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Acta Cryst. (2009). E65, o74    [ doi:10.1107/S1600536808040919 ]

N'-[1-(4-Nitrophenyl)ethylidene]acetohydrazide

Y.-F. Li, L.-C. Du and F.-F. Jian

Abstract top

The title compound, C10H11N3O3, was prepared by the reaction of acetohydrazide and 1-(4-nitrophenyl)ethanone. The asymmetric unit contains two crystallographically independent molecules. Inversion-related molecules form dimers, in which two N-H...O hydrogen bonds generate an intermolecular R22(8) ring.

Comment top

Schiff bases have received considerable attention in the literature. They are attractive from several points of view, such as the possibility of analytical application (Cimerman, et al., 1997). As part of our search for new schiff base compounds we synthesized the title compound (I), and describe its structure here.

As shown in Fig. 1, the asymmetric unit contains two crystallographically independent molecules. The C3—N2 bond length of 1.277 (3) Å and C13—N5 bond length of 1.287 (3) Å is comparable with C—N double bond [1.281 (2) Å] reported (Girgis, 2006).

In the structure, there exist C-H···O, C-H···N and N-H···N hydrogen bonding interactions. Inversion-related molecules form a dimer structure, in which two N—H···O hydrogen bonds generate an intermolecular R22(8) ring (Table 1).

Related literature top

For possibile analytical applications of Schiff bases, see: Cimerman et al. (1997). For a related structure, see: Girgis (2006).

Experimental top

A mixture of the acetohydrazide (0.1 mol), and 1-(4-nitrophenyl)ethanone (0.1 mol) was stirred in refluxing ethanol (20 mL) for 4 h to afford the title compound (0.086 mol, yield 86%). Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

