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Acta Crystallogr Sect E Struct Rep Online. 2010 April 1; 66(Pt 4): o976.
Published online 2010 March 31. doi:  10.1107/S1600536810011244
PMCID: PMC2983976

4-Nitro-N′-[(E)-3-pyridylmethyl­idene]benzohydrazide

Abstract

In the title moleclue, C13H10N4O3, the methyl­idene–hydrazide [–C(=O)—N—N=C–] fragment is essentially planar, with a maximum deviation of 0.0228 (7) Å. The mean planes of the benzene and pyridine rings make dihedral angles of 25.44 (6) and 5.47 (7)°, respectively, with the mean plane of the methyl­idene–hydrazide fragment. In the crystal structure, inter­molecular N—H(...)N hydrogen bonds link mol­ecules into chains along the b axis. Additional stabilization is provided by weak inter­molecular C—H(...)O hydrogen bonds. The O atoms of the nitro group are disordered over two sets of sites of equal occupancy.

Related literature

For the synthesis of related compounds, see: Zia-ur-Rehman et al. (2009 [triangle]). For the biological activity of benzohydrazides, see: Chakraborty & Patel (1996 [triangle]). For closely related structures, see: Raj et al. (2008 [triangle]); Fun et al. (2008 [triangle]); Wang et al. (2008 [triangle]); Qiu et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o976-scheme1.jpg

Experimental

Crystal data

  • C13H10N4O3
  • M r = 270.25
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o976-efi1.jpg
  • a = 14.6158 (3) Å
  • b = 8.1969 (2) Å
  • c = 10.3645 (2) Å
  • β = 100.609 (1)°
  • V = 1220.49 (5) Å3
  • Z = 4
  • Cu Kα radiation
  • μ = 0.91 mm−1
  • T = 123 K
  • 0.20 × 0.16 × 0.05 mm

Data collection

  • Bruker APEXII diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2004 [triangle]) T min = 0.839, T max = 0.956
  • 10114 measured reflections
  • 2192 independent reflections
  • 2098 reflections with I > 2σ(I)
  • R int = 0.016

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.094
  • S = 1.06
  • 2192 reflections
  • 190 parameters
  • 66 restraints
  • H-atom parameters constrained
  • Δρmax = 0.26 e Å−3
  • Δρmin = −0.26 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT and XPREP (Bruker, 2004 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810011244/lh5020sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810011244/lh5020Isup2.hkl

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

Acknowledgments

HLS is grateful to the Institute of Chemistry, University of the Punjab for financial support.

supplementary crystallographic information

Comment

Schiff bases are well known for their anti-bacterial, anti-oxidant, and anti-tumor activities (Zia-ur-Rehman et al., 2009). These are also considered as popular ligands in coordination chemistry due to their ease of synthesis and their ability to be readily modified both electronically and sterically (Chakraborty & Patel, 1996). We have synthesized a novel Schiff base, by the condensation of pyridine-3-carbaldehyde with p-nitrobenzohydrazide, and determined its crystal structure which is presented in this paper.

The structure of the title compound is presented in Fig. 1. The bond distances and angles agree with the cortresponding bond distances and angles reported in closely related compounds (Raj et al., 2008; Fun et al., 2008; Wang et al., 2008; Qiu et al., 2009). The methylidenehydrazide fragment C7/C8/N2/N3/O3 in the title compound is essentially planar with maximum deviation being 0.0228 (7) Å for both C7 and N2 atoms. The mean-planes of the benzene ring (C1–C6) and pyridine ring (C9–C13/N4) make dihedral angles of 25.44 (6) and 5.47 (7)°, respectively, with the mean-plane of the methylidene hydrazide fragment. The structure is stabilized by extensive hydrogen bonding; details have been provided in Table 1.

Experimental

A mixture of para-nitrobenzohydrazide (0.5 g, 2.76 mmoles), pyridine-3-carbaldehyde (0.26 ml, 2.76 mmoles), orthophosphoric acid (0.2 ml) and methanol (50.0 ml) was heated to reflux for a period of 3.5 hours followed by removal of the solvent under vacuum. The contents were allowed to cool and washed with cold methanol to yield the title compound. Crystals suitable for X-ray crystallographic studies were grown from a methanol solution of the title compound at room temperature by slow evaporation. Yield: 92%. M.p. 547 K.

