(E)-4-Hydr­oxy-N′-(4-nitro­benzyl­idene)benzohydrazide

Li, C.-M.; Ban, H.-Y.

doi:10.1107/S1600536809020066

organic compounds

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Volume 65| Part 7| July 2009| Page o1466

doi:10.1107/S1600536809020066

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(E)-4-Hydroxy-N′-(4-nitrobenzylidene)benzohydrazide

Cong-Ming Li ^a ^* and Hong-Yan Ban ^b

^aCollege of Science, Shenyang University, Shenyang 110044, People's Republic of China, and ^bSchool of Chemical Engineering, University of Science and Technology Liaoning, Anshan 114051, People's Republic of China
^*Correspondence e-mail: hongyan_ban@163.com

(Received 22 May 2009; accepted 26 May 2009; online 6 June 2009)

The molecule of the title compound, C₁₄H₁₁N₃O₄, is approximately planar, the dihedral angle between the planes of the two substituted benzene rings being 2.54 (7)°. The molecule exists in a trans configuration with respect to the central methylidene unit. In the crystal structure, molecules are linked through intermolecular O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds, forming layers parallel to (101). The O/N—H⋯O and C—H⋯O interactions form a pair of bifurcated acceptor bonds involving the cabonyl/nitro O atom, generating an R₂¹(6) motif.

Related literature

For the biological activity of hydrazones, see: Zhong et al. (2007 ); Raj et al. (2007 ); Jimenez-Pulido et al. (2008 ). For related structures, see: Ban & Li (2008a ,b ); Li & Ban (2009a ,b ); Yehye et al. (2008 ); Fun et al. (2008a ,b ); Yang et al. (2008 ); Ejsmont et al. (2008 ).

Experimental

Crystal data

C₁₄H₁₁N₃O₄
M_r = 285.26
Monoclinic, P 2₁ /n
a = 7.659 (1) Å
b = 13.587 (2) Å
c = 12.561 (2) Å
β = 92.784 (5)°
V = 1305.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 298 K
0.20 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.979, T_max = 0.981
7862 measured reflections
2835 independent reflections
2109 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.111
S = 1.04
2835 reflections
195 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.82	2.02	2.8131 (15)	164
N2—H2B⋯O4ⁱⁱ	0.90 (1)	2.22 (1)	3.0513 (17)	155 (2)
C7—H7⋯O4ⁱⁱ	0.93	2.41	3.235 (2)	148
C13—H13⋯O1ⁱ	0.93	2.35	3.0713 (19)	134
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{5\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809020066/ci2812sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809020066/ci2812Isup2.hkl

checkCIF report

Comment top

Schiff bases derived from the condensation of aldehydes with hydrazides have been demonstrated to possess excellent biological activities (Zhong et al., 2007; Raj et al., 2007; Jimenez-Pulido et al., 2008). Due to the easy synthesis of such compounds, a great deal of Schiff bases have been synthesized and structurally characterized (Yehye et al., 2008; Fun et al., 2008a,b; Yang et al., 2008; Ejsmont et al., 2008). Recently, we have reported a few such compounds (Ban & Li, 2008a,b; Li & Ban, 2009a,b). We report here the crystal structure of the title new compound.

The title Schiff base molecule (Fig. 1) is nearly planar, with the dihedral angle between the two benzene rings being 2.54 (7)°. The molecule exists in a trans configuration with respect to the central methylidene (C7═N1) unit. The N2—N1—C7—C1 torsion angle is 179.12 (14)°.

In the crystal structure, the molecules are linked through intermolecular O—H···O and N—H···O hydrogen bonds (Table 1), forming layers parallel to the (101) (Fig. 2). Within the layer, C—H···O hydrogen bonds are also observed.

Related literature top

For the biological activity of hydrazones, see: Zhong et al. (2007); Raj et al. (2007); Jimenez-Pulido et al. (2008). For related structures, see: Ban & Li (2008a,b); Li & Ban (2009a,b); Yehye et al. (2008); Fun et al. (2008a,b); Yang et al. (2008); Ejsmont et al. (2008).

