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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o2050.
Published online 2009 July 31. doi:  10.1107/S1600536809029705
PMCID: PMC2977219

(E)-N′-(3,4-Dihydroxy­benzyl­idene)-4-nitro­benzohydrazide

Abstract

In the title Schiff base compound, C14H11N3O5, the dihedral angle between the two benzene rings is 1.6 (1)°. The mol­ecule displays an E configuration about the C=N bond. An intra­molecular O—H(...)O hydrogen bond is observed. In the crystal, mol­ecules are linked into layers parallel to (101) by O—H(...)O, N—H(...)O and C—H(...)O hydrogen bonds. One of the hydroxyl groups is disordered over two positions, with occupancies of 0.643 (5) and 0.357 (5).

Related literature

For the biological properties of Schiff base compounds, see: Kucukguzel et al. (2006 [triangle]); Khattab (2005 [triangle]); Karthikeyan et al. (2006 [triangle]); Okabe et al. (1993 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]). For related structures, see: Shan et al. (2008 [triangle]); Fun et al. (2008 [triangle]); Yang (2008 [triangle]); Ma et al. (2008 [triangle]); Diao et al. (2008a [triangle],b [triangle]); Ejsmont et al. (2008 [triangle]); Qiu & Zhao (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2050-scheme1.jpg

Experimental

Crystal data

  • C14H11N3O5
  • M r = 301.26
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2050-efi1.jpg
  • a = 7.666 (1) Å
  • b = 13.196 (2) Å
  • c = 13.176 (2) Å
  • β = 95.361 (3)°
  • V = 1327.1 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 298 K
  • 0.20 × 0.20 × 0.18 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.977, T max = 0.979
  • 8322 measured reflections
  • 3204 independent reflections
  • 1364 reflections with I > 2σ(I)
  • R int = 0.056

Refinement

  • R[F 2 > 2σ(F 2)] = 0.069
  • wR(F 2) = 0.161
  • S = 1.02
  • 3204 reflections
  • 210 parameters
  • 2 restraints
  • H-atom parameters constrained
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: SMART (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; 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.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809029705/ci2865sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029705/ci2865Isup2.hkl

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

supplementary crystallographic information

Comment

Hydrazones and Schiff bases have been attracted much attention for their excellent biological properties, especially for their potential pharmacological and antitumor properties (Kucukguzel et al., 2006; Khattab et al., 2005; Karthikeyan et al., 2006; Okabe et al., 1993). Recently, a large number of hydrazone derivatives have been prepared and structurally characterized (Shan et al., 2008; Fun et al., 2008; Yang, 2008; Ma et al., 2008; Diao et al., 2008a,b; Ejsmont et al., 2008). As part of the ongoing study (Qiu & Zhao, 2008), we report herein the crystal structure of the title compound.

The molecular structure of the title compound is shown in Fig. 1. The bond distances (Allen et al., 1987) and angles are normal. The dihedral angle between the two benzene rings is 1.6 (1)°. The displays an E configuration about the C═N bond. The nitro group is almost coplanar with the attached benzene ring [O4—N1—C1—C6 = -3.5 (5)° and O5—N1—C1—C2 = -3.1 (5)°].

The molecules are linked into layers parallel to the (101) by O—H···O, N—H···O and C—H···O hydrogen bonds (Fig. 2 and Table 1).

Experimental

3,4-Dihydroxybenzaldehyde (1.0 mmol, 138.1 mg) was dissolved in methanol (50 ml), then 4-nitrobenzohydrazide (1.0 mmol, 181.2 mg) was added slowly into the solution, and the mixture was kept at reflux with continuous stirring for 3 h. After the solution had cooled to room temperature colourless tiny crystals appeared. The tiny crystals were filtered and washed with methanol for three times. Recrystallization from an absolute methanol yielded block-shaped single crystals of the title compound.

Refinement

One of the hydroxyl groups (O3) is disordered over two distinct sites, with occupancies of 0.643 (5) and 0.357 (5). The C—O distances of the two disorder components were restrained to 1.36 (1) Å. H atoms were placed in calculated positions [O-H = 0.82 Å, N-H = 0.90 Å and C-H = 0.93 Å] and refined using a riding model, with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O).

