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

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

doi:10.1107/S1600536809031638

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2162

doi:10.1107/S1600536809031638

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

Zhi-gang Yin,^a ^* Heng-yu Qian,^a Chun-xia Zhang ^a and Zhi-qiang Yao ^a

^aKey Laboratory of Surface and Interface Science of Henan, School of Materials & Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou 450002, People's Republic of China
^*Correspondence e-mail: yinck@263.net

(Received 6 August 2009; accepted 11 August 2009; online 15 August 2009)

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.

Related literature

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

Experimental

Crystal data

C₁₄H₁₃N₃O₃
M_r = 271.27
Triclinic, $[P \overline 1]$
a = 8.2261 (2) Å
b = 9.0200 (2) Å
c = 9.1027 (2) Å
α = 89.166 (2)°
β = 77.549 (2)°
γ = 80.250 (2)°
V = 649.83 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.1 mm⁻¹
T = 296 K
0.12 × 0.10 × 0.07 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
9374 measured reflections
2687 independent reflections
1285 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.136
S = 0.90
2687 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2	0.86	2.00	2.611 (2)	127

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809031638/xu2582sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809031638/xu2582Isup2.hkl

checkCIF report

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.

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

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

C₁₄H₁₃N₃O₃	Z = 2
M_r = 271.27	F(000) = 284
Triclinic, P1	D_x = 1.386 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2261 (2) Å	Cell parameters from 1117 reflections
b = 9.0200 (2) Å	θ = 2.3–26.5°
c = 9.1027 (2) Å	µ = 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 tube	R_int = 0.039
Graphite monochromator	θ_max = 26.5°, θ_min = 2.3°
ω scans	h = −10→10
9374 measured reflections	k = −11→10
2687 independent reflections	l = −11→10

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.136	H-atom parameters constrained
S = 0.90	w = 1/[σ²(F_o²) + (0.0668P)²] where P = (F_o² + 2F_c²)/3
2687 reflections	(Δ/σ)_max < 0.001
182 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₄H₁₃N₃O₃	γ = 80.250 (2)°
M_r = 271.27	V = 649.83 (3) Å³
Triclinic, P1	Z = 2
a = 8.2261 (2) Å	Mo Kα radiation
b = 9.0200 (2) Å	µ = 0.1 mm⁻¹
c = 9.1027 (2) Å	T = 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 reflections	R_int = 0.039
2687 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.136	H-atom parameters constrained
S = 0.90	Δρ_max = 0.19 e Å⁻³
2687 reflections	Δρ_min = −0.17 e Å⁻³
182 parameters

