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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1547.
Published online 2008 July 19. doi:  10.1107/S1600536808022307
PMCID: PMC2962171

(E)-Ethyl N′-(2-hydroxy­benzyl­idene)­hydrazinecarboxyl­ate

Abstract

There are two mol­ecules in the asymmetric unit of the title compound, C10H12N2O3, with identical conformations. Each independent mol­ecule is approximately planar and adopts a trans configuration with respect to the C=N double bond. Intra­molecular O—H(...)N hydrogen bonds are observed in both mol­ecules. The mol­ecules are linked into a ribbon-like structure running along the b axis by inter­molecular N—H(...)O and C—H(...)O hydrogen bonds. The ribbons are arranged into layers parallel to (An external file that holds a picture, illustration, etc.
Object name is e-64-o1547-efi1.jpg02).

Related literature

For the properties of benzaldehyde hydrazone derivatives, see: Parashar et al. (1988 [triangle]); Hadjoudis et al. (1987 [triangle]); Borg et al. (1999 [triangle]). For a related structure, see: Shang et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1547-scheme1.jpg

Experimental

Crystal data

  • C10H12N2O3
  • M r = 208.12
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1547-efi2.jpg
  • a = 11.535 (11) Å
  • b = 22.05 (2) Å
  • c = 9.005 (9) Å
  • β = 111.669 (14)°
  • V = 2129 (4) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 273 (2) K
  • 0.27 × 0.24 × 0.23 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2002 [triangle]) T min = 0.973, T max = 0.978
  • 14192 measured reflections
  • 3713 independent reflections
  • 1445 reflections with I > 2σ(I)
  • R int = 0.146

Refinement

  • R[F 2 > 2σ(F 2)] = 0.058
  • wR(F 2) = 0.150
  • S = 0.78
  • 3713 reflections
  • 274 parameters
  • H-atom parameters constrained
  • Δρmax = 0.29 e Å−3
  • Δρmin = −0.16 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/S1600536808022307/ci2635sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808022307/ci2635Isup2.hkl

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

Acknowledgments

The author acknowledges financial support from Zhejiang Institute of Communications, China.

supplementary crystallographic information

Comment

Benzaldehydehydrazone derivatives have received considerable attention for a long time due to their pharmacological activity (Parashar et al., 1988) and photochromic properties (Hadjoudis et al., 1987). They are important intermediates for 1,3,4-oxadiazoles, which have been reported to be versatile compounds with many properties (Borg et al., 1999). We report here the crystal structure of the title compound.

The asymmetric unit of the title compound contains two independent but essentially identical molecules (Fig. 1). The corresponding bond lengths and angles of the two independent molecules agree with each other and are comparable to those observed for N'-(4-methoxybenzylidene)methoxyformohydrazide (Shang et al., 2007). Each independent molecule is approximately planar and adopts a trans configuration with respect to the C═N bond. The dihedral angle between C1-C6 and O2/O3/N1/N2/C7-C10 planes is 7.6 (1)° and that between C11-C16 and O5/O6/N3/N4/C17-C20 planes is 5.5 (1)°. In both independent molecules intramolecular O—H···N hydrogen bonds are observed.

The molecules are linked into a ribbon-like structure running along the b axis by intermolecular N—H···O and C—H···O hydrogen bonds. (Fig.2). The ribbons are arranged into layers parallel to the (3 0 2) plane.

Experimental

2-Hydroxybenzaldehyde (1.22 g, 0.01 mol) and ethyl hydrazinecarboxylate (1.04 g, 0.01 mol) were dissolved in 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 85% yield. Single crystals suitable for X-ray analysis were obtained by slow evaporation of a methanol solution at room temperature (m.p. 455–457 K).

Refinement

H atoms were positioned geometrically (N-H = 0.86 Å and C-H = 0.95-0.99 Å) and refined using a riding model, with Uiso(H) = 1.2–1.5Ueq(C).

Figures

Fig. 1.
The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level. O—H···N hydrogen bonds are shown as dashed lines.
Fig. 2.
The crystal packing of the title compound, viewed approximately down the a axis. Dashed lines indicate hydrogen bonds.

