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Acta Cryst. (2009). E65, o2162    [ doi:10.1107/S1600536809031638 ]

1-[4-(2-Furyl)but-3-en-2-ylidene]-2-(2-nitrophenyl)hydrazine

Z. Yin, H. Qian, C. Zhang and Z. Yao

Abstract top

In the title Schiff base compound, C14H13N3O3, the furan and benzene rings are oriented at a dihedral angle of 10.24 (13)°. Intramolecular N-H...O hydrogen bonding is observed between the imino and nitro groups.

Comment top

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 work, the title compound (I) is synthesized in our group, and its structure is reported here (Fig. 1).

The molecular structure is non-planar, there is a dihedral angle of 9.19 (9)° between the benzene ring and the N2/N1/C7/C6/C5 plane, while the N2/N1/C7/C6/C5 planar and the furyl ring is nearly planar, making a dihedral angle of 4.26 (11)°. The furan and benzene rings are oriented at a dihedral angle of 10.24 (13)°. Intramolecular N—H···O hydrogen bonding is present between imino and nitro groups (Table 1).

Related literature top

For applications of Schiff base compounds, see: Okabe et al. (1993).

Experimental top

2-Nitrophenylhydrazine (1 mmol, 0.153 g) was dissolved in anhydrous ethanol (15 ml). The mixture was stirred for several min at 351 K, then the furylideneacetone (1 mmol, 0.136 g) in ethanol (8 ml) was added dropwise and the mixture was stirred at refluxing temperature for 2 h. The product was isolated and recrystallized from methanol, red single crystals of (I) were obtained after 3 d.

