(E)-4-Amino-N′-(3-nitro­benzyl­idene)benzohydrazide

Xu, S.-Q.

doi:10.1107/S1600536812014110

organic compounds

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Volume 68| Part 5| May 2012| Page o1320

doi:10.1107/S1600536812014110

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(E)-4-Amino-N′-(3-nitrobenzylidene)benzohydrazide

Shu-Qing Xu ^a ^*

^aSchool of Ocean, Qinzhou University, Qinzhou, Guangxi 535000, People's Republic of China
^*Correspondence e-mail: shuqing_xu@163.com

(Received 30 March 2012; accepted 31 March 2012; online 6 April 2012)

In the title compound, C₁₄H₁₂N₄O₃, the dihedral angle between the benzene rings is 7.6 (4)°. In the crystal, infinite sheets linked by N—H⋯O and bifurcated N—H⋯(O,N) hydrogen bonds propagate in the (10-1) plane, in which R₄⁴(36) loops are apparent. Neighbouring layers may interact by way of very weak π–π stacking interactions [centroid–centroid distances = 3.9329 (13) and 4.0702 (13) Å].

Related literature

For related structures and background references to hydrazones, see: Cao (2009 ); Zhou & Yang (2010 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₄H₁₂N₄O₃
M_r = 284.28
Monoclinic, P 2₁ /n
a = 7.8909 (16) Å
b = 11.153 (2) Å
c = 14.709 (3) Å
β = 92.00 (3)°
V = 1293.7 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.20 × 0.15 × 0.12 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.981, T_max = 0.987
11091 measured reflections
2952 independent reflections
2756 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.161
S = 1.06
2952 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N1ⁱ	0.86	2.47	3.183 (2)	141
N2—H2⋯O3ⁱⁱ	0.86	2.44	3.041 (2)	127
N1—H1A⋯O1ⁱⁱⁱ	0.89	2.27	3.106 (2)	156
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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/S1600536812014110/hb6724sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812014110/hb6724Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812014110/hb6724Isup3.cml

checkCIF report

Comment top

As an extension of recent studies of hydrazone Schiff bases, (Cao, 2009; Zhou & Yang, 2010), the title compound was prepared and characterized.

As shown in Fig. 1, the asymmetric unit of the title compound, (I), contains one independent molecule displaying an E configuration with respect to its C═N double bond. The dihedral angle between the two benzene rings is 7.6 (4) °. The bond lengths and angles are as expected for a compound of this type and agree with the other ligands belonging to the hydrazone series. The C8═N3 and C7═O1 bond lengths of 1.283 (2) and 1.228 (2) Å, respectively, conform to the values for double bonds. Whereas the C1-N1, C8-N3, C11-N4 and N2-N3 [1.385 (2), 1.360 (2), 1.466 (2) and 1.378 (2) Å, respectively] bond lengths correspond to a single bond. In the crystal packing, it is noted that one of amino H (H1A) and amide H2 are involved in forming intermolecular N—H···O and N—H···N hydrogen bonds, which link the molecules into a R⁴₄(36) graph-set notation (Fig. 2 and Table 1). These rings form an alternating sequence, in turn, linking the molecules into a two-dimensional supramolecular sheet structure parallel to (101). Neighboring layers are further interacting with each other through weak π–π stacking interactions [centroid to centroid distances of the benzene C1/C6 and C9/C14 rings are 3.93 (6) and 4.07 (6) Å].

Related literature top

For related structures and background references to hydrazones, see: Cao (2009); Zhou & Yang (2010). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

3-Nitrobenzaldehyde (1 mmol, 0.151 g) and 4-aminobenzohydrazide (1 mmol, 0.151 g) were dissolved in MeOH (20 ml). The mixture was stirred for 6 hours at room temperature to give a yellow solution. Yellow prisms were formed by gradual evaporation of the solvent over a period of 5 days at room temperature.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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, with displacement ellipsoids at the 30% probability level.
	Fig. 2. Crystal packing in the title compound where molecules are linked via N–H···O hydrogen bonds (dashed lines). Except for those involved in hydrogen-bonding interactions, H atoms have been omitted for clarity.