Crystal data

C10H12N2O3F000 = 880
Mr = 208.12Dx = 1.299 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3713 reflections
a = 11.535 (11) Åθ = 1.9–25.0º
b = 22.05 (2) ŵ = 0.10 mm1
c = 9.005 (9) ÅT = 273 (2) K
β = 111.669 (14)ºBlock, colourless
V = 2129 (4) Å30.27 × 0.24 × 0.23 mm
Z = 8

Data collection

Bruker SMART CCD area-detector diffractometer3713 independent reflections
Radiation source: fine-focus sealed tube1445 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.146
T = 273(2) Kθmax = 25.0º
[var phi] and ω scansθmin = 1.9º
Absorption correction: multi-scan(SADABS; Bruker, 2002)h = −13→12
Tmin = 0.973, Tmax = 0.978k = −26→25
14192 measured reflectionsl = −10→10

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.058  w = 1/[σ2(Fo2) + (0.0618P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.150(Δ/σ)max = 0.001
S = 0.78Δρmax = 0.30 e Å3
3713 reflectionsΔρmin = −0.16 e Å3
274 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0017 (5)
Secondary atom site location: difference Fourier map

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
O10.6761 (2)−0.00597 (8)0.5564 (3)0.1012 (8)
H10.62490.00710.47250.121*
O20.43571 (18)−0.01273 (8)0.1327 (2)0.0799 (7)
O30.32487 (19)0.06261 (8)−0.0314 (2)0.0781 (7)
N10.5648 (2)0.07322 (10)0.3410 (3)0.0661 (7)
N20.4749 (2)0.08742 (10)0.1969 (3)0.0740 (8)
H2A0.45780.12460.16790.089*
C10.7458 (3)0.04071 (13)0.6420 (4)0.0744 (10)
C20.8384 (3)0.02856 (15)0.7861 (4)0.0988 (12)
H20.8519−0.01210.82370.119*
C30.9126 (3)0.07430 (16)0.8778 (4)0.1005 (12)
H30.97650.06500.97750.121*
C40.8937 (3)0.13398 (15)0.8240 (4)0.0933 (11)
H40.94430.16580.88590.112*
C50.8007 (3)0.14600 (14)0.6797 (4)0.0804 (10)
H50.78710.18680.64380.096*
C60.7250 (3)0.10084 (12)0.5834 (3)0.0635 (8)
C70.6293 (3)0.11571 (12)0.4328 (3)0.0669 (9)
H7A0.61350.15690.40070.080*
C80.4133 (3)0.04080 (14)0.1007 (4)0.0676 (9)
C90.2552 (3)0.01839 (14)−0.1492 (4)0.0839 (11)
H9A0.2072−0.0083−0.10440.101*
H9B0.3129−0.0071−0.18090.101*
C100.1687 (3)0.05187 (14)−0.2907 (4)0.0954 (11)
H10A0.12090.0228−0.37280.143*
H10B0.21710.0783−0.33380.143*
H10C0.11130.0765−0.25840.143*
O40.44788 (19)0.28071 (8)0.6198 (2)0.0858 (7)
H4A0.49200.25700.68730.103*
O50.7029 (2)0.23103 (9)0.9891 (3)0.0972 (8)
O60.75313 (19)0.14080 (8)1.1180 (2)0.0784 (7)
N30.5222 (2)0.17646 (9)0.7524 (3)0.0661 (7)
N40.5985 (2)0.14460 (10)0.8822 (3)0.0722 (8)
H60.59090.10610.89070.087*
C110.3641 (3)0.24868 (13)0.4965 (4)0.0665 (9)
C120.2807 (3)0.28054 (13)0.3700 (4)0.0814 (10)
H120.28220.32360.37100.098*
C130.1953 (3)0.25032 (15)0.2422 (4)0.0898 (11)
H130.13830.27280.15610.108*
