2-Nitro-N′-[1-(pyridin-2-yl)ethyl­idene]benzohydrazide

Li, X.; An, Y.; Chen, Y.; Chen, L.

doi:10.1107/S1600536811049257

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3353

https://doi.org/10.1107/S1600536811049257

Open

access

2-Nitro-N′-[1-(pyridin-2-yl)ethylidene]benzohydrazide

Xiaofeng Li,^a Yan An,^a ^* Yiqing Chen ^a and Lishen Chen ^a

^aInstitute of Marine Materials Science and Engineering, Shanghai Maritime University, Shanghai 201306, People's Republic of China
^*Correspondence e-mail: yanan@shmtu.edu.cn

(Received 1 November 2011; accepted 8 November 2011; online 19 November 2011)

In the title compound, C₁₄H₁₂N₄O₃, the dihedral angle between the benzene ring and the pyridine ring is 60.9 (2)°. The major twist in the molecule occurs about the (NH)—(CO)—C_ar—C_ar (ar = aromatic) bond, the relevant torsion angle being 63.97 (12)°. In the crystal, inversion dimers linked by pairs of N—H⋯O hydrogen bonds generate R₂²(8) loops.

Related literature

For related structures, see: Mangalam et al. (2009 ); Tang (2011 ).

Experimental

Crystal data

C₁₄H₁₂N₄O₃
M_r = 284.28
Monoclinic, P 2₁ /n
a = 10.8303 (8) Å
b = 8.9112 (7) Å
c = 14.9437 (11) Å
β = 101.483 (1)°
V = 1413.36 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.20 × 0.20 × 0.18 mm

Data collection

Bruker SMART 1K CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.981, T_max = 0.983
7984 measured reflections
3048 independent reflections
2358 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.126
S = 1.05
3048 reflections
194 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O1ⁱ	0.90 (1)	2.13 (1)	3.0290 (15)	173 (2)
Symmetry code: (i) -x, -y+1, -z.

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 I, global. DOI: https://doi.org/10.1107/S1600536811049257/hb6488sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811049257/hb6488Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811049257/hb6488Isup3.cml

checkCIF report

Comment top

As a continuation of the work on the structures of hydrazone compounds the title compound, (I), is now described.

The molecular structure of the title compound is shown as Fig. 1. The dihedral angle between the benzene ring and the pyridine ring is 60.9 (2)°, indicating the molecule of the compound is much distorted. The bond distances comparable to the values observed in similar compounds (Tang, 2011; Mangalam et al., 2009).

In the crystal structure of the compound, adjacent two molecules are linked through two intermolecular N—H···O hydrogen bonds (Table 1) to form a dimer (Fig. 2).

Related literature top

For related structures, see: Mangalam et al. (2009); Tang (2011).

Experimental top

Equimolar quantities (0.5 mmol each) of 2-acetylpyridine and 2-nitrobenzohydrazide were mixed in 30 ml me thanol. The mixture was stirred at reflux for 30 min and cooled to room temperature. Yellow block-shaped single crytals were formed by slow evaporation of the solvent in air.

Structure description top

As a continuation of the work on the structures of hydrazone compounds the title compound, (I), is now described.

In the crystal structure of the compound, adjacent two molecules are linked through two intermolecular N—H···O hydrogen bonds (Table 1) to form a dimer (Fig. 2).

For related structures, see: Mangalam et al. (2009); Tang (2011).

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 the displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The molecular packing of the title compound, viewed along the c axis. Intermolecular N—H···O hydrogen-bonds are shown as dashed lines. H-atoms not involved in the hydrogen bonding have been omitted.