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

	x	y	z	U_iso*/U_eq
N2	0.15950 (19)	0.59694 (17)	0.52496 (19)	0.0473 (5)
H2A	0.1972	0.5044	0.5403	0.057*
N1	0.2372 (2)	0.66928 (18)	0.40298 (19)	0.0470 (5)
O	0.58672 (18)	0.12781 (16)	0.35428 (17)	0.0599 (5)
C9	0.0217 (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)
C7	0.3716 (2)	0.5962 (2)	0.3164 (2)	0.0461 (6)
O1	−0.0875 (2)	0.41053 (18)	0.9101 (2)	0.0751 (5)
C6	0.4454 (2)	0.4401 (2)	0.3302 (2)	0.0481 (6)
H6A	0.3927	0.3866	0.4093	0.058*
O2	0.1291 (2)	0.38750 (17)	0.72528 (19)	0.0727 (5)
C10	−0.0499 (3)	0.8183 (2)	0.5884 (3)	0.0519 (6)
H10A	−0.0067	0.8594	0.4969	0.062*
C3	0.7845 (3)	0.1262 (2)	0.1462 (3)	0.0581 (7)
H3A	0.8526	0.1572	0.0600	0.070*
C4	0.6560 (2)	0.2129 (2)	0.2398 (2)	0.0480 (6)
C11	−0.1819 (3)	0.9011 (2)	0.6869 (3)	0.0606 (7)
H11A	−0.2263	0.9974	0.6615	0.073*
C5	0.5839 (2)	0.3679 (2)	0.2372 (2)	0.0486 (6)
H5A	0.6390	0.4249	0.1628	0.058*
C8	0.4503 (3)	0.6843 (2)	0.1883 (3)	0.0645 (7)
H8A	0.3815	0.7816	0.1884	0.097*
H8B	0.4589	0.6319	0.0952	0.097*
H8C	0.5610	0.6961	0.1990	0.097*
C13	−0.1892 (3)	0.7005 (3)	0.8576 (3)	0.0588 (7)
H13A	−0.2368	0.6600	0.9479	0.071*
C12	−0.2507 (3)	0.8442 (3)	0.8237 (3)	0.0633 (7)
H12A	−0.3376	0.9029	0.8917	0.076*
C2	0.7968 (3)	−0.0203 (3)	0.2030 (3)	0.0648 (7)
H2B	0.8740	−0.1046	0.1615	0.078*
C1	0.6766 (3)	−0.0147 (3)	0.3274 (3)	0.0659 (7)
H1B	0.6563	−0.0965	0.3878	0.079*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N2	0.0478 (10)	0.0362 (10)	0.0488 (12)	−0.0004 (8)	0.0038 (9)	0.0049 (9)
N1	0.0481 (10)	0.0431 (10)	0.0440 (11)	−0.0059 (8)	0.0013 (9)	0.0049 (9)
O	0.0627 (10)	0.0535 (10)	0.0539 (11)	−0.0022 (8)	0.0025 (8)	0.0052 (8)
C9	0.0403 (11)	0.0419 (12)	0.0415 (14)	−0.0082 (9)	−0.0047 (10)	−0.0008 (10)
C14	0.0456 (12)	0.0465 (13)	0.0440 (14)	−0.0111 (10)	−0.0078 (11)	0.0050 (11)
N3	0.0626 (13)	0.0520 (12)	0.0534 (13)	−0.0170 (10)	−0.0103 (11)	0.0130 (10)
C7	0.0441 (12)	0.0452 (13)	0.0458 (14)	−0.0076 (10)	−0.0023 (10)	−0.0006 (11)
O1	0.0893 (12)	0.0741 (12)	0.0618 (12)	−0.0307 (10)	−0.0041 (10)	0.0247 (9)
C6	0.0484 (12)	0.0458 (13)	0.0460 (14)	−0.0057 (10)	−0.0030 (11)	0.0015 (11)
O2	0.0690 (11)	0.0546 (10)	0.0825 (13)	0.0023 (8)	−0.0015 (10)	0.0187 (9)
C10	0.0535 (13)	0.0425 (13)	0.0514 (15)	−0.0020 (10)	0.0017 (11)	0.0051 (11)
C3	0.0548 (14)	0.0449 (14)	0.0628 (17)	−0.0019 (11)	0.0080 (12)	0.0013 (12)
C4	0.0465 (13)	0.0467 (13)	0.0480 (15)	−0.0096 (10)	−0.0028 (11)	0.0033 (12)
C11	0.0580 (14)	0.0459 (14)	0.0684 (18)	0.0011 (11)	−0.0007 (13)	−0.0017 (13)
C5	0.0470 (12)	0.0457 (13)	0.0499 (15)	−0.0082 (10)	−0.0034 (11)	−0.0021 (11)
C8	0.0672 (15)	0.0504 (14)	0.0618 (17)	−0.0025 (12)	0.0106 (13)	0.0065 (13)
C13	0.0563 (14)	0.0671 (16)	0.0476 (15)	−0.0122 (12)	0.0020 (12)	0.0023 (13)
C12	0.0538 (14)	0.0635 (16)	0.0607 (17)	−0.0011 (12)	0.0072 (12)	−0.0124 (14)
C2	0.0687 (16)	0.0495 (15)	0.0655 (18)	0.0015 (12)	0.0003 (14)	−0.0011 (13)
C1	0.0757 (17)	0.0452 (14)	0.0707 (18)	−0.0023 (12)	−0.0089 (15)	0.0070 (13)

Geometric parameters (Å, º) top

N2—C9	1.364 (2)	C10—H10A	0.9300
N2—N1	1.372 (2)	C3—C4	1.344 (3)
N2—H2A	0.8600	C3—C2	1.407 (3)
N1—C7	1.293 (2)	C3—H3A	0.9300
O—C4	1.367 (2)	C4—C5	1.425 (3)
O—C1	1.367 (2)	C11—C12	1.382 (3)
C9—C10	1.394 (3)	C11—H11A	0.9300
C9—C14	1.409 (3)	C5—H5A	0.9300
C14—C13	1.389 (3)	C8—H8A	0.9600
C14—N3	1.440 (3)	C8—H8B	0.9600
N3—O1	1.232 (2)	C8—H8C	0.9600
N3—O2	1.238 (2)	C13—C12	1.366 (3)
C7—C6	1.451 (3)	C13—H13A	0.9300
C7—C8	1.494 (3)	C12—H12A	0.9300
C6—C5	1.337 (2)	C2—C1	1.328 (3)
C6—H6A	0.9300	C2—H2B	0.9300
C10—C11	1.366 (3)	C1—H1B	0.9300