(E)-4-Amino-N'-(3-nitrobenzylidene)benzohydrazide top

Crystal data top

C₁₄H₁₂N₄O₃	F(000) = 592
M_r = 284.28	D_x = 1.460 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3352 reflections
a = 7.8909 (16) Å	θ = 1.4–27.5°
b = 11.153 (2) Å	µ = 0.11 mm⁻¹
c = 14.709 (3) Å	T = 296 K
β = 92.00 (3)°	Prism, yellow
V = 1293.7 (4) Å³	0.20 × 0.15 × 0.12 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	2952 independent reflections
Radiation source: fine-focus sealed tube	2756 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.981, T_max = 0.987	k = −14→14
11091 measured reflections	l = −19→18

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.161	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0851P)² + 0.6295P] where P = (F_o² + 2F_c²)/3
2952 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₄H₁₂N₄O₃	V = 1293.7 (4) Å³
M_r = 284.28	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.8909 (16) Å	µ = 0.11 mm⁻¹
b = 11.153 (2) Å	T = 296 K
c = 14.709 (3) Å	0.20 × 0.15 × 0.12 mm
β = 92.00 (3)°

Data collection top

Bruker SMART CCD diffractometer	2952 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2756 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.987	R_int = 0.044
11091 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.161	H-atom parameters constrained
S = 1.06	Δρ_max = 0.22 e Å⁻³
2952 reflections	Δρ_min = −0.22 e Å⁻³
190 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
O1	0.13734 (17)	0.68729 (12)	0.42167 (9)	0.0318 (3)
O2	−0.0202 (2)	0.28779 (13)	0.14494 (10)	0.0405 (4)
O3	0.00112 (17)	0.09872 (13)	0.11390 (9)	0.0352 (4)
N1	0.3895 (2)	0.95096 (15)	0.79084 (11)	0.0333 (4)
H1B	0.3783	1.0286	0.7780	0.040*
H1A	0.4796	0.9306	0.8255	0.040*
N2	0.2130 (2)	0.52763 (13)	0.50999 (10)	0.0280 (4)
H2	0.2400	0.5032	0.5640	0.034*
N3	0.18734 (19)	0.44493 (14)	0.44124 (10)	0.0270 (3)
N4	0.02597 (19)	0.18540 (14)	0.16438 (10)	0.0286 (4)
C1	0.3493 (2)	0.87791 (17)	0.71707 (12)	0.0266 (4)
C2	0.2528 (2)	0.92102 (17)	0.64211 (12)	0.0294 (4)
H2A	0.2201	1.0011	0.6402	0.035*
C3	0.2060 (2)	0.84555 (16)	0.57111 (12)	0.0278 (4)
H3	0.1413	0.8756	0.5222	0.033*
C4	0.2540 (2)	0.72489 (16)	0.57130 (12)	0.0253 (4)
C5	0.3551 (2)	0.68367 (17)	0.64523 (12)	0.0286 (4)
