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Acta Crystallogr Sect E Struct Rep Online. 2009 May 1; 65(Pt 5): o1085.
Published online 2009 April 22. doi:  10.1107/S1600536809014172
PMCID: PMC2977764

Methyl N′-[(E)-2-methoxy­benzyl­idene]­hydrazinecarboxyl­ate

Abstract

The title compound, C10H12N2O3, crystallizes with two independent mol­ecules in the asymmetric unit. The side chains in the two independent mol­ecules have slightly different orientations, with the C=N—N—C torsion angle being 169.19 (14)° in one of the mol­ecules and −179.86 (14)° in the other. Each independent mol­ecule adopts a trans configuration with respect to the C=N bond. In the crystal structure, mol­ecules are linked into chains running along [001] by N—H(...)O, N—H(...)N and C—H(...)O hydrogen bonds. In addition, an inter­molecular C—H(...)π inter­action is observed.

Related literature

For applications of benzaldehydehydrazone derviatives, see: Parashar et al. (1988 [triangle]); Hadjoudis et al. (1987 [triangle]); Borg et al. (1999 [triangle]). For metal complexes of Schiff base ligands, see: Kahwa et al. (1986 [triangle]); Santos et al. (2001 [triangle]). For a related structure, see: Shang et al. (2007 [triangle]).

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Object name is e-65-o1085-scheme1.jpg

Experimental

Crystal data

  • C10H12N2O3
  • M r = 208.22
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1085-efi1.jpg
  • a = 17.221 (5) Å
  • b = 7.442 (2) Å
  • c = 16.611 (6) Å
  • β = 95.423 (12)°
  • V = 2119.4 (12) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 223 K
  • 0.24 × 0.21 × 0.19 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2002 [triangle]) T min = 0.977, T max = 0.989
  • 11064 measured reflections
  • 3723 independent reflections
  • 2834 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.120
  • S = 1.08
  • 3723 reflections
  • 271 parameters
  • H-atom parameters constrained
  • Δρmax = 0.21 e Å−3
  • Δρmin = −0.18 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/S1600536809014172/ci2777sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809014172/ci2777Isup2.hkl

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

Acknowledgments

The authors thank the Science and Technology Project of Zhejiang Province (grant No. 2007 F70077) for financial support.

supplementary crystallographic information

Comment

Benzaldehydehydrazone derivatives have attracted much attention due to their pharmacological activity (Parashar et al., 1988) and their photochromic properties (Hadjoudis et al., 1987). They are important intermediates of 1,3,4-oxadiazoles, which have been reported to be versatile compounds with many interesting properties (Borg et al., 1999). Metal complexes based on Schiff bases have received considerable attention because they can be utilized as model compounds of active centres in various proteins and enzymes (Kahwa et al., 1986; Santos et al., 2001). We report here the crystal structure of the title compound (Fig. 1).

The title compound contains two independent, but almost identical molecules in the asymmetric unit. Each independent molecule adopts a trans configuration with respect to the C═N bond. The N1/N2/O2/O3/C8/C9 and N3/N4/O5/O6/C18/C19 planes form dihedral angles of 3.20 (6)° and 11.61 (5)°, respectively, with the C2—C7 and C12—C17 planes. The dihedral angle between the two independent benzene rings is 49.19 (7)°. The bond lengths and angles are comparable to those observed for methylN'-[(E)-4-methoxybenzylidene]hydrazinecarboxylate (Shang et al., 2007).

In the crystal structure, the molecules are linked into chains running along the [001] by N—H···O, N—H···N and C—H···O hydrogen bonds. In addition, an intermolecular C—H···π interaction is observed (Table 1).

Experimental

2-Methoxybenzaldehyde (1.36 g, 0.01 mol) and methyl hydrazinecarboxylate (0.90 g, 0.01 mol) were dissolved in stirred methanol (25 ml) and left for 2.5 h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound in 95% yield. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature (m.p. 428–430 K).

Refinement

H atoms were positioned geometrically (N-H = 0.86 Å and C-H = 0.93 or 0.96 Å) and refined using a riding model, with Uiso(H) = 1.2Ueq(C,N) and 1.5Ueq(Cmethyl). In the absence of significant anomalous scattering effects, Friedel pairs were averaged.

Figures

Fig. 1.
The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level. Dashed lines indicate hydrogen bonds.
Fig. 2.
Crystal packing of the title compound. Hydrogen bonds are shown as dashed lines.

