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Acta Crystallogr Sect E Struct Rep Online. 2008 April 1; 64(Pt 4): o679–o680.
Published online 2008 March 7. doi:  10.1107/S1600536808005825
PMCID: PMC2961021

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

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

An external file that holds a picture, illustration, etc.
Object name is e-64-0o679-scheme1.jpg

Experimental

Crystal data

  • C13H9N5O7
  • M r = 347.25
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o679-efi1.jpg
  • 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 [triangle]) 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
  • Δρmax = 0.47 e Å−3
  • Δρmin = −0.33 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 [triangle]); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

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

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.

Refinement

O– and N-bound H atoms were located in a difference map and refined isotropically. The remaining H atoms were placed in calculated positions (C—H = 0.93 Å) and refined using a riding model, with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atomic numbering scheme. Hydrogen bonds are shown as dashed lines.
Fig. 2.
The crystal packing of the title compound, viewed along the c axis. Hydrogen bonds are shown as dashed lines.

Crystal data

C13H9N5O7F000 = 712
Mr = 347.25Dx = 1.726 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3255 reflections
a = 12.7543 (5) Åθ = 2.8–33.1º
b = 8.1898 (3) ŵ = 0.14 mm1
c = 13.8618 (5) ÅT = 100.0 (1) K
β = 112.683 (2)ºBlock, orange
V = 1335.94 (9) Å30.29 × 0.27 × 0.11 mm
Z = 4

Data collection

Bruker SMART APEXII CCD area-detector diffractometer3513 reflections with I > 2σ(I)
Detector resolution: 8.33 pixels mm-1Rint = 0.056
ω scansθmax = 33.4º
Absorption correction: multi-scan(SADABS; Bruker, 2005)θmin = 2.8º
Tmin = 0.960, Tmax = 0.985h = −19→19
24539 measured reflectionsk = −10→12
5195 independent reflectionsl = −21→20

Refinement

Refinement on F2H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.0708P)2 + 0.0132P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.050(Δ/σ)max = 0.001
wR(F2) = 0.145Δρmax = 0.47 e Å3
S = 1.09Δρmin = −0.33 e Å3
5195 reflectionsExtinction correction: none
234 parameters

