12—O5—C11166.29 (13)
C9—C7—C6—C4−4.5 (2)C5—C4—O2—C277.45 (18)
O2—C4—C6—O37.15 (19)C6—C4—O2—C2−106.16 (16)
C5—C4—C6—O3−176.39 (13)C7—C6—O3—C3−1.6 (2)
O2—C4—C6—C7−172.45 (13)C4—C6—O3—C3178.83 (14)
C5—C4—C6—C74.0 (2)C8—C5—O1—C15.2 (2)
C9—C8—C5—O1175.76 (14)C4—C5—O1—C1−176.66 (15)
C9—C8—C5—C4−2.3 (2)O4—C11—N2—N1−9.3 (2)
O2—C4—C5—O1−2.5 (2)O5—C11—N2—N1172.11 (11)
C6—C4—C5—O1−178.86 (13)C9—C10—N1—N2173.88 (12)
O2—C4—C5—C8175.78 (13)C11—N2—N1—C10170.86 (13)
C6—C4—C5—C8−0.6 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O4i0.861.982.8167 (17)165
C2—H2A···O10.962.533.062 (2)115
C1—H1C···Cg1i0.962.923.755 (2)146
Symmetry codes: (i) x, y+1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O4i0.861.982.8167 (17)165
C2—H2A···O10.962.533.062 (2)115
C1—H1C···Cg1i0.962.923.755 (2)146
Symmetry codes: (i) x, y+1, z.
Acknowledgements top

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

references
References top

Bruker (2002). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

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.

Shang, Z.-H., Zhang, H.-L. & Ding, Y. (2007). Acta Cryst. E63, o3394.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.