Crystal data

C10H12N2O3F(000) = 880
Mr = 208.22Dx = 1.305 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3723 reflections
a = 17.221 (5) Åθ = 1.2–25.0°
b = 7.442 (2) ŵ = 0.10 mm1
c = 16.611 (6) ÅT = 223 K
β = 95.423 (12)°Block, colourless
V = 2119.4 (12) Å30.24 × 0.21 × 0.19 mm
Z = 8

Data collection

Bruker SMART CCD area-detector diffractometer3723 independent reflections
Radiation source: fine-focus sealed tube2834 reflections with I > 2σ(I)
graphiteRint = 0.026
[var phi] and ω scansθmax = 25.0°, θmin = 1.2°
Absorption correction: multi-scan (SADABS; Bruker, 2002)h = −20→20
Tmin = 0.977, Tmax = 0.989k = −8→8
11064 measured reflectionsl = −19→18

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120H-atom parameters constrained
S = 1.08w = 1/[σ2(Fo2) + (0.0639P)2 + 0.1492P] where P = (Fo2 + 2Fc2)/3
3723 reflections(Δ/σ)max = 0.001
271 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = −0.18 e Å3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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
O10.27964 (7)−0.12236 (16)0.66716 (7)0.0579 (3)
O30.41712 (7)0.63135 (17)0.50573 (7)0.0644 (4)
O20.36311 (7)0.49059 (17)0.39394 (7)0.0649 (4)
O60.45355 (6)0.3646 (2)0.82317 (7)0.0676 (4)
O40.06692 (7)0.15183 (19)0.84498 (9)0.0716 (4)
N30.26187 (7)0.29235 (18)0.74487 (8)0.0478 (3)
O50.40316 (7)0.3884 (2)0.69432 (8)0.0733 (4)
N10.31881 (7)0.21928 (19)0.49137 (8)0.0483 (3)
N20.35854 (8)0.37207 (19)0.51936 (8)0.0522 (4)
H2N0.37070.38690.57030.063*
N40.32825 (7)0.3208 (2)0.79597 (8)0.0525 (4)
H4N0.32700.31400.84750.063*
C70.26100 (8)−0.0607 (2)0.52867 (9)0.0460 (4)
C170.13105 (9)0.1853 (2)0.72717 (11)0.0506 (4)
C180.20343 (9)0.2284 (2)0.77764 (10)0.0497 (4)
H180.20670.20930.83320.060*
C80.30274 (8)0.1085 (2)0.54641 (10)0.0479 (4)
H80.31830.13660.60010.057*
C90.37808 (9)0.4974 (2)0.46625 (10)0.0492 (4)
C160.12959 (10)0.1783 (3)0.64363 (12)0.0616 (5)
H160.17460.20630.61940.074*
C40.18349 (10)−0.3883 (3)0.50054 (12)0.0635 (5)
H40.1581−0.49760.49100.076*
C30.21174 (10)−0.3421 (2)0.57816 (11)0.0569 (5)
H30.2052−0.41990.62080.068*
C50.19269 (10)−0.2740 (3)0.43723 (11)0.0630 (5)
H50.1730−0.30540.38510.076*
C10.26395 (13)−0.2246 (3)0.73518 (11)0.0735 (6)
H1A0.2882−0.16910.78330.110*
H1B0.2843−0.34380.73040.110*
H1C0.2086−0.23060.73820.110*
C20.25007 (8)−0.1791 (2)0.59263 (10)0.0470 (4)
C200.53167 (10)0.3890 (3)0.80043 (15)0.0834 (7)
H20A0.56780.39010.84810.125*
H20B0.53480.50100.77220.125*
H20C0.54440.29220.76580.125*
C100.44366 (12)0.7734 (3)0.45624 (14)0.0771 (6)
H10A0.47070.86210.49010.116*
H10B0.39970.82790.42580.116*
H10C0.47830.72470.41980.116*