C140.1915 (3)0.18688 (15)0.2380 (4)0.0929 (11)
H140.13370.16600.14920.111*
C150.2741 (3)0.15531 (14)0.3664 (4)0.0786 (10)
H150.27150.11220.36470.094*
C160.3610 (3)0.18441 (12)0.4981 (3)0.0623 (8)
C170.4436 (3)0.14927 (13)0.6327 (3)0.0638 (8)
H170.43890.10630.63110.077*
C180.6864 (3)0.17732 (15)0.9965 (4)0.0728 (9)
C190.8531 (3)0.17077 (14)1.2461 (4)0.0906 (11)
H19A0.81800.19761.30720.109*
H19B0.90370.19581.20140.109*
C200.9322 (3)0.12260 (14)1.3527 (4)0.1046 (12)
H20A0.99740.14161.44410.157*
H20B0.97100.09811.29280.157*
H20C0.88020.09661.39090.157*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.141 (2)0.0421 (13)0.0963 (17)0.0008 (13)0.0154 (15)0.0104 (12)
O20.0980 (16)0.0357 (11)0.0895 (16)0.0003 (11)0.0154 (13)0.0015 (10)
O30.0861 (15)0.0492 (12)0.0760 (15)0.0038 (11)0.0029 (13)−0.0049 (11)
N10.0828 (18)0.0437 (14)0.0631 (17)0.0054 (13)0.0167 (15)−0.0015 (12)
N20.0922 (19)0.0389 (14)0.0692 (18)0.0031 (13)0.0045 (16)−0.0030 (13)
C10.097 (3)0.049 (2)0.070 (2)0.0103 (18)0.022 (2)0.0070 (17)
C20.121 (3)0.062 (2)0.092 (3)0.023 (2)0.014 (3)0.023 (2)
C30.103 (3)0.093 (3)0.078 (3)0.023 (2)0.001 (2)0.012 (2)
C40.100 (3)0.071 (2)0.085 (3)0.004 (2)0.007 (2)0.000 (2)
C50.092 (2)0.0501 (19)0.077 (2)0.0031 (18)0.005 (2)0.0025 (17)
C60.073 (2)0.0487 (18)0.063 (2)0.0105 (16)0.0182 (18)0.0068 (16)
C70.084 (2)0.0419 (17)0.065 (2)0.0046 (16)0.0151 (18)−0.0006 (15)
C80.078 (2)0.051 (2)0.068 (2)0.0029 (18)0.0194 (19)−0.0028 (17)
C90.090 (2)0.062 (2)0.081 (3)−0.0088 (18)0.009 (2)−0.0169 (18)
C100.102 (3)0.084 (2)0.076 (2)0.000 (2)0.005 (2)0.0031 (19)
O40.1091 (17)0.0377 (11)0.0897 (16)−0.0034 (11)0.0121 (14)0.0022 (11)
O50.128 (2)0.0383 (13)0.0981 (17)−0.0128 (12)0.0095 (15)−0.0045 (11)
O60.0879 (16)0.0554 (13)0.0721 (15)−0.0046 (11)0.0062 (13)0.0023 (11)
N30.0805 (18)0.0402 (14)0.0678 (17)0.0020 (13)0.0159 (15)0.0016 (13)
N40.0864 (19)0.0336 (13)0.0771 (18)−0.0030 (13)0.0075 (16)0.0018 (13)
C110.081 (2)0.0425 (18)0.072 (2)−0.0037 (16)0.0228 (19)−0.0017 (16)
C120.095 (3)0.0512 (19)0.089 (3)0.0076 (19)0.023 (2)0.0140 (19)
C130.101 (3)0.068 (2)0.083 (3)0.004 (2)0.014 (2)0.018 (2)
C140.099 (3)0.070 (2)0.088 (3)−0.006 (2)0.009 (2)0.008 (2)
C150.091 (2)0.0497 (18)0.079 (2)−0.0087 (18)0.012 (2)−0.0058 (18)
C160.070 (2)0.0446 (17)0.070 (2)0.0015 (15)0.0234 (18)0.0022 (15)
C170.073 (2)0.0402 (16)0.072 (2)0.0004 (16)0.0197 (18)0.0004 (16)
C180.082 (2)0.055 (2)0.069 (2)0.0013 (19)0.015 (2)−0.0019 (18)
C190.097 (3)0.075 (2)0.079 (2)−0.008 (2)0.008 (2)0.0001 (19)
C200.103 (3)0.096 (3)0.092 (3)0.000 (2)0.010 (2)0.010 (2)

Geometric parameters (Å, °)