2-Nitro-N'-[1-(pyridin-2-yl)ethylidene]benzohydrazide top

Crystal data top

C₁₄H₁₂N₄O₃	F(000) = 592
M_r = 284.28	D_x = 1.336 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3300 reflections
a = 10.8303 (8) Å	θ = 2.6–28.3°
b = 8.9112 (7) Å	µ = 0.10 mm⁻¹
c = 14.9437 (11) Å	T = 298 K
β = 101.483 (1)°	Block, yellow
V = 1413.36 (18) Å³	0.20 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker SMART 1K CCD diffractometer	3048 independent reflections
Radiation source: fine-focus sealed tube	2358 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
ω scan	θ_max = 27.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→9
T_min = 0.981, T_max = 0.983	k = −11→11
7984 measured reflections	l = −18→19

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0611P)² + 0.2704P] where P = (F_o² + 2F_c²)/3
3048 reflections	(Δ/σ)_max < 0.001
194 parameters	Δρ_max = 0.23 e Å⁻³
1 restraint	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₄H₁₂N₄O₃	V = 1413.36 (18) Å³
M_r = 284.28	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.8303 (8) Å	µ = 0.10 mm⁻¹
b = 8.9112 (7) Å	T = 298 K
c = 14.9437 (11) Å	0.20 × 0.20 × 0.18 mm
β = 101.483 (1)°