Refinement top

All H atoms were positioned geometrically and refined as riding with C—H = 0.93 (aromatic), 0.96 Å (methyl) and N—H = 0.86 Å, and refined in riding mode with Uiso(H) = 1.5Ueq(C) for methyl H atoms and Uiso(H) = 1.2Ueq(C,N) for the others.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bond is shown in dashed line.
1-[4-(2-Furyl)but-3-en-2-ylidene]-2-(2-nitrophenyl)hydrazine top
Crystal data top
C14H13N3O3Z = 2
Mr = 271.27F(000) = 284
Triclinic, P1Dx = 1.386 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.2261 (2) ÅCell parameters from 1117 reflections
b = 9.0200 (2) Åθ = 2.3–26.5°
c = 9.1027 (2) ŵ = 0.1 mm−1
α = 89.166 (2)°T = 296 K
β = 77.549 (2)°Plate, red
γ = 80.250 (2)°0.12 × 0.10 × 0.07 mm
V = 649.83 (3) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer		1285 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.039
graphiteθmax = 26.5°, θmin = 2.3°
ω scansh = −10→10
9374 measured reflectionsk = −11→10
2687 independent reflectionsl = −11→10
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.136H-atom parameters constrained
S = 0.90 w = 1/[σ2(Fo2) + (0.0668P)2]
where P = (Fo2 + 2Fc2)/3
2687 reflections(Δ/σ)max < 0.001
182 parametersΔρmax = 0.19 e Å−3
0 restraintsΔρmin = −0.17 e Å−3
Crystal data top
C14H13N3O3γ = 80.250 (2)°
Mr = 271.27V = 649.83 (3) Å3
Triclinic, P1Z = 2
a = 8.2261 (2) ÅMo Kα radiation
b = 9.0200 (2) ŵ = 0.1 mm−1
c = 9.1027 (2) ÅT = 296 K
α = 89.166 (2)°0.12 × 0.10 × 0.07 mm
β = 77.549 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		1285 reflections with I > 2σ(I)
9374 measured reflectionsRint = 0.039
2687 independent reflectionsθmax = 26.5°
Refinement top
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.136Δρmax = 0.19 e Å−3
S = 0.90Δρmin = −0.17 e Å−3
2687 reflectionsAbsolute structure: ?
182 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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) top
xyzUiso*/Ueq
N20.15950 (19)0.59694 (17)0.52496 (19)0.0473 (5)
H2A0.19720.50440.54030.057*
N10.2372 (2)0.66928 (18)0.40298 (19)0.0470 (5)
O0.58672 (18)0.12781 (16)0.35428 (17)0.0599 (5)
C90.0217 (2)0.6737 (2)0.6216 (2)0.0417 (5)
C14−0.0559 (2)0.6146 (2)0.7579 (2)0.0453 (6)
N3−0.0014 (2)0.4629 (2)0.8002 (2)0.0556 (5)
C70.3716 (2)0.5962 (2)0.3164 (2)0.0461 (6)
O1−0.0875 (2)0.41053 (18)0.9101 (2)0.0751 (5)
C60.4454 (2)0.4401 (2)0.3302 (2)0.0481 (6)
H6A0.39270.38660.40930.058*
O20.1291 (2)0.38750 (17)0.72528 (19)0.0727 (5)
C10−0.0499 (3)0.8183 (2)0.5884 (3)0.0519 (6)
H10A−0.00670.85940.49690.062*
C30.7845 (3)0.1262 (2)0.1462 (3)0.0581 (7)
H3A0.85260.15720.06000.070*
C40.6560 (2)0.2129 (2)0.2398 (2)0.0480 (6)
C11−0.1819 (3)0.9011 (2)0.6869 (3)0.0606 (7)
H11A−0.22630.99740.66150.073*
C50.5839 (2)0.3679 (2)0.2372 (2)0.0486 (6)
H5A0.63900.42490.16280.058*
C80.4503 (3)0.6843 (2)0.1883 (3)0.0645 (7)
H8A0.38150.78160.18840.097*
H8B0.45890.63190.09520.097*
H8C0.56100.69610.19900.097*
C13−0.1892 (3)0.7005 (3)0.8576 (3)0.0588 (7)
H13A−0.23680.66000.94790.071*
C12−0.2507 (3)0.8442 (3)0.8237 (3)0.0633 (7)
H12A−0.33760.90290.89170.076*
C20.7968 (3)−0.0203 (3)0.2030 (3)0.0648 (7)
H2B0.8740−0.10460.16150.078*
C10.6766 (3)−0.0147 (3)0.3274 (3)0.0659 (7)
H1B0.6563−0.09650.38780.079*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N20.0478 (10)0.0362 (10)0.0488 (12)−0.0004 (8)0.0038 (9)0.0049 (9)
N10.0481 (10)0.0431 (10)0.0440 (11)−0.0059 (8)0.0013 (9)0.0049 (9)
O0.0627 (10)0.0535 (10)0.0539 (11)−0.0022 (8)0.0025 (8)0.0052 (8)
C90.0403 (11)0.0419 (12)0.0415 (14)−0.0082 (9)−0.0047 (10)−0.0008 (10)
C140.0456 (12)0.0465 (13)0.0440 (14)−0.0111 (10)−0.0078 (11)0.0050 (11)
N30.0626 (13)0.0520 (12)0.0534 (13)−0.0170 (10)−0.0103 (11)0.0130 (10)
C70.0441 (12)0.0452 (13)0.0458 (14)−0.0076 (10)−0.0023 (10)−0.0006 (11)