O1—C11.358 (3)O4—C111.369 (3)
O1—H10.82O4—H4A0.82
O2—C81.220 (3)O5—C181.205 (3)
O3—C81.338 (3)O6—C181.348 (3)
O3—C91.447 (3)O6—C191.454 (3)
N1—C71.289 (3)N3—C171.274 (3)
N1—N21.365 (3)N3—N41.369 (3)
N2—C81.363 (3)N4—C181.355 (3)
N2—H2A0.86N4—H60.86
C1—C21.368 (4)C11—C121.381 (4)
C1—C61.414 (4)C11—C161.418 (4)
C2—C31.382 (4)C12—C131.379 (4)
C2—H20.95C12—H120.95
C3—C41.391 (4)C13—C141.400 (4)
C3—H30.95C13—H130.95
C4—C51.371 (4)C14—C151.384 (4)
C4—H40.95C14—H140.95
C5—C61.395 (4)C15—C161.395 (4)
C5—H50.95C15—H150.95
C6—C71.436 (4)C16—C171.458 (4)
C7—H7A0.95C17—H170.95
C9—C101.491 (4)C19—C201.495 (4)
C9—H9A0.99C19—H19A0.99
C9—H9B0.99C19—H19B0.99
C10—H10A0.98C20—H20A0.98
C10—H10B0.98C20—H20B0.98
C10—H10C0.98C20—H20C0.98
C1—O1—H1109.4C11—O4—H4A109.4
C8—O3—C9116.4 (2)C18—O6—C19114.9 (2)
C7—N1—N2119.9 (2)C17—N3—N4120.9 (2)
C8—N2—N1117.8 (2)C18—N4—N3116.1 (2)
C8—N2—H2A121.2C18—N4—H6122.0
N1—N2—H2A121.0N3—N4—H6121.9
O1—C1—C2118.8 (3)O4—C11—C12118.4 (3)
O1—C1—C6121.0 (3)O4—C11—C16121.4 (3)
C2—C1—C6120.2 (3)C12—C11—C16120.3 (3)
C1—C2—C3121.2 (3)C13—C12—C11120.5 (3)
C1—C2—H2119.4C13—C12—H12119.7
C3—C2—H2119.4C11—C12—H12119.7
C2—C3—C4120.0 (3)C12—C13—C14120.7 (3)
C2—C3—H3120.0C12—C13—H13119.6
C4—C3—H3120.0C14—C13—H13119.6
C5—C4—C3118.7 (3)C15—C14—C13118.4 (3)
C5—C4—H4120.7C15—C14—H14120.8
C3—C4—H4120.7C13—C14—H14120.8
C4—C5—C6122.8 (3)C14—C15—C16122.4 (3)
C4—C5—H5118.6C14—C15—H15118.8
C6—C5—H5118.6C16—C15—H15118.8
C5—C6—C1117.1 (3)C15—C16—C11117.6 (3)
C5—C6—C7120.7 (3)C15—C16—C17120.4 (3)
C1—C6—C7122.1 (3)C11—C16—C17121.9 (3)
N1—C7—C6120.0 (3)N3—C17—C16119.8 (3)
N1—C7—H7A120.0N3—C17—H17120.1
C6—C7—H7A120.0C16—C17—H17120.1
O2—C8—O3125.7 (3)O5—C18—O6125.3 (3)
O2—C8—N2124.3 (3)O5—C18—N4124.8 (3)
O3—C8—N2110.0 (3)O6—C18—N4110.0 (3)
O3—C9—C10107.9 (3)O6—C19—C20107.7 (3)
O3—C9—H9A110.1O6—C19—H19A110.2
C10—C9—H9A110.1C20—C19—H19A110.2
O3—C9—H9B110.1O6—C19—H19B110.2
C10—C9—H9B110.1C20—C19—H19B110.2
H9A—C9—H9B108.4H19A—C19—H19B108.5
C9—C10—H10A109.5C19—C20—H20A109.5
C9—C10—H10B109.5C19—C20—H20B109.5
H10A—C10—H10B109.5H20A—C20—H20B109.5
C9—C10—H10C109.5C19—C20—H20C109.5
H10A—C10—H10C109.5H20A—C20—H20C109.5
H10B—C10—H10C109.5H20B—C20—H20C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.852.573 (3)147
N2—H2A···O4i0.862.132.979 (4)170
O4—H4A···N30.821.862.586 (3)146
N4—H6···O2ii0.862.082.931 (4)170
C5—H5···O5i0.952.273.184 (4)161
C15—H15···O1ii0.952.463.371 (5)161

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2635).

References

  • Borg, S., Vollinga, R. C., Labarre, M., Payza, K., Terenius, L. & Luthman, K. (1999). J. Med. Chem.42, 4331–4342. [PubMed]
  • 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]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography