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Acta Crystallogr Sect E Struct Rep Online. 2008 July 1; 64(Pt 7): o1341.
Published online 2008 June 25. doi:  10.1107/S1600536808018618
PMCID: PMC2961743

(E)-1-(3-Methoxy­phen­yl)ethanone 4-nitro­phenyl­hydrazone

Abstract

Crystals of the title compound, C15H15N3O3, were obtained from a condensation reaction of 4-nitro­phenyl­hydrazine and 3-methoxy­acetophenone. In the crystal structure, the methoxy­phenyl ring is twisted slightly with respect to the nitro­phenyl­hydrazine plane, making a dihedral angle of 14.81 (8)°. The nitro and meth­oxy groups are each coplanar with the attached benzene rings. The nitro­phenyl and methoxy­phenyl groups are located on opposite sides of the C=N double bond, indicating an E configuration of the mol­ecule. Adjacent mol­ecules are linked together via N—H(...)O hydrogen bonding, forming chains along the [101] direction.

Related literature

For general background, see: Okabe et al. (1993 [triangle]); Shan et al. (2003a [triangle]). For related structures, see: Shan et al. (2003b [triangle], 2004 [triangle], 2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1341-scheme1.jpg

Experimental

Crystal data

  • C15H15N3O3
  • M r = 285.30
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1341-efi3.jpg
  • a = 4.2977 (17) Å
  • b = 24.709 (9) Å
  • c = 13.132 (5) Å
  • β = 96.332 (11)°
  • V = 1386.0 (9) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 295 (2) K
  • 0.32 × 0.26 × 0.22 mm

Data collection

  • Rigaku R-AXIS RAPID IP diffractometer
  • Absorption correction: none
  • 16470 measured reflections
  • 3014 independent reflections
  • 1643 reflections with I > 2σ(I)
  • R int = 0.045

Refinement

  • R[F 2 > 2σ(F 2)] = 0.049
  • wR(F 2) = 0.141
  • S = 1.03
  • 3014 reflections
  • 192 parameters
  • H-atom parameters constrained
  • Δρmax = 0.15 e Å−3
  • Δρmin = −0.17 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 [triangle]); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 [triangle]); program(s) used to solve structure: SIR92 (Altomare et al., 1993 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808018618/om2241sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808018618/om2241Isup2.hkl

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

Acknowledgments

The work was supported by the Natural Science Foundation of Zhejiang Province, China (No. M203027).

supplementary crystallographic information

Comment

Since some phenylhydrazone derivatives have shown to be potential DNA damaging and mutagenic agents (Okabe et al., 1993), a series of new phenylhydrazone derivatives have been prepared in our laboratory (Shan et al., 2003a). As part of the ongoing investigation, the title compound has recently been prepared and its crystal structure is reported here.

The molecular structure of the title compound is shown in Fig. 1. The N1—C7 bond distance of 1.295 (2) Å indicates a typical C=N double bond. The molecule assumes an E configuration, with the nitrophenyl ring and methoxyphenyl rings located on the opposite sites of the C=N bond. The dihedral angle of 1.4 (3)° between nitro group and C10-benzene ring and the C1—C2—C3—C4 torsion angle of 0.9 (3)° suggest that nitro and methoxyl groups are co-planar with the individual benzene rings. The methoxyphenyl ring is slightly twisted with respect to the nitrophenylhydrazine mean plane by a small dihedral angle of 14.81 (8)°, indicating the molecule is approximately co-planar except for methyl H atoms.

In the crystal structure adjacent molecules are linked via N—H···O hydrogen bonding to form chains along the [1 0 1] direction (Table 1 and Fig. 2). Although π-π stacking was found between 4-nitrophenyl rings in several related structures previously reported, benzil 4-nitrophenylhydrazone (Shan et al., 2003b), 2-chloro-3,4-dimethoxybenzaldehyde 4-nitrophenylhydrazone (Shan et al., 2004) and acetylpyrazine 4-nitrophenylhydrazone (Shan et al., 2008), no π-π stacking is observed in the crystal structure.

