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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1531.
Published online 2008 July 19. doi:  10.1107/S1600536808021429
PMCID: PMC2962156

1-(4-Nitro­phen­yl)-2-(3-phenyl­allyl­idene)hydrazine

Abstract

In the title compound, C15H13N3O2, the nitro­benzene and benzene rings make a dihedral angle of 9.1 (2)°. The crystal structure is consolidated by inter­molecular N—H(...)O hydrogen bonds.

Related literature

For related literature, see: Okabe et al. (1993 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1531-scheme1.jpg

Experimental

Crystal data

  • C15H13N3O2
  • M r = 267.28
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1531-efi1.jpg
  • a = 6.1011 (3) Å
  • b = 12.4505 (6) Å
  • c = 9.0076 (4) Å
  • β = 93.273 (3)°
  • V = 683.12 (6) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 296 (2) K
  • 0.23 × 0.20 × 0.20 mm

Data collection

  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.980, T max = 0.982
  • 5992 measured reflections
  • 1502 independent reflections
  • 783 reflections with I > 2σ(I)
  • R int = 0.045

Refinement

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.101
  • S = 0.94
  • 1502 reflections
  • 185 parameters
  • 3 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.09 e Å−3
  • Δρmin = −0.10 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT (Bruker, 1998 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); 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/S1600536808021429/hg2421sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808021429/hg2421Isup2.hkl

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

supplementary crystallographic information

Comment

4-Nitrophenylhydrazine has applications in organic synthesis and some of its derivatives have been shown to be potentially DNA-damaging and mutagenic agents (Okabe et al., 1993). As part of our interest in the study of the coordination chemistry, we report the synthesis and crystal structure of the title compound (I).

The 4-nitrophenyl group and the benzene ring are slightly twisted, making a dihedral angle of 9.1 (2)°. The dihedral angle between the N1/O1/O2 and its attached benzene ring is 7.4 (2)° (Fig. 1).

The molecules are linked by N—H···O hydrogen bonds to form a zigzag like chain (Fig. 2).

Experimental

4-Nitrophenylhydrazine (1 mmol, 0.153 g) was dissolved in anhydrous methanol and H2SO4 (98% 0.5 ml) was added. The resultant solution was stirred for several minutes at 351 K. Cinnamaldehyde (1 mmol 0.132 g) in methanol (8 ml) was added dropwise and the mixture was stirred at refluxing temperature for 2 h. The product was isolated and recrystallized in dichloromethane. Brown single crystals of (I) were obtained after 6 d.

Refinement

All H atoms were placed in calculated positions, with C—H = 0.93Å (aromatic) with Uiso(H) = 1.2Ueq(C). H2A was located from a difference Fourier map and refined isotropically, with N–H distance restrained to 0.89 (3)Å.

Figures

Fig. 1.
the ORTEP plot of (I). Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as small spheres of arbitrary radii.
Fig. 2.
Packing of (I), showing the intermolecular hydrogen bonds as dashed lines.

Crystal data

C15H13N3O2F000 = 280
Mr = 267.28Dx = 1.299 Mg m3
Monoclinic, PcMo Kα radiation λ = 0.71073 Å
Hall symbol: P -2ycCell parameters from 1143 reflections
a = 6.1011 (3) Åθ = 2.1–25.6º
b = 12.4505 (6) ŵ = 0.09 mm1
c = 9.0076 (4) ÅT = 296 (2) K
β = 93.273 (3)ºBlock, brown
V = 683.12 (6) Å30.23 × 0.20 × 0.20 mm
Z = 2

Data collection

Bruker SMART APEX CCD area-detector diffractometer1502 independent reflections
Radiation source: sealed tube783 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.045
T = 296(2) Kθmax = 27.0º
[var phi] and ω scansθmin = 1.6º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −7→7
Tmin = 0.980, Tmax = 0.982k = −14→15
5992 measured reflectionsl = −11→11