Experimental top

The title compound was prepared by refluxing 4-nitrobenzaldehyde (1.0 mol) with 4-hydroxybenzohydrazide (1.0 mol) in methanol (100 ml). Excess methanol was removed from the mixture by distillation. A colourless solid product was filtered, and washed three times with methanol. Colourless block-shaped crystals of the title compound were obtained from a methanol solution by slow evaporation in air.

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids for the non-hydrogen atoms.
	Fig. 2. The packing diagram of the title compound, viewed along the a axis. Hydrogen bonds are shown as dashed lines.

(E)-4-Hydroxy-N'-(4-nitrobenzylidene)benzohydrazide top

Crystal data top

C₁₄H₁₁N₃O₄	F(000) = 592
M_r = 285.26	D_x = 1.451 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2390 reflections
a = 7.659 (1) Å	θ = 3.0–30.5°
b = 13.587 (2) Å	µ = 0.11 mm⁻¹
c = 12.561 (2) Å	T = 298 K
β = 92.784 (5)°	Block, colourless
V = 1305.6 (3) Å³	0.20 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2835 independent reflections
Radiation source: fine-focus sealed tube	2109 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω scans	θ_max = 27.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.979, T_max = 0.981	k = −17→15
7862 measured reflections	l = −15→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0467P)² + 0.3196P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
2835 reflections	Δρ_max = 0.21 e Å⁻³
195 parameters	Δρ_min = −0.13 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0104 (15)

