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Acta Crystallogr Sect E Struct Rep Online. 2008 July 1; 64(Pt 7): o1302.
Published online 2008 June 19. doi:  10.1107/S1600536808018096
PMCID: PMC2961885

(E)-Methyl N′-(4-hydroxy­benzyl­idene)hydrazinecarboxyl­ate

Abstract

In the title compound, C9H10N2O3, the hydroxy group and the C=N—N unit are coplanar with the benzene ring. The benzene rings of inversion-related mol­ecules are stacked with their centroids separated by a distance of 3.7703 (9) Å, indicating weak π–π inter­actions. In the crystal structure, C—H(...)O, O—H(...)O, N—H(...)O and C—H(...)O hydrogen bonds link molecules into a infinite two-dimensional network along the a axis.

Related literature

For general background, see: Hadjoudis et al. (1987 [triangle]); Borg et al. (1999 [triangle]); Parashar et al. (2005). For a related structure, see: Shang et al. (2007 [triangle]). For related literature, see: Parashar et al. (1988 [triangle]).

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Object name is e-64-o1302-scheme1.jpg

Experimental

Crystal data

  • C9H10N2O3
  • M r = 194.19
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1302-efi1.jpg
  • a = 8.1943 (8) Å
  • b = 12.0512 (11) Å
  • c = 10.1067 (9) Å
  • β = 111.970 (3)°
  • V = 925.57 (15) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 123 (2) K
  • 0.31 × 0.28 × 0.24 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2002 [triangle]) T min = 0.969, T max = 0.978
  • 9552 measured reflections
  • 1623 independent reflections
  • 1487 reflections with I > 2σ(I)
  • R int = 0.021

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.115
  • S = 0.95
  • 1623 reflections
  • 128 parameters
  • H-atom parameters constrained
  • Δρmax = 0.24 e Å−3
  • Δρmin = −0.19 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/S1600536808018096/tk2273sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808018096/tk2273Isup2.hkl

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

Acknowledgments

The author acknowledges financial support from Zhejiang Police College, China.

supplementary crystallographic information

Comment

Benzaldehydehydrazone derivatives have received considerable attention owing to their pharmacological activity (Parashar et al., 1988) and their photochromic properties (Hadjoudis et al., 1987). In addition, they are important intermediates in the synthesis of 1,3,4-oxadiazoles, which have been reported to be versatile compounds (Borg et al., 1999). As a part of an investigation of this type of derivative, the crystal structure of the title compound, C9H10N2O3 (I), is described herein.

In (I), Fig. 1 & Table 1, all non-hydrogen atoms are co-planar to within ±0.699 (4) Å. The molecule is in the E-conformation with respect to the N=C double bond. The bond lengths and angles defining the C=N—N(H)—C group are close to those of the previously reported N'-(4-Methoxybenzylidene)methoxyformohydrazide structure (shang et al., 2007).

The benzene rings of inversion-related molecules are stacked with their centroids separated by a distance of 3.7703 (9) Å, consistent with π-π interactions.

Experimental

4-Hydroxy benzaldehyde (12.2 g, 0.1 mol) and methyl hydrazinecarboxylate (9.0 g, 0.1 mol) were dissolved in methanol (50 ml) solution and stirred for 6 h at room temperature. The resulting solid was filtered off and recrystallized from an ethanol solution to give (I) in 80% yield. Crystals suitable for X-ray analysis were obtained by the slow evaporation of an ethanol solution held at room temperature (m.p. 475–478 K).

Refinement

The H atoms were included in the riding model approximation with O—H = 0.84 Å, N—H = 0.86 Å and C—H = 0.95 - 0.98 Å, and with Uiso(H) = 1.2Ueq(C, N) and 1.5Ueq(O, methyl-C).

Figures

Fig. 1.
Molecular structure of (I), showing 30% probability displacement ellipsoids and the atomic numbering.

Crystal data

C9H10N2O3F000 = 408
Mr = 194.19Dx = 1.394 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1628 reflections
a = 8.1943 (8) Åθ = 2.0–25.0º
b = 12.0512 (11) ŵ = 0.11 mm1
c = 10.1067 (9) ÅT = 123 (2) K
β = 111.970 (3)ºBlock, colourless
V = 925.57 (15) Å30.31 × 0.28 × 0.24 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer1623 independent reflections
Radiation source: fine-focus sealed tube1487 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.021
T = 123(2) Kθmax = 25.0º
[var phi] and ω scansθmin = 2.7º
Absorption correction: multi-scan(SADABS; Bruker, 2002)h = −9→9
Tmin = 0.969, Tmax = 0.978k = −13→14
9552 measured reflectionsl = −11→12