H5	0.3921	0.6045	0.6459	0.034*
C6	0.4007 (2)	0.75809 (17)	0.71689 (12)	0.0289 (4)
H6	0.4663	0.7282	0.7655	0.035*
C7	0.1965 (2)	0.64721 (16)	0.49378 (12)	0.0259 (4)
C8	0.2188 (2)	0.33609 (17)	0.46441 (12)	0.0288 (4)
H8	0.2524	0.3187	0.5242	0.035*
C9	0.2025 (2)	0.23928 (16)	0.39805 (12)	0.0272 (4)
C10	0.1297 (2)	0.25889 (16)	0.31199 (12)	0.0262 (4)
H10	0.0924	0.3350	0.2949	0.031*
C11	0.1133 (2)	0.16422 (16)	0.25250 (12)	0.0259 (4)
C12	0.1707 (2)	0.04973 (17)	0.27327 (13)	0.0317 (4)
H12	0.1596	−0.0123	0.2312	0.038*
C13	0.2455 (3)	0.03068 (17)	0.35892 (14)	0.0345 (4)
H13	0.2862	−0.0450	0.3748	0.041*
C14	0.2596 (2)	0.12410 (18)	0.42087 (13)	0.0320 (4)
H14	0.3078	0.1100	0.4785	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0356 (7)	0.0343 (7)	0.0249 (7)	0.0026 (6)	−0.0065 (5)	0.0016 (5)
O2	0.0494 (9)	0.0321 (8)	0.0390 (8)	0.0013 (6)	−0.0126 (7)	0.0013 (6)
O3	0.0339 (7)	0.0356 (7)	0.0356 (7)	−0.0054 (6)	−0.0054 (6)	−0.0092 (6)
N1	0.0338 (9)	0.0346 (9)	0.0312 (8)	−0.0009 (7)	−0.0027 (7)	−0.0080 (7)
N2	0.0357 (8)	0.0278 (8)	0.0200 (7)	−0.0016 (6)	−0.0046 (6)	−0.0012 (6)
N3	0.0278 (8)	0.0290 (8)	0.0240 (7)	−0.0020 (6)	−0.0015 (6)	−0.0035 (6)
N4	0.0267 (8)	0.0298 (8)	0.0294 (8)	−0.0023 (6)	−0.0011 (6)	−0.0009 (6)
C1	0.0210 (8)	0.0326 (9)	0.0262 (9)	−0.0028 (7)	0.0021 (6)	−0.0045 (7)
C2	0.0314 (9)	0.0256 (8)	0.0312 (9)	−0.0025 (7)	0.0011 (7)	−0.0001 (7)
C3	0.0277 (9)	0.0288 (9)	0.0267 (9)	−0.0001 (7)	−0.0016 (7)	0.0021 (7)
C4	0.0237 (8)	0.0290 (9)	0.0233 (8)	−0.0012 (7)	0.0008 (6)	−0.0008 (7)
C5	0.0282 (9)	0.0270 (9)	0.0302 (9)	0.0004 (7)	−0.0031 (7)	−0.0019 (7)
C6	0.0263 (9)	0.0344 (10)	0.0255 (9)	0.0006 (7)	−0.0057 (7)	−0.0009 (7)
C7	0.0233 (8)	0.0302 (9)	0.0239 (8)	0.0002 (7)	−0.0008 (6)	0.0000 (7)
C8	0.0283 (9)	0.0320 (9)	0.0256 (9)	0.0004 (7)	−0.0043 (7)	−0.0011 (7)
C9	0.0248 (8)	0.0292 (9)	0.0274 (9)	−0.0001 (7)	−0.0011 (7)	−0.0008 (7)
C10	0.0233 (8)	0.0258 (8)	0.0294 (9)	−0.0009 (7)	0.0002 (7)	−0.0005 (7)
C11	0.0240 (8)	0.0282 (9)	0.0254 (9)	−0.0017 (7)	0.0001 (7)	−0.0002 (7)
C12	0.0343 (10)	0.0271 (9)	0.0337 (10)	0.0014 (8)	0.0025 (8)	−0.0030 (7)
C13	0.0377 (10)	0.0282 (9)	0.0376 (10)	0.0084 (8)	0.0013 (8)	0.0012 (8)
C14	0.0323 (10)	0.0344 (10)	0.0292 (9)	0.0046 (8)	−0.0017 (7)	0.0030 (7)