Special details

Geometry. Experimental. The low-temperature data was collected with the Oxford Crysosystem Cobra low-temperature attachement.All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
O10.71240 (8)0.91583 (13)0.22343 (8)0.0228 (2)
O20.61439 (9)1.12841 (14)0.22968 (8)0.0282 (2)
O30.39947 (10)1.41385 (15)−0.08171 (9)0.0340 (3)
O40.45224 (10)1.41148 (14)−0.21219 (8)0.0307 (3)
O50.94762 (8)0.81549 (12)−0.11896 (7)0.0189 (2)
O61.34597 (9)0.33913 (14)0.11735 (8)0.0300 (3)
O71.29887 (9)0.41281 (13)0.24496 (8)0.0259 (2)
N10.80661 (9)0.91651 (14)0.08340 (9)0.0164 (2)
N20.87737 (9)0.86266 (13)0.03680 (8)0.0157 (2)
N30.66026 (9)1.04241 (14)0.18460 (8)0.0187 (2)
N40.46053 (10)1.36459 (15)−0.12555 (9)0.0208 (2)
N51.28791 (9)0.41996 (14)0.15301 (9)0.0184 (2)
C10.64902 (11)1.08800 (16)0.07968 (9)0.0160 (2)
C20.56488 (11)1.20121 (16)0.02874 (10)0.0179 (2)
H2A0.52091.24650.0620.021*
C30.54779 (10)1.24505 (16)−0.07199 (10)0.0172 (2)
C40.61284 (11)1.17695 (16)−0.12363 (10)0.0171 (2)
H4A0.59931.2067−0.19210.02*
C50.69644 (11)1.06624 (16)−0.07233 (10)0.0165 (2)
H5A0.73921.0211−0.10690.02*
C60.71925 (10)1.01896 (15)0.03210 (9)0.0150 (2)
C70.96469 (10)0.78013 (15)0.09632 (9)0.0151 (2)
H7A0.97820.76780.16680.018*
C81.04195 (10)0.70636 (15)0.05474 (9)0.0142 (2)
C91.03109 (10)0.72528 (15)−0.05001 (9)0.0151 (2)
C101.10725 (11)0.64726 (16)−0.08556 (10)0.0168 (2)
H10A1.10090.6634−0.1540.02*
C111.19152 (10)0.54678 (16)−0.02006 (10)0.0169 (2)
H11A1.24120.4933−0.0440.02*
C121.20051 (10)0.52732 (15)0.08265 (10)0.0159 (2)
C131.12875 (10)0.60635 (15)0.12052 (10)0.0153 (2)
H13A1.13820.5930.190.018*
H1N10.8262 (16)0.891 (2)0.1508 (16)0.038 (5)*
H1O50.905 (2)0.854 (3)−0.082 (2)0.067 (8)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0238 (5)0.0253 (5)0.0220 (5)0.0056 (4)0.0118 (4)0.0049 (4)
O20.0377 (6)0.0307 (6)0.0253 (5)0.0079 (5)0.0222 (5)−0.0004 (4)
O30.0317 (6)0.0461 (7)0.0298 (6)0.0207 (5)0.0181 (5)0.0077 (5)
O40.0379 (6)0.0342 (6)0.0228 (5)0.0153 (5)0.0150 (5)0.0087 (4)
O50.0201 (4)0.0210 (5)0.0162 (4)0.0047 (4)0.0076 (3)0.0023 (3)
O60.0284 (5)0.0335 (6)0.0285 (5)0.0145 (5)0.0114 (4)0.0014 (4)
O70.0269 (5)0.0307 (6)0.0197 (5)0.0070 (4)0.0086 (4)0.0059 (4)
N10.0163 (5)0.0196 (5)0.0155 (5)0.0030 (4)0.0085 (4)0.0005 (4)
N20.0158 (5)0.0157 (5)0.0177 (5)0.0000 (4)0.0089 (4)−0.0017 (4)
N30.0193 (5)0.0220 (6)0.0183 (5)−0.0015 (4)0.0112 (4)−0.0006 (4)
N40.0209 (5)0.0224 (6)0.0204 (5)0.0049 (4)0.0097 (4)0.0004 (4)
N50.0170 (5)0.0177 (5)0.0203 (5)0.0010 (4)0.0070 (4)0.0005 (4)
C10.0177 (5)0.0183 (6)0.0144 (5)−0.0009 (4)0.0088 (4)−0.0011 (4)
C20.0176 (5)0.0191 (6)0.0195 (6)0.0006 (5)0.0099 (5)−0.0033 (5)
C30.0161 (5)0.0174 (6)0.0194 (6)0.0029 (5)0.0081 (5)0.0005 (4)
C40.0194 (6)0.0174 (6)0.0158 (5)−0.0005 (5)0.0085 (4)−0.0005 (4)
C50.0169 (5)0.0185 (6)0.0160 (5)0.0001 (5)0.0085 (4)−0.0023 (4)
C60.0147 (5)0.0150 (6)0.0163 (5)−0.0019 (4)0.0070 (4)−0.0017 (4)
C70.0161 (5)0.0151 (6)0.0158 (5)−0.0009 (4)0.0081 (4)−0.0004 (4)
C80.0151 (5)0.0143 (5)0.0142 (5)−0.0009 (4)0.0068 (4)−0.0013 (4)
C90.0156 (5)0.0142 (6)0.0156 (5)−0.0007 (4)0.0062 (4)−0.0002 (4)
C100.0190 (6)0.0181 (6)0.0156 (5)−0.0011 (5)0.0093 (4)−0.0010 (4)
C110.0159 (5)0.0174 (6)0.0200 (6)−0.0012 (4)0.0096 (5)−0.0024 (4)
C120.0134 (5)0.0140 (6)0.0190 (6)0.0010 (4)0.0048 (4)0.0005 (4)
C130.0160 (5)0.0147 (6)0.0161 (5)−0.0009 (4)0.0072 (4)0.0000 (4)

Geometric parameters (Å, °)