Refinement

Though all the H atoms could be distinguished in the difference Fourier map the H-atoms bonded to C-atoms were included at geometrically idealized positions and refined in riding-model approximation with N—H = 0.88 Å and C—H = 0.95 Å; the Uiso(H) were allowed at 1.2Ueq(C/N). The final difference map was essentially featurless. The nitro group was disordered over two sites with N and O atoms occupying equal site occupancy factors, commands SIMU and EADP in SHELXL-97 (Sheldrick, 2008) were used to model the disorder.

Figures

Fig. 1.
The asymmetric unit of the title compound with the displacement ellipsoids plotted at 50% probability level (Farrugia, 1997); nitro group was disordered over two sites.

Crystal data

C13H10N4O3F(000) = 560
Mr = 270.25Dx = 1.471 Mg m3
Monoclinic, P21/cMelting point: 547 K
Hall symbol: -P 2ybcCu Kα radiation, λ = 1.54178 Å
a = 14.6158 (3) ÅCell parameters from 10114 reflections
b = 8.1969 (2) Åθ = 3.0–68.0°
c = 10.3645 (2) ŵ = 0.91 mm1
β = 100.609 (1)°T = 123 K
V = 1220.49 (5) Å3Plate, yellow
Z = 40.20 × 0.16 × 0.05 mm

Data collection

Bruker APEXII diffractometer2192 independent reflections
Radiation source: fine-focus sealed tube2098 reflections with I > 2σ(I)
graphiteRint = 0.016
ω and [var phi] scansθmax = 68.0°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2004)h = −17→17
Tmin = 0.839, Tmax = 0.956k = −9→9
10114 measured reflectionsl = −12→12