Refinement top

N-bonded H atoms were found from a difference Fourier map and refined freely. C-bonded H atoms were fixed geometrically and allowed to ride on their attached atoms, with C—H = 0.93-0.96 Å, and with Uiso=1.2–1.5Ueq.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of the title compound showing 30% probability displacement ellipsoids and the atom-numbering scheme.
N'-[1-(4-Nitrophenyl)ethylidene]acetohydrazide top
Crystal data top
C10H11N3O3Z = 4
Mr = 221.22F(000) = 464
Triclinic, P1Dx = 1.347 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.4453 (17) ÅCell parameters from 1553 reflections
b = 9.5438 (19) Åθ = 2.9–23.0°
c = 14.820 (3) ŵ = 0.10 mm−1
α = 72.66 (3)°T = 293 K
β = 77.37 (3)°Block, yellow
γ = 75.59 (3)°0.25 × 0.20 × 0.18 mm
V = 1090.7 (4) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer		2570 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.027
graphiteθmax = 25.5°, θmin = 2.3°
φ and ω scansh = −10→10
6035 measured reflectionsk = −8→11
4037 independent reflectionsl = −17→17
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)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.159H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0784P)2 + 0.1468P]
where P = (Fo2 + 2Fc2)/3
4037 reflections(Δ/σ)max < 0.001
297 parametersΔρmax = 0.22 e Å−3
0 restraintsΔρmin = −0.21 e Å−3
Crystal data top
C10H11N3O3γ = 75.59 (3)°
Mr = 221.22V = 1090.7 (4) Å3
Triclinic, P1Z = 4
a = 8.4453 (17) ÅMo Kα radiation
b = 9.5438 (19) ŵ = 0.10 mm−1
c = 14.820 (3) ÅT = 293 K
α = 72.66 (3)°0.25 × 0.20 × 0.18 mm
β = 77.37 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		2570 reflections with I > 2σ(I)
6035 measured reflectionsRint = 0.027
4037 independent reflectionsθmax = 25.5°
Refinement top
R[F2 > 2σ(F2)] = 0.052H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.159Δρmax = 0.22 e Å−3
S = 1.04Δρmin = −0.21 e Å−3
4037 reflectionsAbsolute structure: ?
297 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
N50.6357 (2)0.18317 (19)0.43057 (12)0.0478 (4)
N40.6040 (2)0.3087 (2)0.46328 (13)0.0517 (5)
C200.7190 (3)−0.0804 (3)0.37732 (16)0.0553 (6)
H20A0.7913−0.05770.40760.066*
O40.6882 (2)0.4455 (2)0.53613 (14)0.0762 (6)
C130.5290 (2)0.1642 (2)0.38741 (14)0.0463 (5)
C150.5727 (3)0.0223 (2)0.35793 (14)0.0458 (5)
C180.6510 (3)−0.2475 (3)0.30826 (16)0.0540 (6)
C190.7587 (3)−0.2144 (3)0.35260 (17)0.0585 (6)
H19A0.8567−0.28140.36570.070*
C160.4685 (3)−0.0151 (3)0.31179 (16)0.0574 (6)
H16A0.37080.05160.29750.069*
N60.6913 (3)−0.3924 (2)0.28399 (15)0.0688 (6)
C120.7182 (3)0.3345 (3)0.50456 (18)0.0597 (6)
O60.5902 (3)−0.4215 (2)0.24812 (16)0.0985 (7)
O50.8220 (3)−0.4769 (2)0.30177 (14)0.0845 (6)
C140.3713 (3)0.2712 (3)0.36615 (19)0.0659 (7)
H14A0.36140.35680.38980.099*
H14B0.27940.22290.39670.099*
H14C0.37190.30280.29820.099*
C170.5074 (3)−0.1501 (3)0.28661 (17)0.0629 (6)
H17A0.4370−0.17380.25560.076*
N20.3467 (2)0.3952 (2)0.09154 (13)0.0517 (5)
O1−0.0396 (2)0.6256 (2)0.07168 (13)0.0729 (5)
N10.1929 (2)0.4531 (2)0.06573 (15)0.0559 (5)
C100.6576 (3)0.3176 (2)0.14039 (15)0.0505 (5)
H10A0.58930.40610.15070.061*
C30.4436 (3)0.2916 (2)0.05675 (15)0.0497 (5)
C80.9053 (3)0.1382 (3)0.15882 (16)0.0537 (6)
C50.6075 (3)0.2378 (2)0.09008 (15)0.0468 (5)
C60.7135 (3)0.1075 (3)0.07434 (17)0.0601 (6)
H6A0.68340.05340.04020.072*
C90.8052 (3)0.2683 (2)0.17494 (16)0.0532 (6)
