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Acta Cryst. (2009). E65, o1548    [ doi:10.1107/S1600536809021631 ]

(E)-Methyl N'-(2-hydroxy-3-methoxybenzylidene)hydrazinecarboxylate

L.-P. Lv, W.-B. Yu, W.-W. Li, Y.-Z. Zhang and X.-C. Hu

Abstract top

The title compound, C10H12N2O4, adopts a trans configuration with respect to the C=N double bond. The non-H atoms of the molecule are essentially coplanar, with a maximum deviation of 0.015 (2) Å. An intramolecular O-H...N interaction is observed. In the crystal structure, the molecules are linked into a two-dimensional network parallel to the ac plane by N-H...O hydrogen bonds involving the methoxy O atom and by two C-H...O hydrogen bonds involving the carbonyl O atom. In addition, an intermolecular C-H...[pi] interaction is observed.

Comment top

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.

The title molecule adopts a trans configuration with respect to the C═N bond. The non-hydrogen atoms of the molecule are essentially coplanar, with a maximum deviation of 0.015 (2) Å for atom C(7). The bond lengths and angles are comparable to those observed for methylN'-[(E)-4-methoxybenzylidene]hydrazinecarboxylate (Shang et al., 2007). An intramolecular O—H···N interaction is observed.

In the crystal structure, the molecules are linked into a two-dimensional network parallel to the ac plane by N—H···O and C—H···O hydrogen bonds (Table 1 and Fig.2). In addition, C—H···π interactions are observed.

Related literature top

For general background to the properties of benzaldehydehydrazone derivatives, see: Parashar et al. (1988); Hadjoudis et al. (1987); Borg et al. (1999). For the use of metal complexes of Schiff bases as model compounds of active centres in various proteins and enzymes, see: Kahwa et al. (1986); Santos et al. (2001). For a related structure, see: Shang et al. (2007). Cg1 is the centroid of the C1–C6 ring.

Experimental top

2-Hydroxy-3-methoxybenzaldehyde (1.52 g, 0.01 mol) and methyl hydrazinecarboxylate (0.90g, 0.01 mol) were dissolved in stirred methanol (20 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 in 90% yield. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature (m.p. 415–418 K).

Refinement top

H atoms were positioned geometrically (O-H = 0.82 Å, 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.