Data collection top

Bruker SMART 1K CCD diffractometer	3048 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2358 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.983	R_int = 0.015
7984 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	1 restraint
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.23 e Å⁻³
3048 reflections	Δρ_min = −0.19 e Å⁻³
194 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
N1	0.12218 (13)	1.12660 (15)	0.19162 (9)	0.0549 (3)
N2	0.13344 (11)	0.83590 (12)	0.03440 (8)	0.0444 (3)
N3	0.09007 (12)	0.69373 (13)	0.00993 (8)	0.0476 (3)
N4	0.39424 (14)	0.72128 (18)	0.02669 (11)	0.0702 (4)
O1	0.09268 (11)	0.50167 (12)	−0.08683 (8)	0.0591 (3)
O2	0.47052 (19)	0.8063 (2)	0.07159 (12)	0.1265 (8)
O3	0.36144 (14)	0.60537 (16)	0.05665 (10)	0.0845 (4)
C1	0.14756 (12)	1.05765 (15)	0.11797 (9)	0.0416 (3)
C2	0.21742 (15)	1.12613 (17)	0.06083 (11)	0.0535 (4)
H2	0.2356	1.0747	0.0109	0.064*
C3	0.25946 (17)	1.27091 (18)	0.07897 (13)	0.0629 (4)
H3A	0.3046	1.3194	0.0407	0.075*
C4	0.23368 (17)	1.34274 (18)	0.15460 (12)	0.0631 (5)
H4	0.2610	1.4404	0.1686	0.076*
C5	0.16671 (18)	1.26654 (19)	0.20863 (12)	0.0641 (5)
H5	0.1510	1.3147	0.2604	0.077*
C6	0.09516 (13)	0.90373 (15)	0.09935 (9)	0.0416 (3)
C7	0.00521 (17)	0.8435 (2)	0.15426 (12)	0.0616 (4)
H7A	−0.0685	0.8058	0.1140	0.092*
H7B	−0.0185	0.9222	0.1914	0.092*
H7C	0.0448	0.7637	0.1928	0.092*
C8	0.13068 (14)	0.62602 (15)	−0.05927 (10)	0.0452 (3)
C9	0.21832 (14)	0.71408 (15)	−0.10665 (10)	0.0460 (3)
C10	0.33825 (15)	0.76293 (16)	−0.06705 (11)	0.0519 (4)
C11	0.41041 (18)	0.8496 (2)	−0.11371 (14)	0.0666 (5)
H11	0.4896	0.8832	−0.0848	0.080*
C12	0.3637 (2)	0.8853 (2)	−0.20298 (15)	0.0751 (6)
H12	0.4120	0.9420	−0.2354	0.090*
C13	0.2465 (2)	0.8381 (2)	−0.24480 (14)	0.0759 (6)
H13	0.2152	0.8628	−0.3055	0.091*
C14	0.17386 (18)	0.7532 (2)	−0.19668 (11)	0.0611 (4)
H14	0.0939	0.7221	−0.2257	0.073*
H3	0.0368 (15)	0.640 (2)	0.0371 (13)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0659 (8)	0.0473 (7)	0.0524 (7)	−0.0064 (6)	0.0134 (6)	−0.0128 (6)
N2	0.0521 (7)	0.0348 (6)	0.0491 (7)	−0.0093 (5)	0.0172 (5)	−0.0071 (5)
N3	0.0570 (7)	0.0385 (6)	0.0534 (7)	−0.0140 (5)	0.0257 (6)	−0.0098 (5)
N4	0.0666 (9)	0.0687 (10)	0.0739 (10)	−0.0229 (8)	0.0109 (8)	0.0082 (8)
O1	0.0779 (8)	0.0422 (6)	0.0646 (7)	−0.0196 (5)	0.0320 (6)	−0.0173 (5)
O2	0.1304 (14)	0.1325 (16)	0.0997 (12)	−0.0800 (12)	−0.0180 (11)	0.0141 (11)
O3	0.0905 (10)	0.0725 (9)	0.0852 (9)	−0.0211 (7)	0.0049 (7)	0.0280 (7)
C1	0.0429 (7)	0.0365 (7)	0.0433 (7)	−0.0008 (5)	0.0038 (5)	−0.0034 (5)
C2	0.0646 (9)	0.0412 (8)	0.0570 (9)	−0.0072 (7)	0.0176 (7)	−0.0042 (7)
C3	0.0719 (11)	0.0439 (9)	0.0733 (11)	−0.0115 (7)	0.0154 (9)	0.0046 (8)
C4	0.0726 (11)	0.0378 (8)	0.0733 (11)	−0.0093 (7)	0.0007 (9)	−0.0071 (8)
C5	0.0777 (11)	0.0503 (9)	0.0618 (10)	−0.0057 (8)	0.0077 (8)	−0.0203 (8)
C6	0.0445 (7)	0.0398 (7)	0.0410 (7)	−0.0042 (5)	0.0094 (5)	−0.0038 (5)
C7	0.0698 (10)	0.0616 (10)	0.0604 (10)	−0.0224 (8)	0.0298 (8)	−0.0164 (8)
C8	0.0539 (8)	0.0367 (7)	0.0481 (8)	−0.0081 (6)	0.0179 (6)	−0.0062 (6)
C9	0.0601 (8)	0.0325 (7)	0.0516 (8)	−0.0031 (6)	0.0258 (7)	−0.0049 (6)
C10	0.0611 (9)	0.0394 (8)	0.0607 (9)	−0.0077 (6)	0.0255 (7)	0.0005 (7)
C11	0.0694 (11)	0.0533 (10)	0.0869 (13)	−0.0105 (8)	0.0394 (10)	0.0058 (9)
C12	0.0996 (15)	0.0567 (11)	0.0852 (13)	−0.0009 (10)	0.0576 (12)	0.0125 (9)
C13	0.1131 (17)	0.0669 (12)	0.0576 (10)	0.0116 (11)	0.0404 (11)	0.0133 (9)
C14	0.0751 (11)	0.0581 (10)	0.0540 (10)	0.0025 (8)	0.0225 (8)	−0.0023 (7)

Geometric parameters (Å, º) top

N1—C1	1.3360 (18)	C4—H4	0.9300
N1—C5	1.343 (2)	C5—H5	0.9300
N2—C6	1.2805 (17)	C6—C7	1.493 (2)
N2—N3	1.3752 (15)	C7—H7A	0.9600
N3—C8	1.3446 (18)	C7—H7B	0.9600
N3—H3	0.903 (9)	C7—H7C	0.9600
N4—O3	1.2071 (19)	C8—C9	1.5118 (19)
N4—O2	1.219 (2)	C9—C14	1.380 (2)
N4—C10	1.459 (2)	C9—C10	1.386 (2)
O1—C8	1.2245 (16)	C10—C11	1.382 (2)
C1—C2	1.390 (2)	C11—C12	1.367 (3)
C1—C6	1.4892 (19)	C11—H11	0.9300
C2—C3	1.377 (2)	C12—C13	1.365 (3)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.375 (3)	C13—C14	1.391 (3)
C3—H3A	0.9300	C13—H13	0.9300
C4—C5	1.368 (3)	C14—H14	0.9300

