1-(But-2-enyl­idene)-2-(2-nitro­phen­yl)hydrazine

Yin, Z.-G.; Qian, H.-Y.; Zhu, X.-W.; Zhang, C.-X.

doi:10.1107/S1600536809037179

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2491

doi:10.1107/S1600536809037179

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1-(But-2-enylidene)-2-(2-nitrophenyl)hydrazine

Zhi-Gang Yin,^a ^* Heng-Yu Qian,^a Xue-Wen Zhu ^a and Chun-Xia Zhang ^a

^aKey Laboratory of Surface and Interface Science of Henan, School of Materials and Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou 450002, People's Republic of China
^*Correspondence e-mail: yinck@263.net

(Received 11 September 2009; accepted 14 September 2009; online 19 September 2009)

The molecule of the title Schiff base compound, C₁₀H₁₁N₃O₂, adopts an E geometry with respect to the C=N double bond. The molecule is roughly planar, with the largest deviation from the mean plane being 0.111 (2) Å, The enylidene-hydrazine group is, however, slightly twisted with respect to the phenyl ring, making a dihedral angle of 6.5 (3)°. An intramolecular N—H⋯O hydrogen bond may be responsible for the planar conformation. An intermolecular N—H⋯O hydrogen bond links two molecules around an inversion center, building a pseudo dimer.

Related literature

For the role played by Schiff base compounds in the development of various proteins and enzymes, see: Kahwa et al. (1986 ); Santos et al. (2001 ).

Experimental

Crystal data

C₁₀H₁₁N₃O₂
M_r = 205.22
Triclinic, $[P \overline 1]$
a = 4.2390 (6) Å
b = 11.456 (2) Å
c = 11.9840 (17) Å
α = 113.271 (15)°
β = 96.534 (12)°
γ = 95.595 (13)°
V = 524.64 (16) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.25 × 0.19 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.979, T_max = 0.982
3321 measured reflections
1758 independent reflections
587 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.080
S = 0.68
1758 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.11 e Å⁻³

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	2.615 (3)	127
N2—H2A⋯O2ⁱ	0.86	2.53	3.353 (3)	160
Symmetry code: (i) -x+2, -y, -z.

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: ORTEPIII (Burnett & Johnson, 1996 ), ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809037179/dn2487sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809037179/dn2487Isup2.hkl

checkCIF report

Comment top

The chemistry of Schiff base has attracted a great deal of interest in recent years. These compounds play an important role in the development of various proteins and enzymes (Kahwa et al., 1986; Santos et al., 2001). As part of our in the study of the coordination chemistry of Schiff bases, we synthesized the title compound and determined its crystal structure.

The molecule is roughly planar with the largest deviation from the mean plane being -0.111 (2) Å at O1 (Fig. 1). The enylidene-hydrazine group is however slightly twisted with respect to the phenyl ring making a dihedral angle of 6.5 (3)° .

Intramolecular N—H···O bond may be responsible for the planar conformation whereas intermolecular N—H···O links two molecules around the inversion center buiding a pseudo dimer (Table 1, Fig. 2).

Related literature top

For the role played by Schiff base compounds in the development of various proteins and enzymes, see: Kahwa et al. (1986); Santos et al. (2001).

Experimental top

2-Nitrophenylhydrazine (1 mmol, 0.153 g) was dissolved in anhydrous ethanol (15 ml), The mixture was stirred for several minitutes at 351 K, but-2-enal (1 mmol, 0.070 g) in ethanol (8 mm l) 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) was obtained after 3 d.

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: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular view of (I) with the atomlabeling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Partial packing of (I), showing the intra and intermolecular hydrogen bonds as dashed lines. H atoms not involved in hydrogen bonds have been omitted for clarity. [Symmetry codes: (i) -x+2, -y, -z]

1-(But-2-enylidene)-2-(2-nitrophenyl)hydrazine top

Crystal data top

C₁₀H₁₁N₃O₂	Z = 2
M_r = 205.22	F(000) = 216
Triclinic, P1	D_x = 1.299 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.2390 (6) Å	Cell parameters from 1958 reflections
b = 11.456 (2) Å	θ = 3.2–26.0°
c = 11.9840 (17) Å	µ = 0.09 mm⁻¹
α = 113.271 (15)°	T = 296 K
β = 96.534 (12)°	Block, red
γ = 95.595 (13)°	0.25 × 0.19 × 0.18 mm
V = 524.64 (16) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	1758 independent reflections
Radiation source: fine-focus sealed tube	587 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ω scans	θ_max = 25.0°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −5→4
T_min = 0.979, T_max = 0.982	k = −13→12
3321 measured reflections	l = 0→14

