(E)-1-(2,4-Dinitro­phen­yl)-2-[1-(3-fluoro­phen­yl)ethyl­idene]hydrazine

Suchada Chantrapromma; Boonlerd Nilwanna; Thawanrat Kobkeatthawin; Patcharaporn Jansrisewangwong; Hoong-Kun Fun

doi:10.1107/S160053681201937X

. 2012 May 5;68(Pt 6):o1644–o1645. doi: 10.1107/S160053681201937X

(E)-1-(2,4-Dinitrophenyl)-2-[1-(3-fluorophenyl)ethylidene]hydrazine

Suchada Chantrapromma ^a,^*,^‡, Boonlerd Nilwanna ^a, Thawanrat Kobkeatthawin ^a, Patcharaporn Jansrisewangwong ^a, Hoong-Kun Fun ^b,^§

PMCID: PMC3379246 PMID: 22719444

Abstract

The molecule of the title hydrazone derivative, C₁₄H₁₁FN₄O₄, is nearly planar, with a dihedral angle between the benzene rings of 3.71 (7)°. The central ethylidenehydrazine N—N=C—C plane makes dihedral angles of 5.32 (10) and 9.02 (10)° with the 2,4-dinitro- and 3-fluoro-substituted benzene rings, respectively. An intramolecular N—H⋯O bond generates an S(6) ring motif. In the crystal, molecules are linked by weak C—H⋯O interactions into a sheet parallel to (10-1). The molecules are further stacked along the a axis by π–π interactions with centroid–centroid distances of 3.6314 (9) and 3.7567 (10) Å. A C⋯F short contact [2.842 (3) Å] is observed. The 3-fluorophenyl group is disordered over two orientations with a site-occupancy ratio of 0.636 (3):0.364 (3).

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For related structures, see: Chantrapromma et al. (2011 ▶); Fun et al. (2011 ▶, 2012 ▶); Nilwanna et al. (2011 ▶). For background to and the biological activity of hydrozones, see: Cui et al. (2010 ▶); Gokce et al. (2009 ▶); Krishnamoorthy et al. (2011 ▶); Molyneux (2004 ▶); Wang et al. (2009 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶). graphic file with name e-68-o1644-scheme1.jpg

Experimental

Crystal data

C₁₄H₁₁FN₄O₄
M _r = 318.27
Monoclinic,
a = 7.0165 (6) Å
b = 13.3336 (11) Å
c = 14.4498 (12) Å
β = 94.791 (2)°
V = 1347.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 100 K
0.39 × 0.15 × 0.14 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.952, T _max = 0.982
15079 measured reflections
3874 independent reflections
3126 reflections with I > 2σ(I)
R _int = 0.054

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.155
S = 1.07
3874 reflections
223 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.59 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/S160053681201937X/is5116sup1.cif

e-68-o1644-sup1.cif^{(25.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681201937X/is5116Isup2.hkl

e-68-o1644-Isup2.hkl^{(189.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681201937X/is5116Isup3.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—H1N2⋯O1	0.89 (2)	1.90 (2)	2.6038 (18)	135 (2)
C9—H9A⋯O1ⁱ	0.93	2.58	3.413 (2)	150
C13—H13A⋯O4ⁱⁱ	0.93	2.44	3.176 (2)	137

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

Acknowledgments

BN, TK and PJ thank the Crystal Materials Research Unit, Prince of Songkla University, for financial support. The authors thank Prince of Songkla University and Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160.

supplementary crystallographic information

Comment

The variety of interesting biological activities of hydrazones and their complexes such as antibacterial, antifungal, anti-inflammatory as well as antioxidant properties (Cui et al., 2010; Gokce et al., 2009; Krishnamoorthy et al., 2011; Wang et al., 2009) has prompted us to synthesize several hydrazone derivatives and to study for their biological activities. However the title compound (I) which was synthesized for the evaluation of its antioxidant activity by DPPH scavenging (Molyneux, 2004) was found to be inactive. Herein we report the synthesis and crystal structure of (I).

In the molecular structure of (I), C₁₄H₁₁FN₄O₄, the F atoms of the 3-fluorophenyl group is disordered over two positions with the major component A and the minor B component rotated by 180° about the C7—C8 bond and having a refined site-occupancy ratio of 0.636 (3):0.364 (3) (Fig. 1). The molecule is nearly planar with a dihedral angle between the two benzene rings being 3.71 (7)°. The middle ethylidenehydrazine bridge is planar with the torsion angle N2–N1–C7–C14 = 0.8 (2)°. The mean plane through this middle bridge makes dihedral angles of 5.32 (10) and 9.02 (10)° with the 2,4-dinitrophenyl and 3-fluorophenyl rings, respectively. The two nitro groups of the 2,4-dinitrophenyl unit are slightly twisted with the attached benzene ring as indicated by the torsion angles O1–N3–C2–C1 = -3.8 (2)°, O2–N3–C2–C1 = 176.52 (15)°, O3–N4–C4–C3 = -8.3 (2)° and O4–N4–C4–C3 = 171.96 (16)°. An intramolecular N2—H1N2···O1 hydrogen bond (Fig.1 and Table 1) generates an S(6) ring motif (Bernstein et al., 1995). The bond distances are in normal ranges (Allen et al., 1987) and are comparable with the closely related structures (Chantrapromma et al., 2011; Fun et al., 2011, 2012; Nilwanna et al., 2011).

In the crystal packing (Fig. 2), the molecules are linked by weak C—H···O interactions (Table 1) into a sheet parallel to the (101) plane and these sheets are stacked along the a axis by π–π interactions with centroid-to-centroid distances Cg1···Cg2 = 3.7567 (10)ⁱⁱⁱ and 3.6314 (9)^iv Å [symmetry codes (iii) = -x, 1-y, 1-z and (iv) = 1-x, 1-y, 1-z)]. A C14···F1B^v [2.905 (3) Å ; symmetry code (v) = -x, -1/2+y, 1/2-z] short contact is observed.

Experimental

The title compound (I) was synthesized by dissolving 2,4-dinitrophenylhydrazine (0.40 g, 2 mmol) in ethanol (10.00 ml) and H₂SO₄ (conc.) (98 %, 0.50 ml) was slowly added with stirring. 3-Fluoroacetophenone (0.25 ml, 2 mmol) was then added to the solution with continuous stirring. The solution was stirred for 1 hr yielding an yellow solid, which was filtered off and washed with methanol. Yellow block-shaped single crystals of the title compound suitable for x-ray structure determination were recrystallized from ethanol by slow evaporation of the solvent at room temperature over several days. M.p. 503-504 K.