C60.23130 (10)−0.1116 (3)0.45094 (11)0.0578 (5)
H60.2375−0.03540.40760.069*
C14−0.00378 (13)0.0922 (3)0.63078 (16)0.0853 (7)
H14−0.04890.06200.59840.102*
C190.39555 (9)0.3595 (2)0.76374 (10)0.0477 (4)
C13−0.00495 (11)0.0976 (3)0.71332 (16)0.0752 (6)
H13−0.05070.07080.73650.090*
C120.06241 (9)0.1433 (2)0.76246 (12)0.0582 (5)
C150.06312 (12)0.1308 (3)0.59552 (14)0.0783 (6)
H150.06360.12500.53960.094*
C11−0.00264 (13)0.1165 (3)0.88362 (16)0.0942 (8)
H11A0.00850.12680.94120.141*
H11B−0.0208−0.00280.87030.141*
H11C−0.04220.20190.86520.141*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0726 (7)0.0557 (8)0.0444 (7)−0.0051 (6)0.0008 (5)0.0033 (5)
O30.0752 (8)0.0550 (8)0.0625 (8)−0.0139 (6)0.0050 (6)−0.0052 (6)
O20.0852 (8)0.0594 (9)0.0491 (8)−0.0064 (6)0.0008 (6)0.0032 (6)
O60.0470 (6)0.0963 (11)0.0579 (8)−0.0085 (6)−0.0042 (5)0.0026 (7)
O40.0582 (7)0.0764 (10)0.0818 (10)−0.0074 (6)0.0150 (6)0.0087 (7)
N30.0471 (7)0.0452 (8)0.0496 (8)0.0012 (6)−0.0030 (6)0.0025 (6)
O50.0682 (8)0.1061 (12)0.0457 (8)−0.0207 (7)0.0058 (6)0.0028 (7)
N10.0514 (7)0.0468 (9)0.0464 (8)0.0006 (6)0.0027 (6)−0.0005 (7)
N20.0624 (8)0.0539 (10)0.0392 (7)−0.0041 (7)−0.0002 (6)−0.0016 (6)
N40.0462 (7)0.0693 (10)0.0408 (7)−0.0045 (6)−0.0018 (6)0.0058 (7)
C70.0417 (8)0.0506 (10)0.0461 (9)0.0046 (7)0.0065 (6)−0.0014 (8)
C170.0474 (8)0.0382 (10)0.0648 (11)0.0069 (7)−0.0018 (7)−0.0028 (8)
C180.0489 (9)0.0466 (10)0.0528 (10)0.0038 (7)0.0009 (7)0.0009 (8)
C80.0482 (8)0.0540 (11)0.0416 (9)0.0036 (7)0.0047 (7)−0.0010 (8)
C90.0526 (9)0.0483 (11)0.0462 (10)0.0050 (7)0.0021 (7)−0.0018 (8)
C160.0562 (10)0.0587 (12)0.0681 (12)0.0111 (8)−0.0036 (8)−0.0107 (9)
C40.0579 (10)0.0629 (13)0.0704 (13)−0.0092 (9)0.0093 (9)−0.0139 (10)
C30.0579 (10)0.0535 (12)0.0605 (11)−0.0032 (8)0.0110 (8)0.0008 (9)
C50.0601 (10)0.0758 (14)0.0525 (11)−0.0061 (9)0.0012 (8)−0.0149 (10)
C10.1031 (15)0.0659 (14)0.0504 (11)−0.0079 (11)0.0014 (10)0.0094 (10)
C20.0439 (8)0.0485 (10)0.0488 (10)0.0050 (7)0.0058 (7)−0.0025 (8)
C200.0483 (10)0.0993 (18)0.1017 (17)−0.0118 (10)0.0030 (10)−0.0090 (14)
C100.0798 (13)0.0608 (14)0.0931 (16)−0.0161 (10)0.0202 (12)−0.0003 (11)
C60.0569 (10)0.0692 (13)0.0477 (10)−0.0006 (9)0.0067 (8)−0.0018 (9)
C140.0684 (13)0.0708 (15)0.1093 (19)0.0035 (11)−0.0308 (13)−0.0254 (13)
C190.0511 (9)0.0468 (10)0.0441 (10)−0.0031 (7)−0.0004 (7)−0.0015 (7)
C130.0499 (10)0.0543 (13)0.119 (2)−0.0044 (9)−0.0018 (11)−0.0084 (12)
C120.0512 (9)0.0415 (11)0.0810 (14)0.0022 (7)0.0016 (9)−0.0019 (9)
C150.0744 (13)0.0752 (16)0.0804 (14)0.0126 (11)−0.0187 (11)−0.0219 (12)
C110.0803 (14)0.0885 (18)0.119 (2)−0.0205 (12)0.0373 (13)0.0061 (15)