H9A0.83690.32220.20870.064*
C70.8626 (3)0.0568 (3)0.10851 (18)0.0640 (7)
H7A0.9327−0.03070.09770.077*
C20.0951 (3)0.5678 (3)0.09904 (17)0.0555 (6)
N31.0610 (3)0.0837 (3)0.19712 (18)0.0759 (6)
C10.1551 (3)0.6207 (3)0.16819 (19)0.0722 (7)
H1B0.07410.70250.18560.108*
H1C0.25740.65340.13900.108*
H1D0.17240.54020.22440.108*
C40.4032 (3)0.2229 (3)−0.0121 (2)0.0814 (9)
H4B0.29380.2695−0.02640.122*
H4C0.40840.11760.01600.122*
H4D0.48160.2376−0.07010.122*
O31.0875 (3)0.1457 (3)0.2518 (2)0.1159 (9)
O21.1593 (3)−0.0208 (3)0.1728 (2)0.1231 (10)
C110.8785 (3)0.2256 (3)0.5105 (3)0.0922 (10)
H11A0.94740.25740.54100.138*
H11B0.93310.22080.44710.138*
H11C0.85820.12850.54700.138*
H4A0.513 (3)0.378 (3)0.4600 (17)0.071 (8)*
H1A0.162 (3)0.426 (3)0.0248 (17)0.054 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N50.0487 (10)0.0441 (10)0.0552 (10)−0.0028 (8)−0.0128 (8)−0.0215 (8)
N40.0477 (11)0.0475 (11)0.0665 (12)0.0030 (9)−0.0180 (9)−0.0281 (9)
C200.0533 (13)0.0543 (14)0.0685 (15)−0.0050 (11)−0.0214 (11)−0.0269 (12)
O40.0687 (11)0.0712 (12)0.1096 (14)0.0064 (9)−0.0348 (10)−0.0562 (11)
C130.0445 (11)0.0492 (13)0.0455 (11)−0.0056 (10)−0.0105 (9)−0.0132 (10)
C150.0492 (12)0.0451 (12)0.0441 (11)−0.0079 (10)−0.0100 (9)−0.0122 (9)
C180.0669 (15)0.0476 (13)0.0536 (13)−0.0128 (11)−0.0091 (11)−0.0209 (10)
C190.0583 (14)0.0495 (14)0.0731 (15)−0.0017 (11)−0.0171 (12)−0.0262 (12)
C160.0570 (13)0.0577 (14)0.0645 (14)−0.0059 (11)−0.0239 (11)−0.0204 (12)
N60.0906 (17)0.0570 (14)0.0680 (13)−0.0219 (13)−0.0070 (12)−0.0275 (11)
C120.0513 (13)0.0621 (15)0.0749 (16)0.0020 (11)−0.0226 (12)−0.0328 (13)
O60.1239 (17)0.0867 (15)0.1170 (17)−0.0298 (13)−0.0324 (14)−0.0567 (13)
O50.0999 (16)0.0583 (12)0.0976 (15)−0.0030 (11)−0.0112 (12)−0.0367 (11)
C140.0587 (15)0.0656 (16)0.0808 (17)0.0078 (12)−0.0275 (13)−0.0345 (13)
C170.0732 (16)0.0644 (16)0.0653 (15)−0.0189 (13)−0.0224 (13)−0.0250 (13)
N20.0469 (10)0.0518 (11)0.0593 (11)−0.0039 (9)−0.0174 (9)−0.0169 (9)
O10.0565 (10)0.0775 (12)0.0890 (12)0.0072 (9)−0.0307 (9)−0.0306 (10)
N10.0523 (11)0.0576 (12)0.0642 (12)−0.0025 (9)−0.0227 (10)−0.0222 (10)
C100.0500 (13)0.0439 (12)0.0622 (13)−0.0045 (10)−0.0143 (10)−0.0204 (10)
C30.0524 (13)0.0453 (13)0.0557 (13)−0.0062 (10)−0.0169 (10)−0.0164 (10)
C80.0481 (12)0.0546 (14)0.0582 (13)−0.0047 (11)−0.0146 (10)−0.0141 (11)
C50.0485 (12)0.0460 (12)0.0483 (12)−0.0071 (10)−0.0115 (9)−0.0148 (10)
C60.0635 (15)0.0550 (14)0.0718 (15)0.0016 (12)−0.0231 (12)−0.0330 (12)
C90.0518 (13)0.0522 (14)0.0634 (14)−0.0092 (11)−0.0140 (11)−0.0237 (11)
C70.0594 (15)0.0549 (15)0.0794 (17)0.0070 (12)−0.0170 (12)−0.0305 (13)
C20.0506 (13)0.0542 (14)0.0624 (14)−0.0043 (11)−0.0173 (11)−0.0148 (11)
N30.0552 (13)0.0743 (16)0.1008 (18)0.0038 (12)−0.0305 (12)−0.0271 (13)
C10.0635 (15)0.0743 (18)0.0880 (19)0.0043 (13)−0.0270 (14)−0.0383 (15)
C40.0746 (18)0.087 (2)0.105 (2)0.0091 (15)−0.0418 (16)−0.0579 (18)
O30.0844 (15)0.132 (2)0.159 (2)0.0139 (14)−0.0718 (15)−0.0699 (18)
O20.0765 (14)0.1116 (19)0.196 (3)0.0364 (14)−0.0630 (16)−0.0769 (19)
C110.0635 (17)0.089 (2)0.148 (3)0.0211 (15)−0.0522 (18)−0.070 (2)
Geometric parameters (Å, °) top
N5—C131.287 (3)N1—C21.349 (3)
N5—N41.368 (2)N1—H1A0.83 (2)
N4—C121.353 (3)C10—C91.372 (3)
N4—H4A0.88 (3)C10—C51.397 (3)
C20—C191.376 (3)C10—H10A0.9300
C20—C151.398 (3)C3—C51.489 (3)