Experimental

4-Nitrophenylhydrazine (0.31 g, 2 mmol) was dissolved in ethanol (10 ml), then H2SO4 solution (98%, 0.5 ml) was added slowly to the ethanol solution with stirring. The solution was heated at about 333 K for several minutes until the solution cleared. An ethanol solution (5 ml) of 3-methoxyacetophenone (0.30 g, 2 mmol) was dropped slowly into the above solution with continuous stirring, and the mixture solution was kept at about 333 K for 0.5 h. When the solution had cooled to room temperature, red microcrystals appeared. They were separated and washed with cold water three times to get the product 0.45 g. Single crystals of the title compound were obtained by recrystallization from an absolute ethanol solution.

Refinement

Methyl H atoms were placed in calculated positions with C—H = 0.96 Å and the torsion angle was refined to fit the electron density, Uiso(H) = 1.5Ueq(C). Other H atoms were placed in calculated positions with C—H = 0.93 and N—H = 0.86 Å, and refined in riding mode with Uiso(H) = 1.2Ueq(C,N).

Figures

Fig. 1.
The molecular structure of the title compound with 30% probability displacement ellipsoids for non-H atoms.
Fig. 2.
A diagram showing the N—H···O hydrogen bond chain (dashed lines) [symmetry code: (i) -1 + x, 3/2 - y, -1/2 + z].

Crystal data

C15H15N3O3F000 = 600
Mr = 285.30Dx = 1.367 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4665 reflections
a = 4.2977 (17) Åθ = 2.0–25.0º
b = 24.709 (9) ŵ = 0.10 mm1
c = 13.132 (5) ÅT = 295 (2) K
β = 96.332 (11)ºPrism, red
V = 1386.0 (9) Å30.32 × 0.26 × 0.22 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID IP diffractometer3014 independent reflections
Radiation source: fine-focus sealed tube1643 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.045
Detector resolution: 10.00 pixels mm-1θmax = 27.0º
T = 295(2) Kθmin = 1.7º
ω scansh = −5→5
Absorption correction: nonek = −30→31
16470 measured reflectionsl = −16→15

