(2E)-2-(3-Eth­oxy-2-hy­droxy­benzyl­idene)hydrazinecarboxamide

A Ambili Aravindakshan; M Sithambaresan; M R Prathapachandra Kurup

doi:10.1107/S1600536813007617

. 2013 Mar 23;69(Pt 4):o586–o587. doi: 10.1107/S1600536813007617

(2E)-2-(3-Ethoxy-2-hydroxybenzylidene)hydrazinecarboxamide

A Ambili Aravindakshan ^a, M Sithambaresan ^b,^*, M R Prathapachandra Kurup ^a

PMCID: PMC3629631 PMID: 23634118

Abstract

The title compound, C₁₀H₁₃N₃O₃, adopts an E conformation with respect to the azomethine bond and crystallizes in the amide form. A classical intramolecular O—H⋯N hydrogen bond is present. The two N atoms of the hydrazinecarboxamide unit are also involved in intermolecular N—H⋯O hydrogen bonds, with the O atom of the hydrazinecarboxamide group acting as the acceptor. Pairs of N—H⋯O hydrogen bond link the molecules into centrosymmetric dimers, which are linked by further N—H⋯O hydrogen bonds into chains along the b axis. The chains are linked by C—H⋯π interactions.

Related literature

For biological applications of hydrazinecarboxamide and its derivatives, see: Afrasiabi et al. (2005 ▶); Siji et al. (2010 ▶); Beraldo & Gambino (2004 ▶). For related structures and background references, see: Sithambaresan & Kurup (2011 ▶); Noblía et al. (2004, ▶ 2005 ▶); Benítez et al. (2009 ▶, 2011 ▶); Rivadeneira et al. (2009 ▶); Gambino et al. (2011 ▶). For standard bond-length data, see: Allen et al. (1987 ▶); Kala et al. (2007 ▶). For the synthesis, see: Sreekanth et al. (2004 ▶).

Experimental

Crystal data

C₁₀H₁₃N₃O₃
M _r = 223.23
Triclinic,
a = 5.0676 (4) Å
b = 7.0426 (7) Å
c = 15.8394 (15) Å
α = 97.509 (4)°
β = 98.819 (3)°
γ = 105.790 (4)°
V = 528.62 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.969, T _max = 0.979
2559 measured reflections
1794 independent reflections
1496 reflections with I > 2σ(I)
R _int = 0.011

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.109
S = 1.05
1794 reflections
163 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg, 2010 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Supplementary Material

Click here for additional data file.^{(20.1KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813007617/fj2621sup1.cif

e-69-0o586-sup1.cif^{(20.1KB, cif)}

Click here for additional data file.^{(88.3KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813007617/fj2621Isup2.hkl

e-69-0o586-Isup2.hkl^{(88.3KB, hkl)}

Click here for additional data file.^{(4.4KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813007617/fj2621Isup3.cml

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

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

Cg is the centroid of the C1–C6 ring

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O3ⁱ	0.85 (1)	2.06 (1)	2.9034 (19)	173 (2)
O2—H2′⋯N1	0.84 (1)	1.89 (1)	2.6736 (15)	155 (2)
N2—H2⋯O3ⁱⁱ	0.87 (1)	2.06 (1)	2.8965 (17)	161 (2)
C9—H9A⋯Cg ⁱⁱⁱ	0.97	2.75	3.5896 (19)	145

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

Acknowledgments

AAA thanks the Council of Scientific and Industrial Research, New Delhi, India, for financial support in the form of a Junior Research Fellowship. The authors are grateful to the Sophisticated Analytical Instruments Facility, Cochin University of Science and Technology, Kochi-22, India, for the data collection. MRPK thanks the University Grants Commission, New Delhi, for a UGC–BSR one-time grant to faculty.

supplementary crystallographic information

Comment

The importance of semicarbazones lies in its pharmacological activities such as antitumoral (Afrasiabi et al., 2005), antimicrobial (Siji et al., 2010), antihypertensive, hypolipidemic, antineoplastic, hypnotic and anticonvulsant properties (Beraldo & Gambino, 2004). As the literature reports, the title compound, C₁₀H₁₃N₃O₃, is a tridentate semicarbazone ligand which formed complexes with vanadium (Noblía et al., 2004, 2005; Rivadeneira et al., 2009; Benítez et al., 2009; Benítez et al., 2011), and gallium (Gambino et al., 2011) and have demonstrated to possess biological activity as antitumor and antiparasitic agents.

