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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1563.
Published online 2008 July 23. doi:  10.1107/S1600536808022332
PMCID: PMC2962185

(E)-Methyl N′-(2-hydroxy­benzyl­idene)­hydrazinecarboxyl­ate at 123 K

Abstract

In the title mol­ecule, C9H10N2O3, the hydrazinecarboxylic acid mean plane and the benzene ring form a dihedral angle of 11.1 (1)°. In the crystal structure, inter­molecular N—H(...)O hydrogen bonds link the mol­ecules into chains extending along the b axis. An intra­molecular O—H(...)N hydrogen bond is also present.

Related literature

For applications of benzaldehyde­hydrazone derivatives, see: Parashar et al. (1988 [triangle]); Hadjoudis et al. (1987 [triangle]); Borg et al. (1999 [triangle]). For related structures, see: Cheng (2008 [triangle]).

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Object name is e-64-o1563-scheme1.jpg

Experimental

Crystal data

  • C9H10N2O3
  • M r = 194.19
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1563-efi1.jpg
  • a = 9.3998 (17) Å
  • b = 9.0945 (16) Å
  • c = 22.319 (4) Å
  • V = 1908.0 (6) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 123 (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 = 0.965, T max = 0.968
  • 18306 measured reflections
  • 1679 independent reflections
  • 1427 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.120
  • S = 1.05
  • 1679 reflections
  • 128 parameters
  • H-atom parameters constrained
  • Δρmax = 0.19 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/S1600536808022332/cv2431sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808022332/cv2431Isup2.hkl

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

Acknowledgments

We acknowledge financial support from Zhejiang Police College, China.

supplementary crystallographic information

Comment

Benzaldehydehydrazone derivatives have received considerable attentions for a long time due to their pharmacological activity (Parashar et al., 1988) and their photochromic properties (Hadjoudis et al., 1987). Meanwhile, it's an important intermidiate of 1,3,4-oxadiazoles, which have been reported to be versatile compounds with many useful properties (Borg et al., 1999). As a further investigation of this type of derivatives, the crystal structure of the title compound, C9H10N2O3, is described here.

The title molecule (Fig. 1) adopts a trans configuration with respect to the C=N bond. Intramolecular O—H···N hydrogen bond (Table 1) influences the molecular conformation. The hydrazine carboxylic acid methyl ester group is slightly twisted away from the attached ring. The dihedral angle between the C1-C6 ring and the C8/C9/N1/N2/O2/O3 plane is 11.1 (1)°. The bond lengths and angles agree with those observed for (E)-Methyl N'-(4-hydroxybenzylidene) hydrazinecarboxylate (Cheng, 2008).

In the crystal, intermolecular N–H···O (Table 1) hydrogen bonds link the molecules into chains extended along b axis.

Experimental

2-hydroxy benzaldehyde (1.22 g, 0.01 mol) and methyl hydrazinecarboxylate (0.90 g, 0.01 mol) were dissolved in stirred methanol (20 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. Crystals suitable for X-ray analysis were obtained by slow evaporation of a ethanol solution at room temperature (m.p. 465–468 K).

Refinement

All H atoms were positioned geometrically (N—H 0.88 Å, O—H 0.84 Å, C—H 0.95-0.98 Å) and refined in the riding model approximation,, with Uiso(H) = 1.2–1.5Ueq of the parent atom.

Figures

Fig. 1.
Molecular structure of (I), showing 30% probability displacement ellipsoids and the atomic numbering. Dashed line denotes intramolecular hydrogen bond.

Crystal data

C9H10N2O3F000 = 816
Mr = 194.19Dx = 1.352 Mg m3
Orthorhombic, PbcaMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 1679 reflections
a = 9.3998 (17) Åθ = 2.0–25.0º
b = 9.0945 (16) ŵ = 0.10 mm1
c = 22.319 (4) ÅT = 123 (2) K
V = 1908.0 (6) Å3Block, colourless
Z = 80.27 × 0.24 × 0.23 mm

Data collection

Bruker SMART CCD area-detector diffractometer1679 independent reflections
Radiation source: fine-focus sealed tube1427 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.026
T = 123(2) Kθmax = 25.0º
[var phi] and ω scansθmin = 1.8º
Absorption correction: multi-scan(SADABS; Bruker, 2002)h = −10→11
Tmin = 0.965, Tmax = 0.968k = −10→10
18306 measured reflectionsl = −26→26