C20—H20A0.9300C3—C41.500 (3)
O4—C121.231 (3)C8—C91.371 (3)
C13—C151.481 (3)C8—C71.376 (3)
C13—C141.493 (3)C8—N31.460 (3)
C15—C161.391 (3)C5—C61.389 (3)
C18—C171.367 (3)C6—C71.380 (3)
C18—C191.374 (3)C6—H6A0.9300
C18—N61.472 (3)C9—H9A0.9300
C19—H19A0.9300C7—H7A0.9300
C16—C171.389 (3)C2—C11.492 (3)
C16—H16A0.9300N3—O21.218 (3)
N6—O61.222 (3)N3—O31.219 (3)
N6—O51.223 (3)C1—H1B0.9600
C12—C111.489 (3)C1—H1C0.9600
C14—H14A0.9600C1—H1D0.9600
C14—H14B0.9600C4—H4B0.9600
C14—H14C0.9600C4—H4C0.9600
C17—H17A0.9300C4—H4D0.9600
N2—C31.277 (3)C11—H11A0.9600
N2—N11.368 (3)C11—H11B0.9600
O1—C21.232 (3)C11—H11C0.9600
C13—N5—N4119.06 (18)C5—C10—H10A119.3
C12—N4—N5119.98 (19)N2—C3—C5115.09 (19)
C12—N4—H4A114.2 (17)N2—C3—C4125.2 (2)
N5—N4—H4A125.8 (17)C5—C3—C4119.7 (2)
C19—C20—C15121.5 (2)C9—C8—C7122.0 (2)
C19—C20—H20A119.2C9—C8—N3118.9 (2)
C15—C20—H20A119.2C7—C8—N3119.1 (2)
N5—C13—C15114.65 (18)C6—C5—C10117.9 (2)
N5—C13—C14125.5 (2)C6—C5—C3122.1 (2)
C15—C13—C14119.81 (19)C10—C5—C3120.00 (19)
C16—C15—C20117.6 (2)C7—C6—C5121.2 (2)
C16—C15—C13121.3 (2)C7—C6—H6A119.4
C20—C15—C13121.07 (18)C5—C6—H6A119.4
C17—C18—C19121.9 (2)C8—C9—C10118.8 (2)
C17—C18—N6119.2 (2)C8—C9—H9A120.6
C19—C18—N6118.9 (2)C10—C9—H9A120.6
C18—C19—C20118.9 (2)C8—C7—C6118.7 (2)
C18—C19—H19A120.6C8—C7—H7A120.7
C20—C19—H19A120.6C6—C7—H7A120.7
C17—C16—C15121.3 (2)O1—C2—N1119.6 (2)
C17—C16—H16A119.4O1—C2—C1122.2 (2)
C15—C16—H16A119.4N1—C2—C1118.3 (2)
O6—N6—O5123.9 (2)O2—N3—O3122.8 (2)
O6—N6—C18117.5 (2)O2—N3—C8118.8 (2)
O5—N6—C18118.5 (2)O3—N3—C8118.4 (2)
O4—C12—N4120.0 (2)C2—C1—H1B109.5
O4—C12—C11121.8 (2)C2—C1—H1C109.5
N4—C12—C11118.2 (2)H1B—C1—H1C109.5
C13—C14—H14A109.5C2—C1—H1D109.5
C13—C14—H14B109.5H1B—C1—H1D109.5
H14A—C14—H14B109.5H1C—C1—H1D109.5
C13—C14—H14C109.5C3—C4—H4B109.5
H14A—C14—H14C109.5C3—C4—H4C109.5
H14B—C14—H14C109.5H4B—C4—H4C109.5
C18—C17—C16118.8 (2)C3—C4—H4D109.5
C18—C17—H17A120.6H4B—C4—H4D109.5
C16—C17—H17A120.6H4C—C4—H4D109.5
C3—N2—N1120.00 (19)C12—C11—H11A109.5
C2—N1—N2119.4 (2)C12—C11—H11B109.5
C2—N1—H1A118.7 (16)H11A—C11—H11B109.5
N2—N1—H1A121.5 (16)C12—C11—H11C109.5
C9—C10—C5121.4 (2)H11A—C11—H11C109.5
C9—C10—H10A119.3H11B—C11—H11C109.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.84 (3)2.16 (3)2.989 (3)170 (2)
N4—H4A···O4ii0.88 (3)2.08 (3)2.952 (3)172 (2)
C4—H4B···N10.962.422.826 (3)105
C4—H4B···O1i0.962.283.243 (3)175
C10—H10A···O6iii0.932.493.216 (3)135
C14—H14A···N40.962.412.821 (3)105
C14—H14A···O4ii0.962.363.317 (3)173
C16—H16A···O3iv0.932.503.388 (4)159
C20—H20A···N50.932.432.740 (3)100
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z+1; (iii) x, y+1, z; (iv) x−1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.84 (3)2.16 (3)2.989 (3)170 (2)
N4—H4A···O4ii0.88 (3)2.08 (3)2.952 (3)172 (2)
C4—H4B···N10.962.422.826 (3)105
C4—H4B···O1i0.962.283.243 (3)175
C10—H10A···O6iii0.932.493.216 (3)135
C14—H14A···N40.962.412.821 (3)105
C14—H14A···O4ii0.962.363.317 (3)173
C16—H16A···O3iv0.932.503.388 (4)159
C20—H20A···N50.932.432.740 (3)100
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z+1; (iii) x, y+1, z; (iv) x−1, y, z.
references
References top

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Cimerman, Z., Galic, N. & Bosner, B. (1997). Anal. Chim. Acta, 343, 145–153.

Girgis, A. S. (2006). J. Chem. Res. pp. 81–85.

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