Crystal data top

C₁₄H₁₁N₃O₄	V = 1305.6 (3) Å³
M_r = 285.26	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.659 (1) Å	µ = 0.11 mm⁻¹
b = 13.587 (2) Å	T = 298 K
c = 12.561 (2) Å	0.20 × 0.20 × 0.18 mm
β = 92.784 (5)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2835 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2109 reflections with I > 2σ(I)
T_min = 0.979, T_max = 0.981	R_int = 0.027
7862 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	1 restraint
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.21 e Å⁻³
2835 reflections	Δρ_min = −0.13 e Å⁻³
195 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
N1	0.20673 (17)	0.97706 (9)	1.04460 (10)	0.0410 (3)
N2	0.26363 (19)	1.05171 (9)	0.98149 (10)	0.0431 (3)
N3	0.0157 (2)	0.54652 (10)	1.21921 (11)	0.0504 (4)
O1	0.18428 (15)	1.16731 (8)	1.09824 (8)	0.0472 (3)
O2	0.51173 (18)	1.44263 (8)	0.75115 (9)	0.0541 (3)
H2	0.5548	1.4194	0.6982	0.081*
O3	0.0321 (2)	0.46801 (10)	1.17422 (12)	0.0883 (6)
O4	−0.04623 (18)	0.55386 (9)	1.30667 (10)	0.0611 (4)
C1	0.1672 (2)	0.80400 (11)	1.06387 (12)	0.0391 (4)
C2	0.1011 (2)	0.80979 (11)	1.16524 (12)	0.0423 (4)
H2A	0.0898	0.8707	1.1980	0.051*
C3	0.0527 (2)	0.72557 (12)	1.21665 (12)	0.0418 (4)
H3	0.0085	0.7288	1.2842	0.050*
C4	0.0707 (2)	0.63608 (11)	1.16619 (12)	0.0402 (4)
C5	0.1366 (2)	0.62796 (12)	1.06648 (13)	0.0455 (4)
H5	0.1483	0.5668	1.0344	0.055*
C6	0.1845 (2)	0.71259 (12)	1.01580 (12)	0.0450 (4)
H6	0.2290	0.7087	0.9484	0.054*
C7	0.2198 (2)	0.89103 (11)	1.00586 (13)	0.0439 (4)
H7	0.2642	0.8835	0.9387	0.053*
C8	0.25098 (19)	1.14649 (11)	1.01458 (11)	0.0354 (3)
C9	0.32220 (19)	1.22217 (11)	0.94326 (11)	0.0348 (3)
C10	0.3187 (2)	1.32057 (11)	0.97329 (12)	0.0404 (4)
H10	0.2734	1.3378	1.0381	0.048*
C11	0.3812 (2)	1.39297 (11)	0.90850 (13)	0.0447 (4)
H11	0.3772	1.4585	0.9298	0.054*
C12	0.4503 (2)	1.36889 (11)	0.81144 (12)	0.0390 (4)
C13	0.4543 (2)	1.27096 (11)	0.78040 (12)	0.0410 (4)
H13	0.4995	1.2538	0.7156	0.049*
C14	0.3915 (2)	1.19946 (11)	0.84559 (12)	0.0403 (4)
H14	0.3952	1.1340	0.8240	0.048*
H2B	0.303 (3)	1.0358 (15)	0.9176 (10)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0486 (8)	0.0377 (7)	0.0377 (7)	−0.0014 (6)	0.0127 (6)	0.0081 (6)
N2	0.0616 (9)	0.0335 (7)	0.0359 (7)	−0.0021 (6)	0.0200 (6)	0.0028 (5)
N3	0.0650 (10)	0.0397 (8)	0.0477 (8)	−0.0055 (7)	0.0146 (7)	0.0081 (6)
O1	0.0630 (7)	0.0441 (6)	0.0364 (6)	0.0005 (5)	0.0217 (5)	−0.0009 (5)
O2	0.0760 (9)	0.0361 (6)	0.0525 (7)	−0.0056 (6)	0.0280 (6)	0.0047 (5)
O3	0.1579 (16)	0.0359 (7)	0.0749 (10)	−0.0156 (9)	0.0465 (10)	−0.0013 (7)
O4	0.0814 (9)	0.0505 (7)	0.0537 (7)	−0.0059 (6)	0.0289 (7)	0.0118 (6)
C1	0.0401 (8)	0.0381 (8)	0.0395 (8)	−0.0015 (6)	0.0068 (6)	0.0070 (6)
C2	0.0511 (10)	0.0350 (8)	0.0413 (9)	−0.0008 (7)	0.0087 (7)	0.0012 (6)
C3	0.0477 (9)	0.0425 (9)	0.0358 (8)	0.0001 (7)	0.0103 (7)	0.0051 (7)
C4	0.0440 (9)	0.0364 (8)	0.0408 (8)	−0.0029 (7)	0.0073 (7)	0.0076 (6)
C5	0.0563 (10)	0.0368 (8)	0.0446 (9)	−0.0019 (7)	0.0129 (8)	0.0002 (7)
C6	0.0546 (10)	0.0436 (9)	0.0379 (8)	−0.0008 (7)	0.0141 (7)	0.0029 (7)
C7	0.0526 (10)	0.0418 (9)	0.0384 (8)	−0.0023 (7)	0.0135 (7)	0.0047 (7)
C8	0.0375 (8)	0.0388 (8)	0.0307 (7)	0.0026 (6)	0.0091 (6)	0.0001 (6)
C9	0.0378 (8)	0.0342 (7)	0.0331 (7)	0.0017 (6)	0.0095 (6)	−0.0003 (6)
C10	0.0495 (9)	0.0379 (8)	0.0352 (8)	0.0012 (7)	0.0158 (7)	−0.0050 (6)
C11	0.0568 (10)	0.0313 (8)	0.0473 (9)	−0.0003 (7)	0.0161 (7)	−0.0051 (7)
C12	0.0432 (9)	0.0333 (7)	0.0414 (8)	−0.0014 (6)	0.0111 (7)	0.0027 (6)
C13	0.0516 (9)	0.0385 (8)	0.0345 (8)	−0.0003 (7)	0.0178 (7)	−0.0022 (6)
C14	0.0529 (9)	0.0302 (7)	0.0394 (8)	−0.0006 (6)	0.0165 (7)	−0.0034 (6)