Figures

Fig. 1.
The molecular structure of the title compound with 30% probability displacement ellipsoids for non-H atoms. Only the major disorder component of a hydroxyl group is shown.
Fig. 2.
Molecular packing as viewed along the a axis. O—H···O and N—H···O hydrogen bonds are shown as dashed lines.

Crystal data

C14H11N3O5F(000) = 624
Mr = 301.26Dx = 1.508 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1038 reflections
a = 7.666 (1) Åθ = 2.5–24.5°
b = 13.196 (2) ŵ = 0.12 mm1
c = 13.176 (2) ÅT = 298 K
β = 95.361 (3)°Block, colourless
V = 1327.1 (3) Å30.20 × 0.20 × 0.18 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer3204 independent reflections
Radiation source: fine-focus sealed tube1364 reflections with I > 2σ(I)
graphiteRint = 0.056
ω scansθmax = 28.3°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −10→10
Tmin = 0.977, Tmax = 0.979k = −16→17
8322 measured reflectionsl = −17→10

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.069Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.161H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.0491P)2 + 0.4176P] where P = (Fo2 + 2Fc2)/3
3204 reflections(Δ/σ)max = 0.001
210 parametersΔρmax = 0.17 e Å3
2 restraintsΔρmin = −0.23 e Å3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

xyzUiso*/UeqOcc. (<1)
O10.6818 (3)1.15446 (15)0.09056 (17)0.0606 (6)
O20.5123 (3)0.56081 (15)0.27427 (16)0.0661 (7)
H2A0.45200.58250.31770.099*
O30.6235 (5)0.5128 (2)0.0971 (3)0.0814 (15)0.643 (5)
H3A0.60130.47820.14600.122*0.643 (5)
O41.0449 (3)1.43595 (18)−0.3087 (2)0.0749 (7)
O50.9668 (4)1.5401 (2)−0.1968 (2)0.1037 (10)
N10.9797 (4)1.4543 (2)−0.2301 (2)0.0648 (8)
N20.7625 (3)1.03529 (18)−0.01803 (18)0.0508 (7)
H2B0.78951.0090−0.07780.061*
N30.7082 (3)0.9614 (2)0.04686 (19)0.0524 (7)
C10.9174 (4)1.3697 (2)−0.1705 (2)0.0513 (8)
C20.8561 (4)1.3914 (2)−0.0783 (3)0.0601 (9)
H20.85171.4579−0.05520.072*
C30.8013 (4)1.3123 (2)−0.0209 (2)0.0572 (9)
H30.75991.32550.04190.069*
C40.8072 (4)1.2134 (2)−0.0558 (2)0.0438 (7)
C50.8690 (4)1.1948 (2)−0.1500 (2)0.0521 (8)
H50.87231.1288−0.17450.063*
C60.9252 (4)1.2736 (2)−0.2070 (2)0.0558 (9)
H60.96791.2613−0.26960.067*