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.101  w = 1/[σ2(Fo2) + (0.0488P)2] where P = (Fo2 + 2Fc2)/3
S = 0.95(Δ/σ)max < 0.001
1502 reflectionsΔρmax = 0.09 e Å3
185 parametersΔρmin = −0.10 e Å3
3 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.027 (6)

Special details

Geometry. 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.
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*/Ueq
O11.0954 (5)0.9273 (2)−0.0961 (4)0.1019 (9)
O21.0374 (5)1.0780 (3)0.0100 (3)0.1053 (11)
N10.9922 (5)0.9832 (3)−0.0132 (3)0.0768 (9)
N20.2734 (4)0.8124 (2)0.2572 (3)0.0689 (8)
N30.1907 (4)0.7139 (2)0.2171 (3)0.0718 (8)
C10.8094 (5)0.9377 (3)0.0590 (4)0.0595 (8)
C20.7374 (5)0.8364 (3)0.0209 (4)0.0663 (10)
H20.80960.7967−0.04880.080*
C30.5603 (5)0.7940 (3)0.0852 (4)0.0644 (9)
H30.51160.72550.05850.077*
C40.4516 (5)0.8519 (3)0.1903 (4)0.0593 (8)
C50.5270 (6)0.9545 (3)0.2290 (4)0.0689 (10)
H50.45670.99410.29980.083*
C60.7040 (5)0.9972 (3)0.1631 (4)0.0695 (9)
H60.75321.06590.18820.083*
C70.0126 (6)0.6853 (3)0.2753 (4)0.0717 (9)
H7−0.05110.73050.34290.086*
C8−0.0884 (6)0.5852 (3)0.2375 (4)0.0742 (10)
H8−0.01700.53930.17470.089*
C9−0.2781 (6)0.5539 (3)0.2868 (4)0.0757 (10)
H9−0.34430.60170.34970.091*
C10−0.3973 (6)0.4540 (3)0.2553 (4)0.0781 (11)
C11−0.3260 (8)0.3749 (4)0.1614 (5)0.0973 (13)
H11−0.19190.38270.11840.117*
C12−0.4506 (11)0.2854 (4)0.1313 (6)0.1188 (19)
H12−0.40120.23380.06640.143*
C13−0.6461 (12)0.2703 (5)0.1945 (7)0.128 (2)
H13−0.73000.20940.17240.153*
C14−0.7170 (8)0.3456 (5)0.2905 (7)0.1205 (19)
H14−0.84790.33460.33630.145*
C15−0.5968 (7)0.4385 (4)0.3210 (5)0.0968 (13)
H15−0.64880.49010.38490.116*
H2A0.205 (5)0.852 (2)0.323 (3)0.080*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0786 (17)0.127 (2)0.1032 (19)−0.0004 (17)0.0351 (16)−0.0009 (18)
O20.104 (2)0.104 (2)0.109 (2)−0.040 (2)0.0197 (18)−0.0008 (18)
N10.068 (2)0.094 (3)0.0691 (19)−0.012 (2)0.0059 (17)0.008 (2)
N20.0610 (19)0.070 (2)0.077 (2)−0.0064 (16)0.0103 (16)−0.0075 (15)
N30.0674 (19)0.0658 (19)0.082 (2)−0.0096 (16)0.0027 (17)0.0023 (16)
C10.0512 (18)0.070 (2)0.0578 (19)−0.0043 (18)0.0033 (16)0.0044 (17)
C20.069 (2)0.069 (2)0.062 (2)0.0083 (19)0.0106 (19)−0.0015 (18)
C30.062 (2)0.055 (2)0.076 (2)0.0008 (18)0.0037 (19)−0.0048 (19)
C40.0539 (19)0.064 (2)0.0598 (19)−0.0012 (17)0.0007 (17)0.0004 (17)
C50.061 (2)0.072 (2)0.074 (2)−0.0022 (18)0.0110 (19)−0.0102 (19)
C60.067 (2)0.065 (2)0.076 (2)−0.011 (2)0.0021 (19)−0.0015 (19)
C70.062 (2)0.075 (2)0.077 (2)−0.007 (2)0.0044 (19)0.0044 (19)
C80.074 (2)0.068 (2)0.080 (3)−0.008 (2)0.000 (2)0.0086 (19)
C90.077 (3)0.074 (2)0.076 (2)−0.016 (2)−0.003 (2)0.0047 (19)
C100.073 (3)0.080 (3)0.079 (3)−0.018 (2)−0.014 (2)0.018 (2)
C110.123 (3)0.086 (3)0.082 (3)−0.024 (3)−0.002 (3)−0.001 (2)
C120.169 (6)0.082 (3)0.102 (4)−0.034 (4)−0.022 (4)0.011 (3)
C130.157 (6)0.098 (4)0.122 (4)−0.061 (4)−0.042 (4)0.025 (4)
C140.096 (3)0.119 (4)0.144 (5)−0.045 (4)−0.022 (3)0.045 (4)
C150.077 (3)0.093 (3)0.119 (3)−0.014 (3)−0.009 (3)0.019 (2)