C1—N1—C5	117.26 (14)	C6—C7—H7B	109.5
C6—N2—N3	119.44 (11)	H7A—C7—H7B	109.5
C8—N3—N2	118.11 (11)	C6—C7—H7C	109.5
C8—N3—H3	116.5 (13)	H7A—C7—H7C	109.5
N2—N3—H3	125.4 (13)	H7B—C7—H7C	109.5
O3—N4—O2	123.02 (17)	O1—C8—N3	121.68 (13)
O3—N4—C10	118.49 (14)	O1—C8—C9	120.83 (12)
O2—N4—C10	118.48 (15)	N3—C8—C9	117.34 (11)
N1—C1—C2	122.05 (13)	C14—C9—C10	116.89 (14)
N1—C1—C6	116.38 (12)	C14—C9—C8	117.24 (14)
C2—C1—C6	121.56 (12)	C10—C9—C8	125.84 (14)
C3—C2—C1	119.31 (15)	C11—C10—C9	122.42 (16)
C3—C2—H2	120.3	C11—C10—N4	117.24 (15)
C1—C2—H2	120.3	C9—C10—N4	120.33 (13)
C4—C3—C2	119.00 (16)	C12—C11—C10	119.04 (18)
C4—C3—H3A	120.5	C12—C11—H11	120.5
C2—C3—H3A	120.5	C10—C11—H11	120.5
C5—C4—C3	118.18 (15)	C13—C12—C11	120.35 (17)
C5—C4—H4	120.9	C13—C12—H12	119.8
C3—C4—H4	120.9	C11—C12—H12	119.8
N1—C5—C4	124.17 (16)	C12—C13—C14	120.08 (18)
N1—C5—H5	117.9	C12—C13—H13	120.0
C4—C5—H5	117.9	C14—C13—H13	120.0
N2—C6—C1	114.05 (12)	C9—C14—C13	121.19 (18)
N2—C6—C7	126.30 (12)	C9—C14—H14	119.4
C1—C6—C7	119.65 (12)	C13—C14—H14	119.4
C6—C7—H7A	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1ⁱ	0.90 (1)	2.13 (1)	3.0290 (15)	173 (2)

Symmetry code: (i) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂N₄O₃
M_r	284.28
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	10.8303 (8), 8.9112 (7), 14.9437 (11)
β (°)	101.483 (1)
V (Å³)	1413.36 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART 1K CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.981, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	7984, 3048, 2358
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.126, 1.05
No. of reflections	3048
No. of parameters	194
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)	0.23, −0.19

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
N3—H3···O1ⁱ	0.903 (9)	2.131 (10)	3.0290 (15)	173.1 (19)

Symmetry code: (i) −x, −y+1, −z.

Acknowledgements

The authors thank the National Natural Science Foundation of China (21141007), the Shanghai Natural Science Foundation (11ZR1414800), the `Chen Guang' project supported by the Shanghai Municipal Education Commission and the Shanghai Education Development Foundation (09 C G52), the Project of the Shanghai Municipal Education Commission (09YZ245, 10YZ111) and Shanghai Maritime University (20110017, 20110013) for financial support.

References

Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Mangalam, N. A., Sivakumar, S., Sheeja, S. R., Kurup, M. R. P. & Tiekink, E. R. T. (2009). Inorg. Chim. Acta, 362, 4191–4197. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tang, C.-B. (2011). Acta Cryst. E67, o271. Web of Science CSD CrossRef IUCr Journals Google Scholar