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.141  w = 1/[σ2(Fo2) + (0.0685P)2 + 0.02P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
3014 reflectionsΔρmax = 0.15 e Å3
192 parametersΔρmin = −0.16 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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
N10.2858 (3)0.59466 (6)0.29114 (11)0.0540 (4)
N20.4535 (3)0.63991 (6)0.27160 (11)0.0573 (4)
H20.44050.65330.21090.069*
N31.2264 (4)0.73954 (7)0.58666 (13)0.0656 (5)
O1−0.4958 (3)0.41329 (6)0.10899 (10)0.0775 (5)
O21.2533 (4)0.71902 (6)0.67268 (11)0.0944 (6)
O31.3617 (4)0.78225 (6)0.56823 (11)0.0865 (5)
C1−0.0634 (4)0.52365 (7)0.24122 (12)0.0507 (5)
C2−0.2090 (4)0.48991 (7)0.16601 (13)0.0563 (5)
H2A−0.20110.49850.09740.068*
C3−0.3663 (4)0.44357 (8)0.19125 (13)0.0574 (5)
C4−0.3852 (5)0.43034 (8)0.29148 (15)0.0680 (6)
H4−0.49000.39930.30870.082*
C5−0.2442 (5)0.46436 (9)0.36672 (14)0.0775 (7)
H5−0.25760.45600.43510.093*
C6−0.0856 (5)0.51000 (8)0.34328 (14)0.0669 (6)
H60.00750.53190.39550.080*
C70.1106 (4)0.57271 (7)0.21575 (13)0.0528 (5)
C80.0787 (5)0.59459 (9)0.10844 (15)0.0818 (7)
H8A0.03960.63280.10990.123*
H8B−0.09260.57690.06860.123*
H8C0.26860.58800.07820.123*
C9−0.6460 (5)0.36382 (8)0.13053 (16)0.0790 (7)
H9A−0.50450.34190.17460.119*
H9B−0.70580.34480.06770.119*
H9C−0.82900.37150.16380.119*
C100.6430 (4)0.66358 (7)0.35048 (13)0.0488 (4)
C110.6824 (4)0.64122 (7)0.44883 (14)0.0574 (5)
H110.57940.60940.46250.069*
C120.8742 (4)0.66645 (8)0.52547 (14)0.0582 (5)
H120.89930.65180.59110.070*
C131.0288 (4)0.71338 (7)0.50517 (13)0.0520 (5)
C140.9974 (4)0.73569 (7)0.40765 (14)0.0566 (5)
H141.10540.76700.39420.068*
C150.8043 (4)0.71083 (7)0.33116 (14)0.0564 (5)
H150.78090.72570.26570.068*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0518 (9)0.0552 (9)0.0533 (9)0.0029 (7)−0.0015 (7)−0.0024 (7)
N20.0604 (10)0.0626 (10)0.0466 (9)−0.0004 (8)−0.0039 (7)0.0005 (7)
N30.0698 (11)0.0610 (11)0.0636 (11)0.0079 (9)−0.0042 (8)−0.0123 (9)
O10.1001 (11)0.0751 (9)0.0548 (8)−0.0272 (8)−0.0025 (7)−0.0045 (7)
O20.1219 (14)0.1013 (12)0.0540 (9)−0.0124 (10)−0.0175 (9)−0.0037 (8)
O30.1030 (12)0.0664 (10)0.0860 (11)−0.0165 (9)−0.0083 (9)−0.0133 (8)
C10.0511 (11)0.0553 (11)0.0446 (10)0.0082 (9)0.0000 (8)−0.0006 (8)
C20.0628 (12)0.0616 (12)0.0435 (10)0.0016 (9)0.0011 (9)−0.0009 (8)
C30.0604 (12)0.0628 (12)0.0472 (11)0.0002 (10)−0.0021 (9)−0.0039 (9)
C40.0795 (15)0.0695 (13)0.0539 (12)−0.0123 (11)0.0031 (10)0.0044 (10)
C50.1069 (18)0.0822 (16)0.0425 (11)−0.0145 (13)0.0039 (11)0.0070 (10)
C60.0812 (15)0.0711 (13)0.0454 (11)−0.0056 (11)−0.0058 (10)−0.0020 (9)
C70.0540 (11)0.0578 (11)0.0456 (11)0.0077 (9)0.0014 (9)−0.0020 (8)
C80.0992 (17)0.0880 (16)0.0542 (12)−0.0295 (13)−0.0098 (11)0.0072 (10)
C90.0948 (16)0.0627 (13)0.0760 (15)−0.0158 (12)−0.0063 (12)−0.0003 (11)
C100.0459 (10)0.0516 (11)0.0481 (10)0.0075 (8)0.0014 (8)−0.0032 (8)
C110.0610 (12)0.0545 (11)0.0557 (12)−0.0037 (9)0.0027 (9)0.0008 (9)
C120.0644 (12)0.0630 (12)0.0465 (11)0.0042 (10)0.0019 (9)0.0022 (9)
C130.0518 (11)0.0514 (11)0.0511 (11)0.0084 (9)−0.0020 (8)−0.0077 (8)
C140.0564 (12)0.0496 (11)0.0625 (12)0.0029 (9)0.0001 (9)−0.0003 (9)
C150.0601 (12)0.0566 (11)0.0509 (11)0.0044 (9)−0.0013 (9)0.0055 (9)

Geometric parameters (Å, °)

