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

Abstract

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,

• 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) ų

• 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[F ² > 2σ(F ²)] = 0.050

• wR(F ²) = 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

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 ▶).

Supplementary Material

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

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

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 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).

Experimental

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

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 U_iso(H) = 1.5U_eq(C) for methyl H atoms and U_iso(H) = 1.2U_eq(C,N) for the others.

Figures

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.

Crystal data

C14H13N3O3	Z = 2
Mr = 271.27	F(000) = 284
Triclinic, P1	Dx = 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

Bruker SMART CCD area-detector diffractometer	1285 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.039
graphite	θmax = 26.5°, θmin = 2.3°
ω scans	h = −10→10
9374 measured reflections	k = −11→10
2687 independent reflections	l = −11→10

Refinement

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(Fo2) + (0.0668P)2] where P = (Fo2 + 2Fc2)/3
2687 reflections	(Δ/σ)max < 0.001
182 parameters	Δρmax = 0.19 e Å−3
0 restraints	Δρmin = −0.17 e Å−3

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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