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H-atom parameters constrained
S = 0.68	w = 1/[σ²(F_o²) + (0.0315P)²] where P = (F_o² + 2F_c²)/3
1758 reflections	(Δ/σ)_max < 0.001
137 parameters	Δρ_max = 0.12 e Å⁻³
0 restraints	Δρ_min = −0.11 e Å⁻³

Crystal data top

C₁₀H₁₁N₃O₂	γ = 95.595 (13)°
M_r = 205.22	V = 524.64 (16) Å³
Triclinic, P1	Z = 2
a = 4.2390 (6) Å	Mo Kα radiation
b = 11.456 (2) Å	µ = 0.09 mm⁻¹
c = 11.9840 (17) Å	T = 296 K
α = 113.271 (15)°	0.25 × 0.19 × 0.18 mm
β = 96.534 (12)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1758 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	587 reflections with I > 2σ(I)
T_min = 0.979, T_max = 0.982	R_int = 0.039
3321 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.080	H-atom parameters constrained
S = 0.68	Δρ_max = 0.12 e Å⁻³
1758 reflections	Δρ_min = −0.11 e Å⁻³
137 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 > 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
C1	1.2639 (7)	0.1906 (3)	−0.4898 (3)	0.0923 (12)
H1A	1.1868	0.2699	−0.4786	0.138*
H1B	1.1535	0.1237	−0.5661	0.138*
H1C	1.4905	0.2007	−0.4916	0.138*
C2	1.2028 (7)	0.1556 (3)	−0.3856 (3)	0.0637 (10)
H2	1.2765	0.0820	−0.3851	0.076*
C3	1.0549 (7)	0.2191 (3)	−0.2947 (3)	0.0601 (10)
H3	0.9757	0.2916	−0.2958	0.072*
C4	1.0060 (7)	0.1857 (3)	−0.1944 (3)	0.0549 (9)
H4	1.0791	0.1129	−0.1913	0.066*
C5	0.6836 (7)	0.2802 (3)	0.0774 (2)	0.0451 (9)
C6	0.6046 (6)	0.4007 (3)	0.0883 (3)	0.0584 (9)
H6	0.6489	0.4308	0.0293	0.070*
C7	0.4654 (7)	0.4732 (3)	0.1834 (3)	0.0681 (10)
H7	0.4153	0.5520	0.1879	0.082*
C8	0.3955 (8)	0.4328 (4)	0.2745 (3)	0.0767 (11)
H8	0.3012	0.4840	0.3394	0.092*
C9	0.4679 (7)	0.3169 (3)	0.2666 (3)	0.0641 (10)
H9	0.4228	0.2883	0.3265	0.077*
C10	0.6101 (7)	0.2408 (3)	0.1686 (2)	0.0497 (9)
N1	0.8634 (6)	0.2541 (2)	−0.1088 (2)	0.0553 (7)
N2	0.8205 (5)	0.2108 (2)	−0.01925 (19)	0.0548 (8)
H2A	0.8807	0.1395	−0.0246	0.066*
N3	0.6751 (6)	0.1190 (3)	0.1671 (2)	0.0634 (8)
O1	0.5896 (6)	0.0865 (2)	0.2464 (2)	0.0933 (9)
O2	0.8241 (5)	0.05249 (18)	0.08917 (18)	0.0722 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.096 (3)	0.119 (3)	0.074 (2)	0.006 (2)	0.027 (2)	0.051 (2)
C2	0.075 (3)	0.063 (2)	0.062 (2)	0.006 (2)	0.0186 (19)	0.0343 (19)
C3	0.069 (3)	0.065 (3)	0.057 (2)	0.014 (2)	0.011 (2)	0.0350 (19)
C4	0.063 (2)	0.052 (2)	0.057 (2)	0.0116 (19)	0.0080 (18)	0.0305 (19)
C5	0.048 (2)	0.041 (2)	0.049 (2)	0.0052 (18)	0.0036 (17)	0.0236 (18)
C6	0.064 (2)	0.053 (2)	0.072 (2)	0.014 (2)	0.0155 (17)	0.0372 (19)
C7	0.084 (3)	0.048 (3)	0.082 (2)	0.017 (2)	0.022 (2)	0.032 (2)
C8	0.080 (3)	0.071 (3)	0.082 (3)	0.025 (2)	0.028 (2)	0.026 (2)
C9	0.079 (3)	0.063 (3)	0.059 (2)	0.016 (2)	0.0244 (18)	0.030 (2)
C10	0.057 (2)	0.045 (2)	0.056 (2)	0.0113 (19)	0.0112 (17)	0.0282 (18)
N1	0.068 (2)	0.056 (2)	0.0565 (16)	0.0143 (15)	0.0179 (15)	0.0347 (16)
N2	0.076 (2)	0.052 (2)	0.0548 (16)	0.0199 (16)	0.0241 (15)	0.0353 (15)
N3	0.073 (2)	0.073 (2)	0.0618 (18)	0.0175 (18)	0.0187 (15)	0.0431 (18)
O1	0.149 (2)	0.084 (2)	0.0911 (17)	0.0467 (17)	0.0603 (16)	0.0652 (16)
O2	0.1081 (19)	0.0611 (18)	0.0802 (14)	0.0410 (15)	0.0499 (13)	0.0479 (13)