O1—N31.2372 (15)C2—H2A0.93
O2—N31.2291 (15)C3—C41.4035 (18)
O3—N41.2262 (15)C4—C51.3711 (18)
O4—N41.2259 (15)C4—H4A0.93
O5—C91.3446 (15)C5—C61.4159 (17)
O5—H1O50.92 (3)C5—H5A0.93
O6—N51.2302 (15)C7—C81.4514 (17)
O7—N51.2288 (14)C7—H7A0.93
N1—C61.3565 (16)C8—C131.3962 (17)
N1—N21.3697 (15)C8—C91.4128 (16)
N1—H1N10.89 (2)C9—C101.4014 (18)
N2—C71.2920 (16)C10—C111.3799 (18)
N3—C11.4541 (16)C10—H10A0.93
N4—C31.4530 (17)C11—C121.3927 (17)
N5—C121.4589 (16)C11—H11A0.93
C1—C21.3876 (18)C12—C131.3795 (17)
C1—C61.4187 (17)C13—H13A0.93
C2—C31.3753 (17)
C9—O5—H1O5105.4 (15)C4—C5—H5A119.2
C6—N1—N2120.62 (11)C6—C5—H5A119.2
C6—N1—H1N1122.4 (13)N1—C6—C5120.57 (11)
N2—N1—H1N1116.6 (13)N1—C6—C1122.75 (11)
C7—N2—N1115.45 (10)C5—C6—C1116.66 (11)
O2—N3—O1122.71 (11)N2—C7—C8120.94 (11)
O2—N3—C1118.60 (11)N2—C7—H7A119.5
O1—N3—C1118.64 (11)C8—C7—H7A119.5
O4—N4—O3123.45 (12)C13—C8—C9118.32 (11)
O4—N4—C3118.12 (11)C13—C8—C7118.27 (11)
O3—N4—C3118.43 (11)C9—C8—C7123.37 (11)
O7—N5—O6123.08 (11)O5—C9—C10117.82 (11)
O7—N5—C12118.31 (11)O5—C9—C8121.85 (11)
O6—N5—C12118.60 (11)C10—C9—C8120.32 (11)
C2—C1—C6122.19 (11)C11—C10—C9120.67 (11)
C2—C1—N3116.05 (11)C11—C10—H10A119.7
C6—C1—N3121.76 (11)C9—C10—H10A119.7
C3—C2—C1118.67 (12)C10—C11—C12118.49 (12)
C3—C2—H2A120.7C10—C11—H11A120.8
C1—C2—H2A120.7C12—C11—H11A120.8
C2—C3—C4121.38 (12)C13—C12—C11122.02 (11)
C2—C3—N4119.01 (11)C13—C12—N5118.45 (11)
C4—C3—N4119.61 (11)C11—C12—N5119.53 (11)
C5—C4—C3119.51 (12)C12—C13—C8120.14 (11)
C5—C4—H4A120.2C12—C13—H13A119.9
C3—C4—H4A120.2C8—C13—H13A119.9
C4—C5—C6121.55 (12)
C6—N1—N2—C7172.84 (11)C2—C1—C6—C5−2.48 (18)
O2—N3—C1—C2−15.33 (17)N3—C1—C6—C5176.74 (11)
O1—N3—C1—C2162.33 (11)N1—N2—C7—C8175.64 (11)
O2—N3—C1—C6165.40 (12)N2—C7—C8—C13−174.24 (11)
O1—N3—C1—C6−16.94 (18)N2—C7—C8—C93.12 (19)
C6—C1—C2—C31.35 (19)C13—C8—C9—O5177.95 (11)
N3—C1—C2—C3−177.92 (11)C7—C8—C9—O50.58 (19)
C1—C2—C3—C40.5 (2)C13—C8—C9—C10−1.09 (18)
C1—C2—C3—N4−179.46 (11)C7—C8—C9—C10−178.46 (11)
O4—N4—C3—C2174.55 (13)O5—C9—C10—C11−176.95 (11)
O3—N4—C3—C2−5.12 (19)C8—C9—C10—C112.12 (19)
O4—N4—C3—C4−5.37 (19)C9—C10—C11—C12−1.25 (19)
O3—N4—C3—C4174.96 (13)C10—C11—C12—C13−0.63 (19)
C2—C3—C4—C5−1.0 (2)C10—C11—C12—N5179.16 (11)
N4—C3—C4—C5178.90 (11)O7—N5—C12—C13−4.77 (17)
C3—C4—C5—C6−0.22 (19)O6—N5—C12—C13174.17 (12)
N2—N1—C6—C52.89 (18)O7—N5—C12—C11175.44 (12)
N2—N1—C6—C1−175.04 (11)O6—N5—C12—C11−5.62 (18)
C4—C5—C6—N1−176.16 (12)C11—C12—C13—C81.65 (19)
C4—C5—C6—C11.89 (18)N5—C12—C13—C8−178.14 (11)
C2—C1—C6—N1175.52 (12)C9—C8—C13—C12−0.75 (18)
N3—C1—C6—N1−5.25 (19)C7—C8—C13—C12176.75 (11)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1N1···O4i0.89 (2)2.54 (2)3.0666 (15)118 (2)
N1—H1N1···O10.89 (2)2.07 (2)2.6477 (15)121 (2)
O5—H1O5···N20.92 (3)1.82 (3)2.6656 (14)150 (2)

Symmetry codes: (i) x+1/2, −y+5/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2567).

References

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