C70.7446 (4)1.1325 (2)0.0104 (2)0.0475 (8)
C80.7224 (4)0.8695 (2)0.0199 (2)0.0501 (8)
H80.76550.8536−0.04180.060*
C90.6702 (4)0.7893 (2)0.0869 (2)0.0468 (8)
C100.6126 (4)0.8135 (2)0.1810 (2)0.0522 (9)
H100.60940.88110.20080.063*
C110.5601 (4)0.7403 (2)0.2447 (2)0.0544 (9)
H110.52320.75820.30760.065*0.643 (5)
C120.5617 (4)0.6395 (2)0.2157 (2)0.0480 (8)
C130.6193 (4)0.6140 (2)0.1230 (2)0.0532 (8)
H130.62240.54640.10340.064*0.357 (5)
C140.6724 (4)0.6884 (2)0.0591 (2)0.0522 (9)
H140.71030.6705−0.00340.063*
O3'0.5167 (10)0.7811 (5)0.3302 (5)0.076 (3)0.357 (5)
H3'0.42250.75790.34390.115*0.357 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0805 (16)0.0506 (14)0.0549 (14)0.0031 (12)0.0283 (12)−0.0007 (11)
O20.0902 (17)0.0484 (14)0.0645 (15)0.0031 (12)0.0320 (13)0.0033 (11)
O30.140 (4)0.037 (2)0.073 (3)0.005 (2)0.046 (2)−0.0088 (18)
O40.0773 (17)0.0780 (18)0.0740 (18)−0.0035 (14)0.0315 (14)0.0168 (14)
O50.155 (3)0.0525 (17)0.111 (2)−0.0188 (18)0.056 (2)0.0086 (16)
N10.072 (2)0.052 (2)0.072 (2)−0.0078 (16)0.0208 (17)0.0113 (17)
N20.0662 (18)0.0403 (16)0.0484 (16)−0.0003 (13)0.0187 (14)−0.0016 (13)
N30.0616 (17)0.0433 (16)0.0541 (16)−0.0017 (13)0.0149 (14)0.0068 (13)
C10.052 (2)0.051 (2)0.053 (2)0.0002 (16)0.0145 (17)0.0112 (16)
C20.072 (2)0.043 (2)0.068 (2)0.0001 (17)0.022 (2)−0.0005 (18)
C30.067 (2)0.051 (2)0.056 (2)0.0041 (18)0.0228 (18)−0.0038 (17)
C40.0455 (18)0.0404 (19)0.0466 (19)0.0010 (14)0.0104 (15)0.0028 (15)
C50.066 (2)0.0407 (19)0.053 (2)0.0041 (16)0.0205 (17)0.0017 (15)
C60.062 (2)0.056 (2)0.052 (2)0.0038 (17)0.0179 (17)0.0021 (17)
C70.0461 (19)0.049 (2)0.048 (2)0.0023 (15)0.0087 (16)−0.0006 (16)
C80.054 (2)0.047 (2)0.051 (2)0.0012 (16)0.0123 (16)0.0010 (16)
C90.0479 (19)0.0414 (19)0.052 (2)−0.0001 (15)0.0093 (16)0.0005 (16)
C100.064 (2)0.0330 (18)0.062 (2)−0.0018 (15)0.0148 (18)−0.0035 (15)
C110.066 (2)0.047 (2)0.052 (2)0.0009 (17)0.0120 (18)−0.0043 (17)
C120.056 (2)0.0382 (19)0.052 (2)−0.0007 (15)0.0152 (17)0.0068 (15)
C130.062 (2)0.0387 (19)0.060 (2)0.0011 (16)0.0156 (18)−0.0049 (17)
C140.057 (2)0.050 (2)0.052 (2)0.0006 (16)0.0160 (17)−0.0035 (16)
O3'0.116 (7)0.066 (5)0.053 (4)−0.018 (4)0.040 (4)−0.011 (3)

Geometric parameters (Å, °)

