2-Hydr­oxy-5-nitro­benzaldehyde 2,4-dinitro­phenyl­hydrazone

Abdassalam A Tameem; Bahruddin Saad; Abdussalam M Salhin; Samuel Robinson Jebas; Hoong-Kun Fun

doi:10.1107/S1600536808005825

. 2008 Mar 7;64(Pt 4):o679–o680. doi: 10.1107/S1600536808005825

2-Hydroxy-5-nitrobenzaldehyde 2,4-dinitrophenylhydrazone

Abdassalam A Tameem ^a, Bahruddin Saad ^a, Abdussalam M Salhin ^a, Samuel Robinson Jebas ^b,^‡, Hoong-Kun Fun ^b,^*

PMCID: PMC2961021 PMID: 21202072

Abstract

In the title compound, C₁₃H₉N₅O₇, one of the nitro groups is twisted away from the attached benzene ring by 16.21 (8)°. The dihedral angle between the two benzene rings is 4.63 (1)°. The molecular structure is stabilized by intramolecular N—H⋯O and O—H⋯N hydrogen bonds which generate an S(6) ring motif. The molecules pack as layers parallel to the ab plane; molecules of adjacent layers are linked into chains along the [101] direction through N—H⋯O hydrogen bonds.

Related literature

For related literature, see: Cordis et al. (1998 ▶); Fun et al. (1996 ▶); Guillaumont & Nakamura (2000 ▶); Hanoune et al. (2006 ▶); Lamberton et al. (1974 ▶); Niknam et al. (2005 ▶); Raj & Kurup (2007 ▶); Salhin et al. (2007 ▶); Shan, Xu et al. (2003 ▶); Shan, Yu et al. (2003 ▶); Tameem et al. (2007 ▶); Uchiyama et al. (2003 ▶); Vogel et al. (2000 ▶); Zegota (1999 ▶); Zlotorzynska & Lai (1999 ▶). For ring motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₃H₉N₅O₇
M _r = 347.25
Monoclinic,
a = 12.7543 (5) Å
b = 8.1898 (3) Å
c = 13.8618 (5) Å
β = 112.683 (2)°
V = 1335.94 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 100.0 (1) K
0.29 × 0.27 × 0.11 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.960, T _max = 0.985
24539 measured reflections
5195 independent reflections
3513 reflections with I > 2σ(I)
R _int = 0.056

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.145
S = 1.09
5195 reflections
234 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); 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, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808005825/ci2567sup1.cif

e-64-0o679-sup1.cif^{(17.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808005825/ci2567Isup2.hkl

e-64-0o679-Isup2.hkl^{(249.3KB, hkl)}

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
N1—H1N1⋯O4ⁱ	0.89 (2)	2.54 (2)	3.0666 (15)	118 (2)
N1—H1N1⋯O1	0.89 (2)	2.07 (2)	2.6477 (15)	121 (2)
O5—H1O5⋯N2	0.92 (3)	1.82 (3)	2.6656 (14)	150 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

FHK and SRJ thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. SRJ thanks the Universiti Sains Malaysia for the award of a post-doctoral research fellowship.

supplementary crystallographic information

Comment

Phenylhydrazone derivatives have been synthesized in order to investigate their structures and analytical applications. 2,4-Dinitrophenylhydrazones play an important role as stabilizers for the detection, characterization and protection of the carbonyl group of compounds than phenylhydrazones (Niknam et al., 2005). 2,4-Dinitrophenylhydrazone derivatives are widely used in various forms of analytical chemistry (Lamberton et al., 1974; Zegota, 1999; Cordis et al., 1998; Zlotorzynska & Lai, 1999) and are also used as dyes (Guillaumont & Nakamura, 2000). They are also found to have versatile coordinating abilities towards different metal ions (Raj et al., 2006). In addition, they are used to determine airborne aldehydes and ketones (Vogel et al., 2000) and as detectors of formaldehyde (Hanoune et al., 2006). These compounds can exist as E and Z stereoisomers (Uchiyama et al., 2003). Their existence as a keto tautomer in the solid state with an E configuration across the C—N bond have been reported (Fun et al., 1996). The title compound, whose structure is reported here, is one of the series of phenylhydrazone derivatives that we have prepared; the crystal structures of some of these compounds have been studied previously (Tameem et al., 2007; Salhin et al., 2007).

The bond lengths and angles in the title compound (Fig.1) have normal values. The molecule is nealy planar, with a maximum deviation from the mean plane of 0.487 (1) Å for atom O1. The dihedral angle between the two benzene rings is 4.63 (1)°. The C—N bond lengths in the hydrazone moiety agree well with those reported earlier (Shan, Xu et al., 2003; Shan, Yu et al., 2003). The asymmetry of the exocyclic angles at C7 [C7—C8—C13 = 118.2 (2)° and C7—C8—C9 = 123.3 (2)°] is more pronounced than that at C6 [N1—C6—C1 = 122.7 (1)° and N1—C6—C5 = 120.5 (1)°]. One of the hydrazone N atoms is involved in an O—H···N intramolecular hydrogen bond with the hydroxy group, while the other is involved in an N—H···O intramolecular hydrogen bond with the nitro group. Each of these hydrogen bonds generate an S(6) ring motif (Bernstein et al.,1995).

The molecules are linked into a chain along the [1 0 1] direction through N—H—O hydrogen bonds. The molecules pack as layers parallel to the ab plane. Within the layer, weak π-π interactions are observed between the C1—C6 and C8—C13 benzene rings, with a centroid-centroid distance of 3.7457 (8) Å.

Experimental

2,4-Dinitrophenylhydrazine (400 mg, 2 mmol) in concentrated sulfuric acid (5 ml) was slowly added to a solution of 2-hydroxy-5-nitrobenzaldehyde (337 mg, 2 mmol) in ethanol (95%, 20 ml). The mixture was stirred for 15 min, and was left to stand at room temperature for 30 min. The resulting product was filtered and washed with 95% ethanol (20 ml) and the orange powder product was collected. Crystals suitable for X-ray diffraction analysis were grown by slow evaporation of a saturated solution of the resulted compound in ethanol.