C9—N2—N1	119.11 (16)	C3—C4—C5	132.1 (2)
C9—N2—H2A	120.4	O—C4—C5	118.40 (18)
N1—N2—H2A	120.4	C10—C11—C12	121.2 (2)
C7—N1—N2	118.00 (17)	C10—C11—H11A	119.4
C4—O—C1	106.09 (16)	C12—C11—H11A	119.4
N2—C9—C10	120.34 (19)	C6—C5—C4	127.0 (2)
N2—C9—C14	123.30 (18)	C6—C5—H5A	116.5
C10—C9—C14	116.36 (18)	C4—C5—H5A	116.5
C13—C14—C9	121.3 (2)	C7—C8—H8A	109.5
C13—C14—N3	117.0 (2)	C7—C8—H8B	109.5
C9—C14—N3	121.75 (18)	H8A—C8—H8B	109.5
O1—N3—O2	121.45 (19)	C7—C8—H8C	109.5
O1—N3—C14	118.91 (19)	H8A—C8—H8C	109.5
O2—N3—C14	119.64 (18)	H8B—C8—H8C	109.5
N1—C7—C6	126.3 (2)	C12—C13—C14	120.4 (2)
N1—C7—C8	114.50 (19)	C12—C13—H13A	119.8
C6—C7—C8	119.16 (18)	C14—C13—H13A	119.8
C5—C6—C7	124.5 (2)	C13—C12—C11	119.0 (2)
C5—C6—H6A	117.7	C13—C12—H12A	120.5
C7—C6—H6A	117.7	C11—C12—H12A	120.5
C11—C10—C9	121.6 (2)	C1—C2—C3	106.61 (19)
C11—C10—H10A	119.2	C1—C2—H2B	126.7
C9—C10—H10A	119.2	C3—C2—H2B	126.7
C4—C3—C2	107.2 (2)	C2—C1—O	110.6 (2)
C4—C3—H3A	126.4	C2—C1—H1B	124.7
C2—C3—H3A	126.4	O—C1—H1B	124.7
C3—C4—O	109.46 (18)

C9—N2—N1—C7	177.25 (18)	C14—C9—C10—C11	3.7 (3)
N1—N2—C9—C10	6.7 (3)	C2—C3—C4—O	0.4 (3)
N1—N2—C9—C14	−173.15 (18)	C2—C3—C4—C5	−178.4 (2)
N2—C9—C14—C13	175.70 (19)	C1—O—C4—C3	−0.3 (3)
C10—C9—C14—C13	−4.2 (3)	C1—O—C4—C5	178.63 (19)
N2—C9—C14—N3	−4.5 (3)	C9—C10—C11—C12	−0.4 (4)
C10—C9—C14—N3	175.66 (18)	C7—C6—C5—C4	−175.9 (2)
C13—C14—N3—O1	9.4 (3)	C3—C4—C5—C6	173.7 (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—C12	1.5 (3)
C9—C14—N3—O2	8.9 (3)	N3—C14—C13—C12	−178.4 (2)
N2—N1—C7—C6	3.5 (3)	C14—C13—C12—C11	2.0 (4)
N2—N1—C7—C8	−178.71 (18)	C10—C11—C12—C13	−2.5 (4)
N1—C7—C6—C5	179.3 (2)	C4—C3—C2—C1	−0.2 (3)
C8—C7—C6—C5	1.6 (3)	C3—C2—C1—O	0.0 (3)
N2—C9—C10—C11	−176.2 (2)	C4—O—C1—C2	0.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2	0.86	2.00	2.611 (2)	127

Experimental details

Crystal data
Chemical formula	C₁₄H₁₃N₃O₃
M_r	271.27
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	8.2261 (2), 9.0200 (2), 9.1027 (2)
α, β, γ (°)	89.166 (2), 77.549 (2), 80.250 (2)
V (Å³)	649.83 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.1
Crystal size (mm)	0.12 × 0.10 × 0.07

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9374, 2687, 1285
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.627

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.136, 0.90
No. of reflections	2687
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.17

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2	0.86	2.00	2.611 (2)	127

Acknowledgements

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

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