N1—C71.295 (2)C6—H60.9300
N1—N21.3699 (19)C7—C81.501 (3)
N2—C101.376 (2)C8—H8A0.9600
N2—H20.8600C8—H8B0.9600
N3—O21.232 (2)C8—H8C0.9600
N3—O31.242 (2)C9—H9A0.9600
N3—C131.443 (2)C9—H9B0.9600
O1—C31.380 (2)C9—H9C0.9600
O1—C91.425 (2)C10—C151.395 (2)
C1—C21.388 (2)C10—C111.398 (3)
C1—C61.395 (2)C11—C121.378 (2)
C1—C71.482 (2)C11—H110.9300
C2—C31.388 (2)C12—C131.377 (3)
C2—H2A0.9300C12—H120.9300
C3—C41.367 (3)C13—C141.387 (2)
C4—C51.385 (3)C14—C151.375 (2)
C4—H40.9300C14—H140.9300
C5—C61.370 (3)C15—H150.9300
C5—H50.9300
C7—N1—N2118.18 (15)C7—C8—H8B109.5
N1—N2—C10119.09 (14)H8A—C8—H8B109.5
N1—N2—H2120.5C7—C8—H8C109.5
C10—N2—H2120.5H8A—C8—H8C109.5
O2—N3—O3121.99 (17)H8B—C8—H8C109.5
O2—N3—C13118.92 (18)O1—C9—H9A109.5
O3—N3—C13119.08 (17)O1—C9—H9B109.5
C3—O1—C9117.53 (15)H9A—C9—H9B109.5
C2—C1—C6117.71 (18)O1—C9—H9C109.5
C2—C1—C7122.00 (16)H9A—C9—H9C109.5
C6—C1—C7120.29 (16)H9B—C9—H9C109.5
C1—C2—C3121.26 (17)N2—C10—C15118.92 (16)
C1—C2—H2A119.4N2—C10—C11121.93 (16)
C3—C2—H2A119.4C15—C10—C11119.14 (16)
C4—C3—O1124.23 (18)C12—C11—C10119.85 (17)
C4—C3—C2120.60 (17)C12—C11—H11120.1
O1—C3—C2115.17 (16)C10—C11—H11120.1
C3—C4—C5118.30 (19)C13—C12—C11120.15 (17)
C3—C4—H4120.8C13—C12—H12119.9
C5—C4—H4120.8C11—C12—H12119.9
C6—C5—C4121.90 (18)C12—C13—C14120.89 (16)
C6—C5—H5119.0C12—C13—N3119.38 (17)
C4—C5—H5119.0C14—C13—N3119.73 (18)
C5—C6—C1120.22 (18)C15—C14—C13119.09 (18)
C5—C6—H6119.9C15—C14—H14120.5
C1—C6—H6119.9C13—C14—H14120.5
N1—C7—C1115.80 (16)C14—C15—C10120.86 (17)
N1—C7—C8123.50 (18)C14—C15—H15119.6
C1—C7—C8120.69 (16)C10—C15—H15119.6
C7—C8—H8A109.5
C7—N1—N2—C10−179.48 (14)C6—C1—C7—C8−166.53 (19)
C6—C1—C2—C3−1.2 (3)N1—N2—C10—C15−177.60 (15)
C7—C1—C2—C3178.84 (16)N1—N2—C10—C113.4 (2)
C9—O1—C3—C4−3.0 (3)N2—C10—C11—C12−179.86 (15)
C9—O1—C3—C2176.82 (17)C15—C10—C11—C121.2 (3)
C1—C2—C3—C40.9 (3)C10—C11—C12—C13−0.5 (3)
C1—C2—C3—O1−178.98 (16)C11—C12—C13—C14−0.7 (3)
O1—C3—C4—C5179.96 (18)C11—C12—C13—N3179.40 (16)
C2—C3—C4—C50.1 (3)O2—N3—C13—C120.4 (3)
C3—C4—C5—C6−0.7 (3)O3—N3—C13—C12−179.01 (17)
C4—C5—C6—C10.3 (3)O2—N3—C13—C14−179.54 (17)
C2—C1—C6—C50.7 (3)O3—N3—C13—C141.1 (3)
C7—C1—C6—C5−179.42 (18)C12—C13—C14—C151.2 (3)
N2—N1—C7—C1179.54 (13)N3—C13—C14—C15−178.92 (16)
N2—N1—C7—C8−0.8 (3)C13—C14—C15—C10−0.5 (3)
C2—C1—C7—N1−166.90 (16)N2—C10—C15—C14−179.69 (15)
C6—C1—C7—N113.2 (2)C11—C10—C15—C14−0.7 (3)
C2—C1—C7—C813.4 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···O3i0.862.453.279 (2)161

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: OM2241).

References

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