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. Displacement ellipsoids are drawn at the 30% probability level. The dashed line indicates a hydrogen bond.
[Figure 2] Fig. 2. Crystal packing of the title compound. Hydrogen bonds are shown as dashed lines.
(E)-Methyl N'-(2-hydroxy-3-methoxybenzylidene)hydrazinecarboxylate top
Crystal data top
C10H12N2O4F(000) = 472
Mr = 224.22Dx = 1.394 Mg m−3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2ycCell parameters from 1049 reflections
a = 11.4348 (13) Åθ = 2.3–26.0°
b = 14.8717 (18) ŵ = 0.11 mm−1
c = 6.3508 (8) ÅT = 223 K
β = 98.538 (4)°Block, colourles
V = 1068.0 (2) Å30.24 × 0.22 × 0.17 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		1049 independent reflections
Radiation source: fine-focus sealed tube948 reflections with I > 2σ(I)
graphiteRint = 0.021
φ and ω scansθmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		h = −14→14
Tmin = 0.975, Tmax = 0.985k = −16→18
5851 measured reflectionsl = −7→7
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.0409P)2 + 0.1415P]
where P = (Fo2 + 2Fc2)/3
1049 reflections(Δ/σ)max = 0.003
148 parametersΔρmax = 0.11 e Å−3
2 restraintsΔρmin = −0.13 e Å−3
Crystal data top
C10H12N2O4V = 1068.0 (2) Å3
Mr = 224.22Z = 4
Monoclinic, CcMo Kα radiation
a = 11.4348 (13) ŵ = 0.11 mm−1
b = 14.8717 (18) ÅT = 223 K
c = 6.3508 (8) Å0.24 × 0.22 × 0.17 mm
β = 98.538 (4)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		1049 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		948 reflections with I > 2σ(I)
Tmin = 0.975, Tmax = 0.985Rint = 0.021
5851 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.075Δρmax = 0.11 e Å−3
S = 1.11Δρmin = −0.13 e Å−3
1049 reflectionsAbsolute structure: ?
148 parametersFlack parameter: ?
2 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
C10.11401 (17)0.33419 (13)0.6468 (3)0.0412 (5)
C20.14440 (19)0.38079 (15)0.4705 (4)0.0446 (5)
C30.0578 (2)0.42357 (16)0.3309 (4)0.0513 (6)
H30.07790.45500.21490.062*
C4−0.0596 (2)0.4195 (2)0.3646 (4)0.0584 (6)
H4−0.11760.44840.27040.070*
C5−0.0906 (2)0.37377 (16)0.5339 (4)0.0528 (6)
H5−0.16960.37110.55310.063*
C6−0.00420 (19)0.33056 (15)0.6795 (3)0.0436 (5)
C7−0.04116 (18)0.28326 (16)0.8601 (3)0.0469 (5)
H7−0.12030.28360.87880.056*
C80.07691 (19)0.15569 (15)1.3010 (3)0.0451 (5)
C90.1022 (3)0.0689 (2)1.6128 (5)0.0690 (8)
H9A0.15350.03041.54670.103*
H9B0.05690.03341.69770.103*
H9C0.14870.11181.70190.103*
C100.2979 (3)0.4277 (2)0.2805 (5)0.0767 (9)
H10A0.25970.40210.14950.115*
H10B0.38210.42310.28680.115*
H10C0.27600.48980.28740.115*
N10.03469 (15)0.24138 (13)0.9926 (3)0.0462 (4)
N2−0.00459 (16)0.19813 (14)1.1600 (3)0.0502 (5)
H2−0.07820.19811.17430.060*
O10.20402 (14)0.29467 (12)0.7790 (3)0.0553 (4)
H10.17760.26970.87700.083*
O20.26239 (14)0.38043 (11)0.4552 (3)0.0561 (4)
O30.18042 (15)0.15245 (13)1.2939 (3)0.0660 (5)
O40.02356 (14)0.11544 (12)1.4512 (3)0.0572 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0391 (10)0.0391 (12)0.0450 (11)0.0002 (8)0.0049 (9)−0.0029 (10)
C20.0418 (10)0.0435 (12)0.0494 (12)−0.0029 (8)0.0099 (9)−0.0048 (9)
C30.0525 (13)0.0533 (14)0.0481 (14)−0.0039 (10)0.0069 (10)0.0079 (11)
C40.0442 (11)0.0696 (17)0.0587 (15)0.0017 (10)−0.0016 (10)0.0162 (12)
C50.0377 (10)0.0573 (15)0.0632 (15)0.0004 (10)0.0066 (10)0.0057 (11)
C60.0419 (10)0.0420 (12)0.0477 (12)−0.0026 (9)0.0087 (8)−0.0025 (9)
C70.0417 (11)0.0477 (14)0.0526 (13)−0.0010 (9)0.0114 (10)−0.0009 (10)
C80.0430 (12)0.0476 (13)0.0466 (12)−0.0036 (9)0.0130 (9)−0.0022 (10)
C90.0701 (16)0.0767 (18)0.0617 (17)0.0157 (14)0.0148 (13)0.0164 (14)
C100.0583 (15)0.098 (2)0.081 (2)−0.0028 (14)0.0332 (14)0.0230 (16)
N10.0457 (9)0.0486 (11)0.0459 (9)−0.0044 (8)0.0120 (8)0.0006 (9)
N20.0388 (9)0.0593 (12)0.0544 (12)−0.0024 (8)0.0135 (8)0.0107 (9)
O10.0429 (8)0.0631 (10)0.0591 (10)0.0033 (8)0.0050 (7)0.0137 (8)
O20.0433 (8)0.0628 (9)0.0653 (10)0.0004 (7)0.0185 (7)0.0103 (8)
O30.0413 (9)0.0889 (13)0.0689 (11)0.0005 (8)0.0122 (7)0.0093 (10)
O40.0499 (8)0.0641 (11)0.0596 (10)0.0070 (7)0.0151 (7)0.0183 (8)
Geometric parameters (Å, °) top
C1—O11.361 (2)C8—O31.192 (3)
C1—C61.399 (3)C8—O41.347 (3)
C1—C21.404 (3)C8—N21.349 (3)
C2—O21.367 (3)C9—O41.438 (3)
C2—C31.382 (3)C9—H9A0.96
C3—C41.392 (3)C9—H9B0.96
C3—H30.93C9—H9C0.96
C4—C51.363 (4)C10—O21.423 (3)
C4—H40.93C10—H10A0.96
C5—C61.405 (3)C10—H10B0.96
C5—H50.93C10—H10C0.96
C6—C71.460 (3)N1—N21.374 (2)
C7—N11.277 (3)N2—H20.86
C7—H70.93O1—H10.82
O1—C1—C6123.41 (19)O3—C8—N2125.9 (2)
O1—C1—C2116.80 (17)O4—C8—N2109.70 (18)
C6—C1—C2119.79 (19)O4—C9—H9A109.5
O2—C2—C3125.2 (2)O4—C9—H9B109.5
O2—C2—C1114.75 (19)H9A—C9—H9B109.5
C3—C2—C1120.00 (19)O4—C9—H9C109.5
C2—C3—C4119.8 (2)H9A—C9—H9C109.5
C2—C3—H3120.1H9B—C9—H9C109.5
C4—C3—H3120.1O2—C10—H10A109.5
C5—C4—C3120.9 (2)O2—C10—H10B109.5
C5—C4—H4119.6H10A—C10—H10B109.5
C3—C4—H4119.6O2—C10—H10C109.5
C4—C5—C6120.5 (2)H10A—C10—H10C109.5
C4—C5—H5119.8H10B—C10—H10C109.5
C6—C5—H5119.8C7—N1—N2118.03 (16)
C1—C6—C5119.0 (2)C8—N2—N1117.36 (17)
C1—C6—C7122.28 (19)C8—N2—H2121.3
C5—C6—C7118.7 (2)N1—N2—H2121.3
N1—C7—C6120.31 (18)C1—O1—H1109.5
N1—C7—H7119.8C2—O2—C10116.9 (2)
C6—C7—H7119.8C8—O4—C9114.74 (19)
O3—C8—O4124.4 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.932.645 (2)145
N2—H2···O2i0.862.423.022 (2)127
C5—H5···O3ii0.932.493.320 (2)149
C7—H7···O3ii0.932.453.291 (2)150
C3—H3···Cg1iii0.932.853.606 (2)139
Symmetry codes: (i) x−1/2, −y+1/2, z+1/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) x, −y+1, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.932.645 (2)145
N2—H2···O2i0.862.423.022 (2)127
C5—H5···O3ii0.932.493.320 (2)149
C7—H7···O3ii0.932.453.291 (2)150
C3—H3···Cg1iii0.932.853.606 (2)139
Symmetry codes: (i) x−1/2, −y+1/2, z+1/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) x, −y+1, z−1/2.
Acknowledgements top

The authors are grateful for financial support from the Zhejiang University of Technology Foundation (grant No. 20080169) and the Analysis and Measurement Foundation of Zhejiang Province (grant No. 2008F70003).

references
References top

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