O1—C71.236 (3)C4—C71.487 (4)
O2—C121.367 (3)C5—C61.375 (4)
O2—H2A0.82C5—H50.93
O3—C131.379 (4)C6—H60.93
O3—H3A0.82C8—C91.458 (4)
O4—N11.216 (3)C8—H80.93
O5—N11.221 (3)C9—C141.382 (4)
N1—C11.469 (4)C9—C101.390 (4)
N2—C71.346 (4)C10—C111.365 (4)
N2—N31.386 (3)C10—H100.93
N2—H2B0.90C11—O3'1.319 (5)
N3—C81.271 (3)C11—C121.385 (4)
C1—C61.360 (4)C11—H110.93
C1—C21.373 (4)C12—C131.380 (4)
C2—C31.377 (4)C13—C141.379 (4)
C2—H20.93C13—H130.93
C3—C41.387 (4)C14—H140.93
C3—H30.93O3'—H3'0.82
C4—C51.390 (4)
C12—O2—H2A109.5O1—C7—C4120.4 (3)
C13—O3—H3A109.5N2—C7—C4118.3 (3)
O4—N1—O5123.0 (3)N3—C8—C9119.2 (3)
O4—N1—C1118.9 (3)N3—C8—H8120.4
O5—N1—C1118.1 (3)C9—C8—H8120.4
C7—N2—N3117.0 (2)C14—C9—C10118.1 (3)
C7—N2—H2B130.3C14—C9—C8121.8 (3)
N3—N2—H2B112.0C10—C9—C8120.1 (3)
C8—N3—N2117.4 (3)C11—C10—C9121.5 (3)
C6—C1—C2122.4 (3)C11—C10—H10119.2
C6—C1—N1119.5 (3)C9—C10—H10119.2
C2—C1—N1118.0 (3)O3'—C11—C10110.5 (4)
C1—C2—C3118.4 (3)O3'—C11—C12129.6 (4)
C1—C2—H2120.8C10—C11—C12119.9 (3)
C3—C2—H2120.8C10—C11—H11120.0
C2—C3—C4120.7 (3)C12—C11—H11120.0
C2—C3—H3119.7O2—C12—C13116.3 (3)
C4—C3—H3119.7O2—C12—C11124.3 (3)
C3—C4—C5119.1 (3)C13—C12—C11119.4 (3)
C3—C4—C7117.4 (3)C14—C13—O3121.6 (3)
C5—C4—C7123.5 (3)C14—C13—C12120.3 (3)
C6—C5—C4120.3 (3)O3—C13—C12118.1 (3)
C6—C5—H5119.9C14—C13—H13119.8
C4—C5—H5119.9C12—C13—H13119.8
C1—C6—C5119.1 (3)C13—C14—C9120.8 (3)
C1—C6—H6120.4C13—C14—H14119.6
C5—C6—H6120.4C9—C14—H14119.5
O1—C7—N2121.3 (3)C11—O3'—H3'109.5
C7—N2—N3—C8179.0 (3)C5—C4—C7—N25.9 (4)
O4—N1—C1—C6−3.5 (5)N2—N3—C8—C9178.7 (3)
O5—N1—C1—C6178.1 (3)N3—C8—C9—C14176.0 (3)
O4—N1—C1—C2175.3 (3)N3—C8—C9—C10−2.7 (5)
O5—N1—C1—C2−3.1 (5)C14—C9—C10—C110.2 (5)
C6—C1—C2—C30.2 (5)C8—C9—C10—C11178.9 (3)
N1—C1—C2—C3−178.5 (3)C9—C10—C11—O3'178.0 (4)
C1—C2—C3—C4−0.3 (5)C9—C10—C11—C12−0.7 (5)
C2—C3—C4—C5−0.2 (5)O3'—C11—C12—O21.3 (7)
C2—C3—C4—C7−179.6 (3)C10—C11—C12—O2179.7 (3)
C3—C4—C5—C60.7 (5)O3'—C11—C12—C13−177.4 (5)
C7—C4—C5—C6−179.8 (3)C10—C11—C12—C131.1 (5)
C2—C1—C6—C50.3 (5)O2—C12—C13—C14−179.8 (3)
N1—C1—C6—C5179.1 (3)C11—C12—C13—C14−1.0 (5)
C4—C5—C6—C1−0.8 (5)O2—C12—C13—O3−0.3 (5)
N3—N2—C7—O1−0.3 (4)C11—C12—C13—O3178.5 (3)
N3—N2—C7—C4178.0 (2)O3—C13—C14—C9−178.9 (3)
C3—C4—C7—O13.6 (4)C12—C13—C14—C90.5 (5)
C5—C4—C7—O1−175.8 (3)C10—C9—C14—C13−0.1 (5)
C3—C4—C7—N2−174.6 (3)C8—C9—C14—C13−178.8 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H3A···O20.822.172.636 (4)116
O2—H2A···O1i0.821.912.722 (3)171
O3'—H3'···O1i0.821.842.548 (7)144
N2—H2B···O4ii0.902.263.121 (3)158
C5—H5···O5ii0.932.483.210 (4)135
C10—H10···O2iii0.932.583.467 (3)159
C11—H11···O1i0.932.563.192 (4)126

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2865).

References

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