(E)-2-(4-Hy­droxy-3-meth­oxy­benzyl­idene)hydrazinecarboxamide

Hoong-Kun Fun; Chin Sing Yeap; Shridhar Malladi; Arun M Isloor

doi:10.1107/S1600536811024068

. 2011 Jun 25;67(Pt 7):o1786. doi: 10.1107/S1600536811024068

(E)-2-(4-Hydroxy-3-methoxybenzylidene)hydrazinecarboxamide

Hoong-Kun Fun ^a,^*,^‡, Chin Sing Yeap ^a,^§, Shridhar Malladi ^b, Arun M Isloor ^b

PMCID: PMC3151979 PMID: 21837159

Abstract

The asymmetric unit of the title compound, C₉H₁₁N₃O₃, consists of two crystallographically independent molecules. Both molecules are almost planar, with r.m.s. deviations of 0.107 and 0.099 Å. In the crystal, the two independent molecules form a dimer with an R ₂ ²(8) ring motif via N—H⋯O hydrogen bonds. The dimers are further linked into a three-dimensional network by O—H⋯O and N—H⋯O hydrogen bonds.

Related literature

For applications of semicarbazone derivatives, see: Warren et al. (1977 ▶); Chandra & Gupta (2005 ▶); Jain et al. (2002 ▶); Pilgram (1978 ▶); Yogeeswari et al. (2004 ▶). For the synthesis, see: Vogel et al. (1978 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₉H₁₁N₃O₃
M _r = 209.21
Orthorhombic,
a = 13.8568 (3) Å
b = 5.0379 (1) Å
c = 26.8582 (5) Å
V = 1874.95 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.56 × 0.21 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.939, T _max = 0.992
27088 measured reflections
3785 independent reflections
3477 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.098
S = 1.05
3785 reflections
305 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811024068/is2735sup1.cif

e-67-o1786-sup1.cif^{(21.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811024068/is2735Isup2.hkl

e-67-o1786-Isup2.hkl^{(185.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811024068/is2735Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2A—H2OA⋯O2Bⁱ	0.86 (3)	2.22 (3)	2.9924 (18)	149 (3)
N2A—H2NA⋯O3B	0.88 (3)	2.03 (3)	2.8966 (19)	171 (3)
N3A—H3NB⋯O3Bⁱⁱ	0.89 (3)	2.10 (3)	2.961 (2)	165 (2)
N2B—H2NB⋯O3A	0.90 (3)	2.00 (3)	2.8812 (18)	169 (2)
N3B—H3ND⋯O3Aⁱⁱⁱ	0.86 (3)	2.09 (3)	2.9415 (19)	172 (3)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

HKF and CSY thank Universiti Sains Malaysia for the Research University Grant 1001/PFIZIK/811160. AMI thanks the Department of Atomic Energy, Board for Research in Nuclear Sciences, Government of India for a Young Scientist award. AMI also thanks the Defence Research and Development Organization, New Delhi, India, for financial support.

supplementary crystallographic information

Comment

In organic chemistry, semicarbazone is a derivative of an aldehyde or ketone formed by condensation between a ketone or aldehyde and a semicarbazide. Semicarbazones find a large number of applications in the field of synthetic chemistry, such as in medicinal chemistry (Warren et al., 1977), organometallics (Chandra & Gupta, 2005), polymers (Jain et al., 2002), and herbicides (Pilgram, 1978). 4-Sulphamoylphenyl semicarbazones were found to possess anti-convulsant activity (Yogeeswari et al., 2004). Prompted by the diverse activities of semicarbazones, we have synthesized the title compound to study its crystal structure.

The asymmetric unit of title compound consists of two crystallographically independent molecules, A and B (Fig. 1). Both molecules are almost planar with the maximum deviation of 0.3177 (16) Å at N3A for molecule A whereas 0.1729 (12) Å at O3B for molecule B. The two independent molecules are interconnected by N2A—H2NA···O3B and N2B—H2NB···O3A hydrogen bonds (Fig. 1, Table 1) generating an R²₂(8) ring motif (Bernstein et al., 1995). In the crystal structure, the molecules are further linked into a three-dimensional network (Fig. 2) by O2A—H2OA···O2B, N3A—H3NB···O3B and N3B—H3ND···O3A hydrogen bonds (Table 1).

Experimental

Semicarbazide hydrochloride (0.86 g, 7.70 mmol) and freshly re-crystallized sodium acetate (0.77 g, 9.40 mmol) were dissolved in water (10 ml) following a literature procedure (Vogel et al., 1978). The reaction mixture was stirred at room temperature for 10 minutes. To this, vanillin (1.1 g, 7.23 mmol) was added and the mixture was shaken well. A little alcohol was added to dissolve the turbidity. The mixture was shaken for a further 10 minutes and allowed to stand. The title compound crystallizes on standing for 6 h. The separated crystals were filtered, washed with cold water and re-crystallized from ethanol. Yield: 1.34 g, 88.74%. M.p.: 502–504 K (Vogel et al., 1978).