(E)-1-(2,4-Di­nitro­phen­yl)-2-(3-eth­oxy-4-hy­droxy­benzyl­idene)hydrazine

Hoong-Kun Fun; Suchada Chantrapromma; Pumsak Ruanwas; Thawanrat Kobkeatthawin; C S Chidan Kumar

doi:10.1107/S1600536813033989

. 2013 Dec 24;70(Pt 1):o89–o90. doi: 10.1107/S1600536813033989

(E)-1-(2,4-Dinitrophenyl)-2-(3-ethoxy-4-hydroxybenzylidene)hydrazine

Hoong-Kun Fun ^a,^*,^‡, Suchada Chantrapromma ^b,^§, Pumsak Ruanwas ^b, Thawanrat Kobkeatthawin ^b, C S Chidan Kumar ^a

PMCID: PMC3914112 PMID: 24527018

Abstract

The molecule of the title hydrazine derivative, C₁₅H₁₄N₄O₆, is essentially planar, the dihedral angle between the substituted benzene rings being 2.25 (9)°. The ethoxy and hydroxy groups are almost coplanar with their bound benzene ring [r.m.s. deviation = 0.0153 (2) Å for the ten non-H atoms]. Intramolecular N—H⋯O and O—H⋯O_ethoxy hydrogen bonds generate S(6) and S(5) ring motifs, respectively. In the crystal, molecules are linked by O—H⋯O_nitro hydrogen bonds into chains propagating in [010]. Weak aromatic π–π interactions, with centroid–centroid distances of 3.8192 (19) and 4.0491 (19) Å, are also observed.

Related literature

For a related structure and background to hydrazones, see: Fun et al. (2013 ▶). For other related structures, see: Fun et al. (2011 ▶, 2012 ▶). For the measurement of anti-oxidant activity, see: Molyneux (2004 ▶). graphic file with name e-70-00o89-scheme1.jpg

Experimental

Crystal data

C₁₅H₁₄N₄O₆
M _r = 346.30
Monoclinic,
a = 10.245 (4) Å
b = 13.679 (5) Å
c = 14.184 (5) Å
β = 129.15 (2)°
V = 1541.5 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 298 K
0.52 × 0.37 × 0.07 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.941, T _max = 0.992
16113 measured reflections
4060 independent reflections
2183 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.131
S = 1.01
4060 reflections
235 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.22 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, PLATON (Spek, 2009 ▶), Mercury (Macrae et al., 2006 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813033989/hb7175sup1.cif

e-70-00o89-sup1.cif^{(25.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813033989/hb7175Isup2.hkl

e-70-00o89-Isup2.hkl^{(199KB, hkl)}

Click here for additional data file.^{(6.3KB, cml)}

Supporting information file. DOI: 10.1107/S1600536813033989/hb7175Isup3.cml

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H1O6⋯O2ⁱ	0.84 (3)	2.21 (3)	2.986 (2)	155 (3)
O6—H1O6⋯O5	0.84 (3)	2.19 (3)	2.663 (3)	116 (2)
N1—H1N1⋯O1	0.86 (2)	2.007 (18)	2.641 (2)	130.0 (18)

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the Prince of Songkla University for generous support. CSCK thanks the Universiti Sains Malaysia for a postdoctoral research fellowship. The authors extend their appreciation to the Malaysian Government and the Universiti Sains Malaysia for the APEX DE2012 grant No. 1002/PFIZIK/910323.

supplementary crystallographic information

1. Comment

As part of our on-going research on diaryl-hydrazones with potential bioactivity, the title compound (I) was synthesized in order to study and compare its antioxidant activity with the other related compounds (Fun et al., 2011; 2012; 2013). In our antioxidant activity evaluation of (I) by DPPH scavenging (Molyneux, 2004) it was found that (I) possesses strong antioxidant activity with 82.71% inhibition, comparison with L-ascorbic acid as a standard (90.39 % inhibition). Herein we report the synthesis and crystal structure of (I).

In Fig. 1, the molecular structure of (I), C₁₅H₁₄N₄O₆, is essentially planar with the dihedral angle between the two substituted benzene rings being 2.25 (9)°. The mean plane through the bridge fragment (N1/N2/C7) makes the dihedral angles of 2.25 (19) and 2.30 (19)° with the C1–C6 and C8–C13 rings, respectively. Both nitro groups of the 2,4-dinitrophenyl are slightly deviated with respect to their attached ring [torsion angles O1—N3—C2—C1 = -8.3 (2)°, O2—N3—C2—C3 = -9.4 (2)°, O3—N4—C4—C3 = -7.0 (2)° and O4—N4—C4—C5 = -7.2 (2)°]. The substituted ethoxy and hydroxy groups are co-planar with the bound benzene ring with the r.m.s. deviation of 0.0153 (2) Å for the ten non H atoms and the torsion angles C9—C10—O5—C14 = -3.1 (2)° and C15—C14—O5—C10 = -178.05 (14)°. Intramolecular N1—H1N1···O1 hydrogen bond (Fig. 1 and Table 1) generates an S(6) ring motif whereas another intramolecular O6—H1O6—O5 hydrogen bond generates S(5) ring motif. These intramolecular hydrogen bonds help to stabilize the planarity of the molecule. Bond distances in (I) are comparable with those observed in the closely related structure (Fun et al., 2013).

In the crystal (Fig. 2), the molecules are linked by intermolecular O6—H1O6···O2 hydrogen bond (Table 1) into chains along [010]. There are weak π–π interactions (Fig. 3) with the distances of Cg₁···Cg₂ⁱⁱ = 3.8192 (19) Å and Cg₁···Cg₂ⁱⁱⁱ = 4.0491 (19) Å [symmetry codes (ii) = 2-x, -1/2+y, 1/2-z (iii) 2-x, -y, -z]; Cg₁ and Cg₂ are the centroids of C1–C6 and C8–C13 rings, respectively.

2. Experimental

2,4-dinitrophenylhydrazine (0.40 g, 2 mmol) was dissolved in ethanol (10 ml) and H₂SO₄ (conc.) (98 %, 0.50 ml) was added slowly with stirring. A solution of 3-ethoxy-4-hydroxybenzaldehyde (0.30 g, 2 mmol) in ethanol (20 ml) was then added to the solution with continuous stirring for 1 hr, yielding an orange solid which was filtered off and washed with methanol. Orange plates of (I) were recrystallized from acetone solution by slow evaporation of the solvent at room temperature over a few weeks, Mp. 515-516 K.