Geometric parameters (Å, °)

O1—C21.3605 (19)C16—H160.93
O1—C11.409 (2)C4—C51.374 (3)
O3—C91.339 (2)C4—C31.378 (3)
O3—C101.440 (2)C4—H40.93
O2—C91.205 (2)C3—C21.391 (2)
O6—C191.3370 (19)C3—H30.93
O6—C201.443 (2)C5—C61.388 (3)
O4—C121.367 (2)C5—H50.93
O4—C111.436 (2)C1—H1A0.96
N3—C181.280 (2)C1—H1B0.96
N3—N41.3742 (17)C1—H1C0.96
O5—C191.1922 (19)C20—H20A0.96
N1—C81.281 (2)C20—H20B0.96
N1—N21.3846 (19)C20—H20C0.96
N2—C91.348 (2)C10—H10A0.96
N2—H2N0.86C10—H10B0.96
N4—C191.353 (2)C10—H10C0.96
N4—H4N0.86C6—H60.93
C7—C61.395 (2)C14—C151.371 (3)
C7—C21.406 (2)C14—C131.374 (3)
C7—C81.466 (2)C14—H140.93
C17—C161.386 (3)C13—C121.396 (3)
C17—C121.403 (2)C13—H130.93
C17—C181.471 (2)C15—H150.93
C18—H180.93C11—H11A0.96
C8—H80.93C11—H11B0.96
C16—C151.379 (3)C11—H11C0.96
C2—O1—C1118.57 (14)O1—C1—H1C109.5
C9—O3—C10116.02 (15)H1A—C1—H1C109.5
C19—O6—C20117.40 (15)H1B—C1—H1C109.5
C12—O4—C11117.97 (16)O1—C2—C3123.94 (16)
C18—N3—N4115.85 (13)O1—C2—C7115.33 (14)
C8—N1—N2114.99 (13)C3—C2—C7120.73 (15)
C9—N2—N1119.64 (13)O6—C20—H20A109.5
C9—N2—H2N120.2O6—C20—H20B109.5
N1—N2—H2N120.2H20A—C20—H20B109.5
C19—N4—N3118.82 (13)O6—C20—H20C109.5
C19—N4—H4N120.6H20A—C20—H20C109.5
N3—N4—H4N120.6H20B—C20—H20C109.5
C6—C7—C2117.76 (16)O3—C10—H10A109.5
C6—C7—C8123.29 (16)O3—C10—H10B109.5
C2—C7—C8118.96 (14)H10A—C10—H10B109.5
C16—C17—C12118.26 (16)O3—C10—H10C109.5
C16—C17—C18120.86 (16)H10A—C10—H10C109.5
C12—C17—C18120.84 (16)H10B—C10—H10C109.5
N3—C18—C17119.80 (15)C5—C6—C7121.06 (17)
N3—C18—H18120.1C5—C6—H6119.5
C17—C18—H18120.1C7—C6—H6119.5
N1—C8—C7122.99 (15)C15—C14—C13120.82 (19)
N1—C8—H8118.5C15—C14—H14119.6
C7—C8—H8118.5C13—C14—H14119.6
O2—C9—O3124.73 (16)O5—C19—O6124.49 (15)
O2—C9—N2125.42 (16)O5—C19—N4126.70 (14)
O3—C9—N2109.84 (14)O6—C19—N4108.79 (14)
C15—C16—C17121.7 (2)C14—C13—C12120.1 (2)
C15—C16—H16119.2C14—C13—H13120.0
C17—C16—H16119.2C12—C13—H13120.0
C5—C4—C3120.38 (18)O4—C12—C13124.25 (18)
C5—C4—H4119.8O4—C12—C17116.00 (15)
C3—C4—H4119.8C13—C12—C17119.75 (19)
C4—C3—C2119.93 (17)C14—C15—C16119.4 (2)
C4—C3—H3120.0C14—C15—H15120.3
C2—C3—H3120.0C16—C15—H15120.3
C4—C5—C6120.14 (17)O4—C11—H11A109.5
C4—C5—H5119.9O4—C11—H11B109.5
C6—C5—H5119.9H11A—C11—H11B109.5
O1—C1—H1A109.5O4—C11—H11C109.5
O1—C1—H1B109.5H11A—C11—H11C109.5
H1A—C1—H1B109.5H11B—C11—H11C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2N···O50.862.082.938 (2)173
N4—H4N···N1i0.862.423.279 (2)177
C1—H1A···O2i0.962.523.472 (2)170
C11—H11B···Cg1ii0.962.873.826 (3)175

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x, y+1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2777).

References

  • Borg, S., Vollinga, R. C., Labarre, M., Payza, K., Terenius, L. & Luthman, K. (1999). J. Med. Chem.42, 4331–4342. [PubMed]
  • Bruker (2002). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Hadjoudis, E., Vittorakis, M. & Moustakali-Mavridis, J. (1987). Tetrahedron, 43, 1345–1360.
  • Kahwa, I. A., Selbin, J., Hsieh, T. Y. & Laine, R. A. (1986). Inorg. Chim. Acta, 151, 201–208.
  • Parashar, R. K., Sharma, R. C., Kumar, A. & Mohanm, G. (1988). Inorg. Chim. Acta, 151, 201–208.
  • Santos, M. L. P., Bagatin, I. A., Pereira, E. M. & Ferreira, A. M. D. C. (2001). J. Chem. Soc. Dalton Trans. pp. 838–844.
  • 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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