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Acta Crystallogr Sect E Struct Rep Online. 2008 November 1; 64(Pt 11): o2127.
Published online 2008 October 18. doi:  10.1107/S1600536808033461
PMCID: PMC2959716

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

Abstract

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(...)π contact further stabilizes the structure.

Related literature

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

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Object name is e-64-o2127-scheme1.jpg

Experimental

Crystal data

  • C13H18N2O5
  • M r = 282.29
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2127-efi1.jpg
  • a = 22.037 (2) Å
  • b = 4.8782 (5) Å
  • c = 14.0212 (15) Å
  • β = 108.239 (4)°
  • V = 1431.5 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 273 (2) K
  • 0.26 × 0.24 × 0.22 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2002 [triangle]) T min = 0.965, T max = 0.968
  • 14449 measured reflections
  • 2520 independent reflections
  • 2108 reflections with I > 2σ(I)
  • R int = 0.029

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.094
  • S = 1.03
  • 2520 reflections
  • 186 parameters
  • H-atom parameters constrained
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.13 e Å−3

Data collection: SMART (Bruker, 2002 [triangle]); cell refinement: SAINT (Bruker, 2002 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808033461/hb2820sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808033461/hb2820Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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

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).

Figures

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.
Fig. 2.
Crystal packing of the title compound, viewed approximately down the a axis. Dashed lines indicate intermolecular hydrogen bonds.

Crystal data

C13H18N2O5F(000) = 600
Mr = 282.29Dx = 1.310 Mg m3
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 mm1
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

Bruker SMART CCD diffractometer2520 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

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) = 0.094w = 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 Å3
186 parametersΔρmin = −0.13 e Å3
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)

Special details

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)

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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2820).

References

  • 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. [PubMed]

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