O10.0893 (12)0.0741 (12)0.0618 (12)−0.0307 (10)−0.0041 (10)0.0247 (9)
C60.0484 (12)0.0458 (13)0.0460 (14)−0.0057 (10)−0.0030 (11)0.0015 (11)
O20.0690 (11)0.0546 (10)0.0825 (13)0.0023 (8)−0.0015 (10)0.0187 (9)
C100.0535 (13)0.0425 (13)0.0514 (15)−0.0020 (10)0.0017 (11)0.0051 (11)
C30.0548 (14)0.0449 (14)0.0628 (17)−0.0019 (11)0.0080 (12)0.0013 (12)
C40.0465 (13)0.0467 (13)0.0480 (15)−0.0096 (10)−0.0028 (11)0.0033 (12)
C110.0580 (14)0.0459 (14)0.0684 (18)0.0011 (11)−0.0007 (13)−0.0017 (13)
C50.0470 (12)0.0457 (13)0.0499 (15)−0.0082 (10)−0.0034 (11)−0.0021 (11)
C80.0672 (15)0.0504 (14)0.0618 (17)−0.0025 (12)0.0106 (13)0.0065 (13)
C130.0563 (14)0.0671 (16)0.0476 (15)−0.0122 (12)0.0020 (12)0.0023 (13)
C120.0538 (14)0.0635 (16)0.0607 (17)−0.0011 (12)0.0072 (12)−0.0124 (14)
C20.0687 (16)0.0495 (15)0.0655 (18)0.0015 (12)0.0003 (14)−0.0011 (13)
C10.0757 (17)0.0452 (14)0.0707 (18)−0.0023 (12)−0.0089 (15)0.0070 (13)
Geometric parameters (Å, °) top
N2—C91.364 (2)C10—H10A0.9300
N2—N11.372 (2)C3—C41.344 (3)
N2—H2A0.8600C3—C21.407 (3)
N1—C71.293 (2)C3—H3A0.9300
O—C41.367 (2)C4—C51.425 (3)
O—C11.367 (2)C11—C121.382 (3)
C9—C101.394 (3)C11—H11A0.9300
C9—C141.409 (3)C5—H5A0.9300
C14—C131.389 (3)C8—H8A0.9600
C14—N31.440 (3)C8—H8B0.9600
N3—O11.232 (2)C8—H8C0.9600
N3—O21.238 (2)C13—C121.366 (3)
C7—C61.451 (3)C13—H13A0.9300
C7—C81.494 (3)C12—H12A0.9300
C6—C51.337 (2)C2—C11.328 (3)
C6—H6A0.9300C2—H2B0.9300
C10—C111.366 (3)C1—H1B0.9300
C9—N2—N1119.11 (16)C3—C4—C5132.1 (2)
C9—N2—H2A120.4O—C4—C5118.40 (18)
N1—N2—H2A120.4C10—C11—C12121.2 (2)
C7—N1—N2118.00 (17)C10—C11—H11A119.4
C4—O—C1106.09 (16)C12—C11—H11A119.4
N2—C9—C10120.34 (19)C6—C5—C4127.0 (2)
N2—C9—C14123.30 (18)C6—C5—H5A116.5
C10—C9—C14116.36 (18)C4—C5—H5A116.5
C13—C14—C9121.3 (2)C7—C8—H8A109.5
C13—C14—N3117.0 (2)C7—C8—H8B109.5
C9—C14—N3121.75 (18)H8A—C8—H8B109.5
O1—N3—O2121.45 (19)C7—C8—H8C109.5
O1—N3—C14118.91 (19)H8A—C8—H8C109.5
O2—N3—C14119.64 (18)H8B—C8—H8C109.5
N1—C7—C6126.3 (2)C12—C13—C14120.4 (2)
N1—C7—C8114.50 (19)C12—C13—H13A119.8
C6—C7—C8119.16 (18)C14—C13—H13A119.8
C5—C6—C7124.5 (2)C13—C12—C11119.0 (2)
C5—C6—H6A117.7C13—C12—H12A120.5
C7—C6—H6A117.7C11—C12—H12A120.5
C11—C10—C9121.6 (2)C1—C2—C3106.61 (19)
C11—C10—H10A119.2C1—C2—H2B126.7
C9—C10—H10A119.2C3—C2—H2B126.7
C4—C3—C2107.2 (2)C2—C1—O110.6 (2)
C4—C3—H3A126.4C2—C1—H1B124.7
C2—C3—H3A126.4O—C1—H1B124.7
C3—C4—O109.46 (18)
C9—N2—N1—C7177.25 (18)C14—C9—C10—C113.7 (3)
N1—N2—C9—C106.7 (3)C2—C3—C4—O0.4 (3)
N1—N2—C9—C14−173.15 (18)C2—C3—C4—C5−178.4 (2)
N2—C9—C14—C13175.70 (19)C1—O—C4—C3−0.3 (3)
C10—C9—C14—C13−4.2 (3)C1—O—C4—C5178.63 (19)
N2—C9—C14—N3−4.5 (3)C9—C10—C11—C12−0.4 (4)
C10—C9—C14—N3175.66 (18)C7—C6—C5—C4−175.9 (2)
C13—C14—N3—O19.4 (3)C3—C4—C5—C6173.7 (2)
C9—C14—N3—O1−170.41 (19)O—C4—C5—C6−5.0 (3)
C13—C14—N3—O2−171.21 (19)C9—C14—C13—C121.5 (3)
C9—C14—N3—O28.9 (3)N3—C14—C13—C12−178.4 (2)
N2—N1—C7—C63.5 (3)C14—C13—C12—C112.0 (4)
N2—N1—C7—C8−178.71 (18)C10—C11—C12—C13−2.5 (4)
N1—C7—C6—C5179.3 (2)C4—C3—C2—C1−0.2 (3)
C8—C7—C6—C51.6 (3)C3—C2—C1—O0.0 (3)
N2—C9—C10—C11−176.2 (2)C4—O—C1—C20.2 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O20.862.002.611 (2)127
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O20.862.002.611 (2)127
Acknowledgements top

The authors would like to express their deep appreciation to the start-up fund for PhDs of the Natural Scientific Research of Zhengzhou University of Light Industry (No. 2005001) and the Fund for Natural Scientific Research of Zhengzhou University of Light Industry, China (000455).

references
References top

Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Okabe, N., Nakamura, T. & Fukuda, H. (1993). Acta Cryst. C49, 1678–1680.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.