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)] = 0.036Hydrogen site location: difference Fourier map
wR(F2) = 0.094H-atom parameters constrained
S = 1.06w = 1/[σ2(Fo2) + (0.0485P)2 + 0.519P] where P = (Fo2 + 2Fc2)/3
2192 reflections(Δ/σ)max = 0.001
190 parametersΔρmax = 0.26 e Å3
66 restraintsΔρmin = −0.26 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 > σ(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)
N1−0.0353 (11)0.277 (2)0.3850 (9)0.0354 (16)0.50
O1−0.086 (3)0.336 (5)0.295 (3)0.059 (3)0.50
O2−0.0552 (6)0.1587 (11)0.4450 (5)0.0550 (12)0.50
N1'−0.0292 (11)0.259 (2)0.4237 (9)0.0354 (16)0.50
O1'−0.082 (3)0.311 (5)0.321 (3)0.059 (3)0.50
O2'−0.0525 (6)0.1572 (11)0.4997 (5)0.0550 (12)0.50
O30.36776 (6)0.53420 (11)0.67517 (8)0.0267 (2)
N20.37145 (6)0.60961 (12)0.46461 (9)0.0179 (2)
H2N0.34420.60310.38170.022*
N30.45517 (6)0.69107 (12)0.49965 (9)0.0183 (2)
N40.66815 (7)1.02086 (12)0.31200 (10)0.0203 (2)
C10.23641 (8)0.46958 (15)0.51171 (12)0.0203 (3)
C20.17661 (9)0.52595 (17)0.40038 (13)0.0261 (3)
H20.19650.60960.34840.031*
C30.08809 (9)0.46038 (19)0.36515 (14)0.0329 (3)
H30.04660.49880.28980.040*
C40.06168 (9)0.33806 (18)0.44215 (16)0.0352 (4)
C50.11925 (10)0.27997 (17)0.55309 (16)0.0361 (4)
H50.09920.19530.60400.043*
C60.20687 (9)0.34797 (16)0.58836 (14)0.0280 (3)
H60.24720.31140.66550.034*
C70.33183 (8)0.54003 (14)0.55923 (11)0.0189 (3)
C80.48376 (8)0.75796 (14)0.40288 (11)0.0182 (3)
H80.44900.74300.31680.022*
C90.56840 (8)0.85680 (14)0.42110 (11)0.0179 (3)
C100.59341 (8)0.92553 (15)0.30967 (11)0.0191 (3)
H100.55520.90350.22700.023*
C110.72083 (8)1.05187 (15)0.42965 (12)0.0212 (3)
H110.77441.11860.43340.025*
C120.70067 (8)0.99095 (15)0.54626 (12)0.0219 (3)
H120.73951.01680.62770.026*
C130.62364 (8)0.89241 (15)0.54267 (11)0.0201 (3)
H130.60850.84970.62130.024*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0219 (18)0.035 (3)0.051 (5)−0.0047 (17)0.010 (4)−0.013 (4)
O10.027 (3)0.086 (9)0.059 (8)−0.015 (4)−0.004 (5)−0.022 (6)
O20.0311 (8)0.0435 (8)0.093 (4)−0.0147 (6)0.018 (3)0.007 (3)
N1'0.0219 (18)0.035 (3)0.051 (5)−0.0047 (17)0.010 (4)−0.013 (4)
O1'0.027 (3)0.086 (9)0.059 (8)−0.015 (4)−0.004 (5)−0.022 (6)
O2'0.0311 (8)0.0435 (8)0.093 (4)−0.0147 (6)0.018 (3)0.007 (3)
O30.0277 (5)0.0329 (5)0.0186 (4)−0.0062 (4)0.0022 (3)0.0030 (4)
N20.0158 (5)0.0208 (5)0.0168 (5)−0.0024 (4)0.0021 (4)−0.0006 (4)
N30.0156 (5)0.0187 (5)0.0205 (5)−0.0013 (4)0.0030 (4)−0.0014 (4)
N40.0184 (5)0.0215 (5)0.0215 (5)0.0005 (4)0.0053 (4)0.0010 (4)
C10.0192 (6)0.0194 (6)0.0240 (6)−0.0001 (4)0.0080 (5)−0.0052 (5)
C20.0207 (6)0.0318 (7)0.0263 (6)−0.0023 (5)0.0058 (5)−0.0034 (5)
C30.0207 (6)0.0429 (8)0.0345 (7)−0.0011 (6)0.0032 (5)−0.0121 (6)
C40.0184 (6)0.0315 (7)0.0579 (9)−0.0057 (5)0.0130 (6)−0.0211 (7)
C50.0293 (7)0.0217 (7)0.0631 (10)−0.0037 (5)0.0234 (7)−0.0006 (7)
C60.0252 (6)0.0227 (6)0.0387 (7)0.0003 (5)0.0126 (5)0.0015 (6)
C70.0197 (6)0.0167 (6)0.0206 (6)0.0005 (4)0.0045 (4)−0.0013 (5)
C80.0178 (5)0.0181 (6)0.0182 (5)0.0010 (4)0.0021 (4)−0.0005 (4)
C90.0170 (6)0.0163 (6)0.0206 (6)0.0023 (4)0.0040 (4)−0.0012 (4)
C100.0180 (6)0.0196 (6)0.0193 (6)0.0012 (4)0.0024 (4)−0.0013 (5)
C110.0161 (5)0.0207 (6)0.0271 (6)−0.0016 (4)0.0045 (5)−0.0013 (5)
C120.0198 (6)0.0235 (6)0.0212 (6)−0.0003 (5)0.0008 (5)−0.0029 (5)
C130.0208 (6)0.0210 (6)0.0191 (6)0.0016 (5)0.0050 (5)0.0004 (5)

Geometric parameters (Å, °)