The compound crystallizes in triclinic, P1 space group. The molecule exists in the E configuration with respect to C7═N1 bond (Sithambaresan & Kurup, 2011) which is confirmed by the torsion angle of -176.32 (13)° of C6—C7—N1—N2 moiety (Fig. 1). The torsion angle value of -169.81 (13)° corresponding to N1—N2—C8—O3 moiety supports the trans configuration of the O3 atom with respect to the hydrazine nitrogen atom N1 similar to its phenyl derivative (Sithambaresan & Kurup, 2011). The torsion angle value of 10.5 (2)° corresponding to N1—N2—C8—N3 moiety supports the cis configuration of the N3 atom with respect to the nitrogen atom N1. Also the torsion angles of -1.8 (2)° and 6.9 (2)° for O2—C1—C6—C7 and C1—C6—C7—N1 moieties respectively confirm the cis configuration of phenolic oxygen O2 and azomethine nitrogen N1 and it favours intramolecular hydrogen bonding between N1 and H attached to O2. The molecule as a whole slightly goes out of planarity with maximum mean plane deviations of 0.392 (2)° at N(3) and -0.345 (1)° at O(3).

Even though atom O1 lies cis to O2, with a torsion angle of -0.8 (2)° (O2—C1—C2—O1) and N1 lies cis to N3, with a torsion angle of 10.5 (2)° (N1—N2—C8—N3), there are no intramolecular hydrogen bonding interactions involving N3—H3'···N1 and O2—H2'···O1 bonds, which makes the title compound different from its phenyl derivative (Sithambaresan & Kurup, 2011). The C7═N1 [1.278 (2) Å] and C8═O3 [1.2481 (17) Å] bond distances are very close to the formal C═N and C═O bond lengths [C═ N; 1.28 Å and C═O; 1.21 Å] (Allen et al., 1987) respectively confirming the azomethine bond formation and the existence of semicarbazone in amido form in solid state. The N1—N2 [1.3749 (17) Å] and C8—N2 [1.352 (2) Å] bond distances lie in between the ideal values of corresponding single and double bonds [N—N; 1.45 and C—N; 1.47, N═N; 1.25 and C═N; 1.28] (Kala et al., 2007) and it clearly proves the extended conjugation in the molecule.

Two conventional intermolecular hydrogen bonds are present in the molecular system (Fig. 2) between the O3 and the H atoms attached to N2 and N3 atoms of the neighbouring molecules with D···A distances of 2.8963 (19) and 2.9032 (18) Å. N2–H2···O3 hydrogen bonds form centrosymmetric dimers and these dimers are connected together by means of N3–H3A···O3 hydrogen bond to construct a 1-D hydrogen bonding chain and such chains are beautifully connected one over the other by C–H···π interaction (Fig. 3) with H···π distance of 2.7500 Å keeping the molecular system stable. Fig. 4 shows the packing diagram of the title compound along b axis.

Experimental

The title compound was prepared by adapting a reported procedure (Sreekanth et al., 2004). To a warm methanolic solution of hydrazinecarboxamide (0.1115 g, 1 mmol), a methanolic solution of 3-ethoxy-2-hydroxybenzaldehyde (0.1662 g, 1 mmol) was added and the resulting solution was refluxed for 6 h after adding 3 drops of conc. HCl. On cooling the solution, colorless crystals were separated out. Single crystals suitable for X-ray diffraction studies were obtained by slow evaporation of its solution in 1:1 mixture of methanol and DMF.