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.035  w = 1/[σ2(Fo2) + (0.0871P)2 + 0.1838P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.115(Δ/σ)max < 0.001
S = 0.95Δρmax = 0.24 e Å3
1623 reflectionsΔρmin = −0.19 e Å3
128 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.288 (19)
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
O10.38082 (14)0.30936 (8)0.37656 (11)0.0529 (3)
H10.31620.31340.28970.079*
O20.97787 (14)−0.29441 (9)0.29627 (10)0.0516 (3)
O31.11604 (14)−0.37383 (8)0.51277 (11)0.0520 (3)
N20.94810 (15)−0.22777 (9)0.49593 (12)0.0440 (3)
H2A0.9787−0.23530.58870.053*
N10.83415 (14)−0.14299 (9)0.42392 (11)0.0395 (3)
C50.57987 (17)0.04812 (11)0.32350 (13)0.0396 (4)
H50.5728−0.00240.24940.047*
C60.69854 (16)0.02765 (10)0.46270 (13)0.0369 (3)
C30.47278 (17)0.14106 (11)0.29260 (13)0.0408 (4)
H30.39320.15380.19760.049*
C10.48094 (16)0.21605 (10)0.39995 (14)0.0390 (4)
C20.59680 (18)0.19579 (11)0.53868 (14)0.0428 (4)
H20.60280.24590.61290.051*
C40.70306 (17)0.10317 (12)0.56872 (14)0.0410 (4)
H40.78150.09040.66410.049*
C81.01137 (16)−0.29807 (11)0.42353 (14)0.0386 (4)
C70.81502 (16)−0.06805 (11)0.50677 (14)0.0398 (4)
H70.8828−0.07550.60580.048*
C91.1945 (2)−0.45473 (13)0.4509 (2)0.0619 (5)
H9A1.2675−0.50540.52530.093*
H9B1.2678−0.41710.40710.093*
H9C1.1018−0.49690.37780.093*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0548 (6)0.0432 (6)0.0517 (6)0.0084 (4)0.0096 (5)−0.0039 (4)
O20.0574 (6)0.0589 (7)0.0365 (6)0.0024 (5)0.0154 (5)−0.0063 (4)
O30.0570 (6)0.0504 (6)0.0506 (6)0.0140 (5)0.0226 (5)0.0073 (4)
N20.0520 (7)0.0473 (7)0.0344 (6)0.0110 (5)0.0181 (5)0.0068 (5)
N10.0390 (6)0.0411 (6)0.0388 (6)0.0018 (4)0.0153 (5)0.0040 (5)
C50.0446 (7)0.0398 (7)0.0358 (7)−0.0025 (5)0.0168 (5)−0.0020 (5)
C60.0376 (6)0.0367 (7)0.0384 (7)−0.0047 (5)0.0164 (5)0.0018 (5)
C30.0416 (7)0.0423 (7)0.0357 (7)−0.0026 (5)0.0111 (5)0.0022 (5)
C10.0383 (7)0.0340 (7)0.0451 (8)−0.0036 (5)0.0161 (6)0.0005 (5)
C20.0464 (7)0.0408 (7)0.0405 (7)−0.0039 (6)0.0155 (6)−0.0063 (6)
C40.0421 (7)0.0435 (8)0.0352 (6)−0.0041 (5)0.0118 (5)−0.0001 (5)
C80.0372 (7)0.0407 (7)0.0381 (7)−0.0041 (5)0.0141 (5)−0.0006 (5)
C70.0419 (7)0.0423 (8)0.0351 (7)−0.0020 (5)0.0142 (5)0.0020 (5)
C90.0611 (10)0.0503 (9)0.0785 (12)0.0113 (7)0.0311 (8)−0.0005 (8)

Geometric parameters (Å, °)

O1—C11.3595 (16)C6—C41.3958 (18)
O1—H10.8400C6—C71.4565 (18)
O2—C81.2114 (17)C3—C11.3943 (19)
O3—C81.3431 (16)C3—H30.9500
O3—C91.4339 (18)C1—C21.3895 (19)
N1—N21.3917 (15)C2—C41.3778 (19)
N2—H2A0.8800C2—H20.9500
N1—C71.2805 (17)C4—H40.9500
N2—C81.3438 (17)C7—H70.9500
C5—C31.3846 (18)C9—H9A0.9800
C5—C61.4007 (18)C9—H9B0.9800
C5—H50.9500C9—H9C0.9800
C1—O1—H1109.5C4—C2—C1120.11 (12)
C8—O3—C9116.56 (12)C4—C2—H2119.9
N1—N2—C8119.88 (11)C1—C2—H2119.9
C8—N2—H2A120.1C2—C4—C6121.73 (12)
N1—N2—H2A120.1C2—C4—H4119.1
N2—N1—C7113.47 (11)C6—C4—H4119.1
C3—C5—C6120.82 (12)O2—C8—O3124.88 (12)
C3—C5—H5119.6O2—C8—N2125.09 (13)
C6—C5—H5119.6O3—C8—N2110.03 (11)
C4—C6—C5117.73 (12)N1—C7—C6125.81 (11)
C4—C6—C7117.09 (11)N1—C7—H7117.1
C5—C6—C7125.16 (12)C6—C7—H7117.1
C5—C3—C1120.46 (12)O3—C9—H9A109.5
C5—C3—H3119.8O3—C9—H9B109.5
C1—C3—H3119.8H9A—C9—H9B109.5
O1—C1—C2117.44 (12)O3—C9—H9C109.5
O1—C1—C3123.41 (12)H9A—C9—H9C109.5
C2—C1—C3119.14 (12)H9B—C9—H9C109.5
C8—N2—N1—C7−165.18 (12)C5—C6—C4—C2−0.82 (19)
C3—C5—C6—C40.84 (18)C7—C6—C4—C2−179.27 (11)
C3—C5—C6—C7179.14 (12)C9—O3—C8—O20.9 (2)
C6—C5—C3—C1−0.14 (19)C9—O3—C8—N2−179.72 (12)
C5—C3—C1—O1179.33 (12)N1—N2—C8—O20.3 (2)
C5—C3—C1—C2−0.60 (19)N1—N2—C8—O3−179.11 (10)
O1—C1—C2—C4−179.31 (12)N2—N1—C7—C6−177.08 (11)
C3—C1—C2—C40.62 (19)C4—C6—C7—N1−176.85 (12)
C1—C2—C4—C60.1 (2)C5—C6—C7—N14.8 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.842.583.068 (2)118
O1—H1···N1i0.842.112.941 (2)169
N2—H2A···O2ii0.882.132.964 (2)158
C7—H7···O2ii0.952.383.188 (2)143

Symmetry codes: (i) −x+1, 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: TK2273).

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]

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