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.038  w = 1/[σ2(Fo2) + (0.0674P)2 + 0.4536P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.120(Δ/σ)max = 0.028
S = 1.05Δρmax = 0.19 e Å3
1679 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: 0.018 (2)
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
O30.37197 (12)0.41375 (11)−0.07538 (5)0.0513 (3)
O20.36215 (12)0.62287 (11)−0.02044 (5)0.0576 (4)
O10.16149 (12)0.69567 (13)0.13213 (5)0.0625 (4)
H10.19060.65250.10120.094*
N20.22056 (13)0.42471 (13)−0.00032 (5)0.0480 (4)
H20.19290.3365−0.01160.058*
N10.16212 (12)0.49157 (13)0.04907 (5)0.0452 (3)
C6−0.00199 (15)0.48908 (16)0.13011 (6)0.0429 (4)
C80.32185 (15)0.49856 (15)−0.03107 (6)0.0431 (4)
C50.05028 (15)0.61971 (16)0.15591 (6)0.0459 (4)
C70.06038 (16)0.42561 (15)0.07632 (6)0.0461 (4)
H70.02550.33470.06130.055*
C1−0.01226 (17)0.67565 (18)0.20764 (7)0.0558 (4)
H1A0.02360.76340.22510.067*
C4−0.11726 (17)0.41942 (18)0.15784 (7)0.0527 (4)
H4−0.15370.33110.14110.063*
C2−0.12633 (18)0.6040 (2)0.23379 (7)0.0568 (5)
H2A−0.16850.64310.26900.068*
C3−0.17925 (17)0.4760 (2)0.20895 (7)0.0573 (4)
H3−0.25770.42720.22690.069*
C90.47848 (19)0.4811 (2)−0.11312 (7)0.0617 (5)
H9A0.50810.4111−0.14410.093*
H9B0.56100.5087−0.08870.093*
H9C0.43860.5690−0.13210.093*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O30.0596 (7)0.0459 (6)0.0484 (6)0.0025 (5)0.0093 (5)−0.0070 (4)
O20.0665 (7)0.0388 (6)0.0674 (7)−0.0022 (5)0.0054 (5)−0.0070 (5)
O10.0605 (7)0.0593 (7)0.0678 (7)−0.0134 (5)0.0108 (5)−0.0181 (6)
N20.0567 (8)0.0389 (7)0.0484 (7)−0.0020 (5)0.0070 (6)−0.0121 (5)
N10.0476 (7)0.0430 (7)0.0451 (7)0.0051 (5)0.0001 (5)−0.0081 (5)
C60.0434 (8)0.0435 (8)0.0419 (8)0.0047 (6)−0.0069 (6)0.0001 (6)
C80.0478 (8)0.0366 (7)0.0448 (8)0.0075 (6)−0.0035 (6)−0.0040 (6)
C50.0457 (8)0.0472 (8)0.0449 (8)0.0032 (6)−0.0052 (6)−0.0023 (6)
C70.0491 (8)0.0406 (8)0.0487 (8)−0.0001 (6)−0.0032 (6)−0.0054 (6)
C10.0603 (10)0.0578 (10)0.0491 (8)0.0048 (8)−0.0057 (7)−0.0124 (7)
C40.0526 (9)0.0508 (9)0.0548 (9)−0.0005 (7)−0.0012 (7)−0.0002 (7)
C20.0586 (9)0.0722 (11)0.0395 (8)0.0159 (8)−0.0004 (7)−0.0001 (7)
C30.0530 (9)0.0651 (10)0.0536 (9)0.0043 (8)0.0057 (7)0.0105 (8)
C90.0589 (10)0.0734 (11)0.0528 (9)0.0014 (8)0.0107 (7)0.0036 (8)

Geometric parameters (Å, °)

O3—C81.3397 (17)C5—C11.392 (2)
O3—C91.4445 (19)C7—H70.9500
O2—C81.2158 (18)C1—C21.384 (2)
O1—C51.3607 (18)C1—H1A0.9500
O1—H10.8400C4—C31.380 (2)
N2—C81.3522 (19)C4—H40.9500
N2—N11.3736 (16)C2—C31.383 (3)
N2—H20.8800C2—H2A0.9500
N1—C71.2823 (19)C3—H30.9500
C6—C41.399 (2)C9—H9A0.9800
C6—C51.409 (2)C9—H9B0.9800
C6—C71.455 (2)C9—H9C0.9800
C8—O3—C9115.49 (12)C2—C1—C5120.34 (15)
C5—O1—H1109.5C2—C1—H1A119.8
C8—N2—N1117.97 (12)C5—C1—H1A119.8
C8—N2—H2121.0C3—C4—C6121.58 (15)
N1—N2—H2121.0C3—C4—H4119.2
C7—N1—N2118.15 (12)C6—C4—H4119.2
C4—C6—C5118.10 (14)C3—C2—C1120.42 (15)
C4—C6—C7119.81 (13)C3—C2—H2A119.8
C5—C6—C7122.09 (14)C1—C2—H2A119.8
O2—C8—O3124.74 (14)C4—C3—C2119.56 (16)
O2—C8—N2125.61 (14)C4—C3—H3120.2
O3—C8—N2109.65 (12)C2—C3—H3120.2
O1—C5—C1117.55 (13)O3—C9—H9A109.5
O1—C5—C6122.45 (13)O3—C9—H9B109.5
C1—C5—C6120.00 (14)H9A—C9—H9B109.5
N1—C7—C6120.40 (13)O3—C9—H9C109.5
N1—C7—H7119.8H9A—C9—H9C109.5
C6—C7—H7119.8H9B—C9—H9C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···N10.841.892.6234 (16)145
N2—H2···O2i0.882.022.8881 (16)169

Symmetry codes: (i) −x+1/2, y−1/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2431).

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.
  • Cheng, X.-W. (2008). Acta Cryst. E64, o1396. [PMC free article] [PubMed]
  • 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.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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