Geometric parameters (Å, °)

O1—N11.221 (4)C7—C81.423 (5)
O2—N11.228 (4)C7—H70.9300
N1—C11.438 (4)C8—C91.322 (5)
N2—C41.365 (4)C8—H80.9300
N2—N31.366 (4)C9—C101.461 (5)
N2—H2A0.89 (3)C9—H90.9300
N3—C71.284 (4)C10—C111.384 (6)
C1—C21.373 (4)C10—C151.397 (5)
C1—C61.382 (4)C11—C121.368 (6)
C2—C31.361 (4)C11—H110.9300
C2—H20.9300C12—C131.364 (8)
C3—C41.388 (4)C12—H120.9300
C3—H30.9300C13—C141.362 (8)
C4—C51.396 (4)C13—H130.9300
C5—C61.369 (4)C14—C151.389 (7)
C5—H50.9300C14—H140.9300
C6—H60.9300C15—H150.9300
O1—N1—O2122.2 (3)N3—C7—H7119.7
O1—N1—C1119.5 (4)C8—C7—H7119.7
O2—N1—C1118.3 (3)C9—C8—C7123.6 (4)
C4—N2—N3119.9 (3)C9—C8—H8118.2
C4—N2—H2A120 (2)C7—C8—H8118.2
N3—N2—H2A120 (2)C8—C9—C10128.4 (4)
C7—N3—N2116.7 (3)C8—C9—H9115.8
C2—C1—C6120.5 (3)C10—C9—H9115.8
C2—C1—N1119.6 (3)C11—C10—C15118.2 (4)
C6—C1—N1119.9 (3)C11—C10—C9123.7 (4)
C3—C2—C1120.1 (3)C15—C10—C9118.1 (4)
C3—C2—H2120.0C12—C11—C10120.7 (5)
C1—C2—H2120.0C12—C11—H11119.6
C2—C3—C4120.7 (3)C10—C11—H11119.6
C2—C3—H3119.7C13—C12—C11121.2 (5)
C4—C3—H3119.7C13—C12—H12119.4
N2—C4—C3122.5 (3)C11—C12—H12119.4
N2—C4—C5118.6 (3)C14—C13—C12119.2 (5)
C3—C4—C5118.8 (3)C14—C13—H13120.4
C6—C5—C4120.3 (3)C12—C13—H13120.4
C6—C5—H5119.9C13—C14—C15121.0 (6)
C4—C5—H5119.9C13—C14—H14119.5
C5—C6—C1119.7 (3)C15—C14—H14119.5
C5—C6—H6120.2C14—C15—C10119.6 (5)
C1—C6—H6120.2C14—C15—H15120.2
N3—C7—C8120.7 (4)C10—C15—H15120.2

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···O2i0.89 (3)2.20 (3)3.082 (4)169 (3)

Symmetry codes: (i) x−1, −y+2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2421).

References

  • Bruker (1998). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Okabe, N., Nakamura, T. & Fukuda, H. (1993). Acta Cryst. C49, 1678–1680.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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