2-(3-Eth­oxy-2-hy­droxy­benz­ylidene)-N-phenyl­hydrazinecarboxamide

M Sithambaresan; M R Prathapachandra Kurup

doi:10.1107/S1600536811041857

. 2011 Oct 22;67(Pt 11):o2972. doi: 10.1107/S1600536811041857

2-(3-Ethoxy-2-hydroxybenzylidene)-N-phenylhydrazinecarboxamide

M Sithambaresan ^a,^*, M R Prathapachandra Kurup ^b

PMCID: PMC3247376 PMID: 22219994

Abstract

The title compound, C₁₆H₁₇N₃O₃, exists in the E configuration with respect to the azomethine double bond. The molecule is close to planar, with a dihedral angle of 6.7 (1)° between the aromatic rings. The phenolic O atom functions as donor and acceptor by forming intramolecular O—H⋯O and intermolecular N—H⋯O hydrogen bonds, respectively. Two-dimensional packing is fashioned through an intermolecular hydrogen bonding network in an offset manner.

Related literature

For background to N-phenylhydrazinecarboxamides and their complexes, see: Reena et al. (2008 ▶). For the synthesis of related compounds, see: Siji et al. (2010 ▶). For related structures, see: Kayed et al. (2011 ▶); Kala et al. (2007 ▶); Kurup et al. (2011 ▶); Reena & Kurup (2010 ▶).

Experimental

Crystal data

C₁₆H₁₇N₃O₃
M _r = 299.33
Monoclinic,
a = 30.1352 (13) Å
b = 5.5552 (3) Å
c = 18.2232 (8) Å
β = 92.753 (2)°
V = 3047.2 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.50 × 0.30 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) ▶ T _min = 0.967, T _max = 0.991
10811 measured reflections
2687 independent reflections
2066 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.137
S = 1.06
2687 reflections
213 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811041857/ng5242sup1.cif

e-67-o2972-sup1.cif^{(18.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811041857/ng5242Isup2.hkl

e-67-o2972-Isup2.hkl^{(132KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811041857/ng5242Isup3.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
N2—H2′⋯O2ⁱ	0.86 (2)	2.13 (2)	2.8799 (19)	145.9 (18)
N3—H3′⋯N1	0.85 (1)	2.25 (2)	2.6604 (17)	110.0 (14)
O2—H2⋯O3ⁱ	0.87 (2)	2.28 (2)	2.8867 (16)	127.1 (18)
O2—H2⋯O1	0.87 (2)	2.14 (2)	2.6206 (16)	114.2 (17)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors are thankful to the SAIF, CUSAT, Kochi-22, for providing the single-crystal XRD data.

supplementary crystallographic information

Comment

The compound crystallizes into a monoclinic space group C2/c. The molecule is almost planar with maximum deviation of 0.218 (1) Å for the atom N1. The dihedral angle between the two aromatic rings is 6.70°. The molecule exists in the E configuration with respect to C7=N1 bond (Fig. 1). A torsion angle value of -176.4 (1)° corresponding to O3–C8–N2–N1 moiety confirms the trans configuration of the O3 atom with respect to hydrazine nitrogen atom N1. As a result, the atom N1 lies cis to N3, with an N1–N2–C8–N3 torsion angle of 3.6 (2). This arrangement favours the intramolecular hydrogen bond interaction between N1 and H attached to N3 atom. Similarly O1 and O2 lie cis to each other with an torsion angle of -0.4 (2) and it favours the intramolecular hydrogen bond interaction between O1 and the H on O2 atom. These two intramolecular hydrogen bonding interactions play an important role by stabilizing this conformation. The C8–N2 bond distance [1.3656 (19) Å] is appreciably close to that of C–N single bond [1.351 (2) Å], confirming the keto form of the ligand (Reena & Kurup, 2010). The existence of 2-(3-ethoxy-2-hydroxybenzyl)-N-phenylhydrazinecarboxamide in the keto form in the solid state is evidenced by the C8–O2 bond distance of 1.2233 (19) Å, which is very close to a formal C=O bond length [1.21 Å] (Kala et al., 2007).

The neighbouring molecules are interconnected by intermolecular hydrogen bonding (Table 1). The molecular array involes two types of hydrogen bonding interactions where the O1 and O3 function as acceptors while the atom O2 acts as donor and acceptor.

In the crystal lattice (Fig. 2), two-dimensional packing is fashioned by the network of intermolecular hydrogen bonding interactions. The repeating units of two adjacent molecules are aligned in offset manner. The distance between two consecutive parallel rings is more than 5 Å and therefore there are very weak π···π or C–H···π interactions between the adjacent molecules. However, the hydrogen bonding plays key role in packing of molecules in the unit cell.

Experimental

The title compound was prepared by adapting a reported procedure (Siji et al., 2010). A methanolic solution (30 ml) of N-phenylhydrazinecarboxamide (1.511 g, 10 mmol) was added to a solution of 3-ethoxy-2-hydroxybenzaldehyde (1.662 g, 10 mmol) in methanol and the reaction mixture was refluxed for 2 h after adding a few drops of dilute acetic acid. On cooling the solution, very pale yellow block-shaped crystals suitable for single-crystal analysis were obtained.