Geometric parameters (Å, º) top

O1—C7	1.228 (2)	C4—C5	1.403 (3)
O2—N4	1.229 (2)	C4—C7	1.490 (2)
O3—N4	1.231 (2)	C5—C6	1.380 (2)
N1—C1	1.385 (2)	C5—H5	0.9300
N1—H1B	0.8899	C6—H6	0.9300
N1—H1A	0.8900	C8—C9	1.458 (2)
N2—C7	1.360 (2)	C8—H8	0.9300
N2—N3	1.378 (2)	C9—C10	1.389 (3)
N2—H2	0.8600	C9—C14	1.398 (3)
N3—C8	1.283 (2)	C10—C11	1.375 (2)
N4—C11	1.466 (2)	C10—H10	0.9300
C1—C6	1.397 (3)	C11—C12	1.385 (3)
C1—C2	1.403 (3)	C12—C13	1.389 (3)
C2—C3	1.382 (3)	C12—H12	0.9300
C2—H2A	0.9300	C13—C14	1.386 (3)
C3—C4	1.398 (3)	C13—H13	0.9300
C3—H3	0.9300	C14—H14	0.9300

C1—N1—H1B	112.8	C5—C6—H6	119.7
C1—N1—H1A	117.1	C1—C6—H6	119.7
H1B—N1—H1A	116.1	O1—C7—N2	122.65 (17)
C7—N2—N3	121.12 (15)	O1—C7—C4	123.07 (17)
C7—N2—H2	119.4	N2—C7—C4	114.27 (15)
N3—N2—H2	119.4	N3—C8—C9	120.75 (17)
C8—N3—N2	114.60 (15)	N3—C8—H8	119.6
O2—N4—O3	123.35 (16)	C9—C8—H8	119.6
O2—N4—C11	118.80 (15)	C10—C9—C14	118.88 (17)
O3—N4—C11	117.84 (15)	C10—C9—C8	121.15 (17)
N1—C1—C6	120.38 (17)	C14—C9—C8	119.97 (16)
N1—C1—C2	121.16 (17)	C11—C10—C9	119.06 (17)
C6—C1—C2	118.44 (17)	C11—C10—H10	120.5
C3—C2—C1	120.58 (17)	C9—C10—H10	120.5
C3—C2—H2A	119.7	C10—C11—C12	123.03 (17)
C1—C2—H2A	119.7	C10—C11—N4	118.02 (16)
C2—C3—C4	121.31 (17)	C12—C11—N4	118.92 (16)
C2—C3—H3	119.3	C11—C12—C13	117.80 (17)
C4—C3—H3	119.3	C11—C12—H12	121.1
C3—C4—C5	117.62 (16)	C13—C12—H12	121.1
C3—C4—C7	118.86 (16)	C14—C13—C12	120.21 (18)
C5—C4—C7	123.52 (17)	C14—C13—H13	119.9
C6—C5—C4	121.40 (17)	C12—C13—H13	119.9
C6—C5—H5	119.3	C13—C14—C9	120.99 (18)
C4—C5—H5	119.3	C13—C14—H14	119.5
C5—C6—C1	120.60 (17)	C9—C14—H14	119.5

C7—N2—N3—C8	175.27 (16)	N2—N3—C8—C9	−178.03 (15)
N1—C1—C2—C3	−176.57 (17)	N3—C8—C9—C10	−9.4 (3)
C6—C1—C2—C3	1.8 (3)	N3—C8—C9—C14	171.08 (18)
C1—C2—C3—C4	−0.5 (3)	C14—C9—C10—C11	1.1 (3)
C2—C3—C4—C5	−1.5 (3)	C8—C9—C10—C11	−178.44 (16)
C2—C3—C4—C7	178.64 (16)	C9—C10—C11—C12	−1.9 (3)
C3—C4—C5—C6	2.3 (3)	C9—C10—C11—N4	176.03 (15)
C7—C4—C5—C6	−177.89 (17)	O2—N4—C11—C10	4.2 (2)
C4—C5—C6—C1	−1.0 (3)	O3—N4—C11—C10	−175.03 (16)
N1—C1—C6—C5	177.33 (17)	O2—N4—C11—C12	−177.78 (17)
C2—C1—C6—C5	−1.1 (3)	O3—N4—C11—C12	3.0 (2)
N3—N2—C7—O1	9.7 (3)	C10—C11—C12—C13	1.0 (3)
N3—N2—C7—C4	−171.05 (15)	N4—C11—C12—C13	−176.84 (16)
C3—C4—C7—O1	14.6 (3)	C11—C12—C13—C14	0.6 (3)
C5—C4—C7—O1	−165.29 (17)	C12—C13—C14—C9	−1.3 (3)
C3—C4—C7—N2	−164.70 (16)	C10—C9—C14—C13	0.5 (3)
C5—C4—C7—N2	15.5 (3)	C8—C9—C14—C13	180.00 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1ⁱ	0.86	2.47	3.183 (2)	141
N2—H2···O3ⁱⁱ	0.86	2.44	3.041 (2)	127
N1—H1A···O1ⁱⁱⁱ	0.89	2.27	3.106 (2)	156

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂N₄O₃
M_r	284.28
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	7.8909 (16), 11.153 (2), 14.709 (3)
β (°)	92.00 (3)
V (Å³)	1293.7 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.20 × 0.15 × 0.12

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.981, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	11091, 2952, 2756
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.161, 1.06
No. of reflections	2952
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.22

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), 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
N2—H2···N1ⁱ	0.86	2.47	3.183 (2)	141
N2—H2···O3ⁱⁱ	0.86	2.44	3.041 (2)	127
N1—H1A···O1ⁱⁱⁱ	0.89	2.27	3.106 (2)	156

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

Acknowledgements

This work was supported by the Natural Science Foundation of Guangxi Province (grant No. 2011GXNSFA018123). The author also acknowledges financial support from the Natural Science Foundation of Education Bureau of Guangxi Province (grant No. 201106LX537).

References

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