N1—O11.19 (3)C2—H20.9500
N1—O21.213 (16)C3—C41.380 (2)
N1—C41.518 (16)C3—H30.9500
N1'—O2'1.236 (15)C4—C51.379 (2)
N1'—O1'1.27 (2)C5—C61.383 (2)
N1'—C41.460 (17)C5—H50.9500
O3—C71.2205 (15)C6—H60.9500
N2—C71.3532 (15)C8—C91.4617 (16)
N2—N31.3826 (13)C8—H80.9500
N2—H2N0.8800C9—C101.3929 (16)
N3—C81.2788 (15)C9—C131.3964 (16)
N4—C101.3397 (16)C10—H100.9500
N4—C111.3411 (16)C11—C121.3886 (17)
C1—C61.3919 (18)C11—H110.9500
C1—C21.3920 (18)C12—C131.3806 (17)
C1—C71.5061 (16)C12—H120.9500
C2—C31.3865 (18)C13—H130.9500
O1—N1—O2124 (2)C4—C5—H5120.8
O1—N1—C4125 (2)C6—C5—H5120.8
O2—N1—C4111.0 (8)C5—C6—C1120.48 (13)
O2'—N1'—O1'125 (2)C5—C6—H6119.8
O2'—N1'—C4124.5 (9)C1—C6—H6119.8
O1'—N1'—C4111 (2)O3—C7—N2124.48 (11)
C7—N2—N3119.29 (9)O3—C7—C1120.77 (11)
C7—N2—H2N120.4N2—C7—C1114.75 (10)
N3—N2—H2N120.4N3—C8—C9121.82 (10)
C8—N3—N2113.72 (9)N3—C8—H8119.1
C10—N4—C11117.17 (10)C9—C8—H8119.1
C6—C1—C2119.84 (12)C10—C9—C13117.86 (11)
C6—C1—C7116.99 (11)C10—C9—C8117.52 (10)
C2—C1—C7123.10 (11)C13—C9—C8124.57 (11)
C3—C2—C1120.18 (13)N4—C10—C9123.95 (11)
C3—C2—H2119.9N4—C10—H10118.0
C1—C2—H2119.9C9—C10—H10118.0
C4—C3—C2118.43 (14)N4—C11—C12123.02 (11)
C4—C3—H3120.8N4—C11—H11118.5
C2—C3—H3120.8C12—C11—H11118.5
C5—C4—C3122.72 (12)C13—C12—C11119.31 (11)
C5—C4—N1'110.9 (4)C13—C12—H12120.3
C3—C4—N1'126.3 (4)C11—C12—H12120.3
C5—C4—N1126.4 (4)C12—C13—C9118.67 (11)
C3—C4—N1110.8 (4)C12—C13—H13120.7
C4—C5—C6118.33 (13)C9—C13—H13120.7
C7—N2—N3—C8−177.02 (10)N1—C4—C5—C6178.1 (7)
C6—C1—C2—C3−0.52 (19)C4—C5—C6—C1−1.3 (2)
C7—C1—C2—C3−177.23 (11)C2—C1—C6—C51.50 (19)
C1—C2—C3—C4−0.57 (19)C7—C1—C6—C5178.40 (11)
C2—C3—C4—C50.7 (2)N3—N2—C7—O3−5.01 (17)
C2—C3—C4—N1'177.6 (8)N3—N2—C7—C1174.08 (9)
C2—C3—C4—N1−177.4 (6)C6—C1—C7—O3−23.95 (17)
O2'—N1'—C4—C52.3 (16)C2—C1—C7—O3152.85 (12)
O1'—N1'—C4—C5−180 (2)C6—C1—C7—N2156.92 (11)
O2'—N1'—C4—C3−174.9 (10)C2—C1—C7—N2−26.28 (17)
O1'—N1'—C4—C33(3)N2—N3—C8—C9176.74 (10)
O2'—N1'—C4—N1168 (6)N3—C8—C9—C10−179.54 (11)
O1'—N1'—C4—N1−14 (4)N3—C8—C9—C13−2.28 (18)
O1—N1—C4—C5174 (3)C11—N4—C10—C9−0.60 (17)
O2—N1—C4—C5−4.7 (15)C13—C9—C10—N41.38 (18)
O1—N1—C4—C3−8(3)C8—C9—C10—N4178.82 (10)
O2—N1—C4—C3173.3 (9)C10—N4—C11—C12−0.44 (17)
O1—N1—C4—N1'158 (7)N4—C11—C12—C130.65 (18)
O2—N1—C4—N1'−21 (4)C11—C12—C13—C90.17 (18)
C3—C4—C5—C60.2 (2)C10—C9—C13—C12−1.11 (17)
N1'—C4—C5—C6−177.1 (7)C8—C9—C13—C12−178.35 (11)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2N···N4i0.882.092.9108 (14)154
C3—H3···O10.952.372.72 (4)101
C5—H5···O2'0.952.302.666 (8)102
C8—H8···O3ii0.952.503.1423 (14)125
C11—H11···O2iii0.952.493.364 (8)152
C11—H11···O2'iii0.952.523.371 (8)150
C13—H13···O3iv0.952.573.1279 (14)118

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y+3/2, z−1/2; (iii) x+1, y+1, z; (iv) −x+1, y+1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH5020).

References

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