Geometric parameters (Å, º) top

N1—C7	1.272 (2)	C4—C5	1.377 (2)
N1—N2	1.3714 (17)	C5—C6	1.373 (2)
N2—C8	1.3581 (19)	C5—H5	0.93
N2—H2B	0.899 (9)	C6—H6	0.93
N3—O3	1.2164 (18)	C7—H7	0.93
N3—O4	1.2219 (17)	C8—C9	1.4848 (19)
N3—C4	1.4590 (19)	C9—C10	1.390 (2)
O1—C8	1.2237 (16)	C9—C14	1.395 (2)
O2—C12	1.3539 (17)	C10—C11	1.377 (2)
O2—H2	0.82	C10—H10	0.93
C1—C6	1.390 (2)	C11—C12	1.392 (2)
C1—C2	1.395 (2)	C11—H11	0.93
C1—C7	1.456 (2)	C12—C13	1.387 (2)
C2—C3	1.374 (2)	C13—C14	1.373 (2)
C2—H2A	0.93	C13—H13	0.93
C3—C4	1.381 (2)	C14—H14	0.93
C3—H3	0.93

C7—N1—N2	115.18 (12)	C1—C6—H6	119.5
C8—N2—N1	119.67 (12)	N1—C7—C1	121.73 (14)
C8—N2—H2B	122.3 (14)	N1—C7—H7	119.1
N1—N2—H2B	117.9 (14)	C1—C7—H7	119.1
O3—N3—O4	122.86 (14)	O1—C8—N2	121.40 (13)
O3—N3—C4	118.74 (14)	O1—C8—C9	122.61 (13)
O4—N3—C4	118.40 (14)	N2—C8—C9	115.99 (12)
C12—O2—H2	109.5	C10—C9—C14	117.70 (13)
C6—C1—C2	119.55 (14)	C10—C9—C8	119.34 (13)
C6—C1—C7	118.28 (14)	C14—C9—C8	122.96 (13)
C2—C1—C7	122.18 (14)	C11—C10—C9	120.99 (14)
C3—C2—C1	120.02 (14)	C11—C10—H10	119.5
C3—C2—H2A	120.0	C9—C10—H10	119.5
C1—C2—H2A	120.0	C10—C11—C12	120.51 (14)
C2—C3—C4	118.84 (14)	C10—C11—H11	119.7
C2—C3—H3	120.6	C12—C11—H11	119.7
C4—C3—H3	120.6	O2—C12—C13	122.66 (13)
C5—C4—C3	122.48 (14)	O2—C12—C11	118.25 (13)
C5—C4—N3	118.35 (14)	C13—C12—C11	119.09 (14)
C3—C4—N3	119.16 (13)	C14—C13—C12	119.87 (13)
C6—C5—C4	118.20 (15)	C14—C13—H13	120.1
C6—C5—H5	120.9	C12—C13—H13	120.1
C4—C5—H5	120.9	C13—C14—C9	121.84 (14)
C5—C6—C1	120.91 (14)	C13—C14—H14	119.1
C5—C6—H6	119.5	C9—C14—H14	119.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.82	2.02	2.8131 (15)	164
N2—H2B···O4ⁱⁱ	0.90 (1)	2.22 (1)	3.0513 (17)	155 (2)
C7—H7···O4ⁱⁱ	0.93	2.41	3.235 (2)	148
C13—H13···O1ⁱ	0.93	2.35	3.0713 (19)	134

Symmetry codes: (i) x+1/2, −y+5/2, z−1/2; (ii) x+1/2, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁N₃O₄
M_r	285.26
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	7.659 (1), 13.587 (2), 12.561 (2)
β (°)	92.784 (5)
V (Å³)	1305.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.20 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.979, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	7862, 2835, 2109
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.111, 1.04
No. of reflections	2835
No. of parameters	195
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.13

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.82	2.02	2.8131 (15)	164
N2—H2B···O4ⁱⁱ	0.90 (1)	2.22 (1)	3.0513 (17)	155 (2)
C7—H7···O4ⁱⁱ	0.93	2.41	3.235 (2)	148
C13—H13···O1ⁱ	0.93	2.35	3.0713 (19)	134

Symmetry codes: (i) x+1/2, −y+5/2, z−1/2; (ii) x+1/2, −y+3/2, z−1/2.

Acknowledgements

The authors acknowledge financial support by the Research Foundation of Liaoning Province (grant No. 2008470).

References

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