Geometric parameters (Å, º) top

C1—C2	1.495 (4)	C6—C7	1.356 (3)
C1—H1A	0.9600	C6—H6	0.9300
C1—H1B	0.9600	C7—C8	1.392 (4)
C1—H1C	0.9600	C7—H7	0.9300
C2—C3	1.314 (3)	C8—C9	1.361 (3)
C2—H2	0.9300	C8—H8	0.9300
C3—C4	1.429 (3)	C9—C10	1.399 (3)
C3—H3	0.9300	C9—H9	0.9300
C4—N1	1.276 (3)	C10—N3	1.442 (3)
C4—H4	0.9300	N1—N2	1.371 (3)
C5—N2	1.351 (3)	N2—H2A	0.8600
C5—C10	1.392 (3)	N3—O1	1.227 (3)
C5—C6	1.411 (3)	N3—O2	1.232 (3)

C2—C1—H1A	109.5	C5—C6—H6	119.4
C2—C1—H1B	109.5	C6—C7—C8	121.7 (3)
H1A—C1—H1B	109.5	C6—C7—H7	119.1
C2—C1—H1C	109.5	C8—C7—H7	119.1
H1A—C1—H1C	109.5	C9—C8—C7	118.7 (3)
H1B—C1—H1C	109.5	C9—C8—H8	120.7
C3—C2—C1	126.1 (3)	C7—C8—H8	120.7
C3—C2—H2	116.9	C8—C9—C10	120.1 (3)
C1—C2—H2	116.9	C8—C9—H9	119.9
C2—C3—C4	125.2 (3)	C10—C9—H9	119.9
C2—C3—H3	117.4	C5—C10—C9	121.9 (3)
C4—C3—H3	117.4	C5—C10—N3	121.8 (3)
N1—C4—C3	121.1 (3)	C9—C10—N3	116.3 (3)
N1—C4—H4	119.5	C4—N1—N2	116.1 (2)
C3—C4—H4	119.5	C5—N2—N1	119.9 (2)
N2—C5—C10	124.5 (3)	C5—N2—H2A	120.0
N2—C5—C6	119.1 (3)	N1—N2—H2A	120.0
C10—C5—C6	116.4 (3)	O1—N3—O2	121.7 (3)
C7—C6—C5	121.1 (3)	O1—N3—C10	118.9 (3)
C7—C6—H6	119.4	O2—N3—C10	119.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2	0.86	2.00	2.615 (3)	127
N2—H2A···O2ⁱ	0.86	2.53	3.353 (3)	160

Symmetry code: (i) −x+2, −y, −z.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₁N₃O₂
M_r	205.22
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	4.2390 (6), 11.456 (2), 11.9840 (17)
α, β, γ (°)	113.271 (15), 96.534 (12), 95.595 (13)
V (Å³)	524.64 (16)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.25 × 0.19 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.979, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	3321, 1758, 587
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.080, 0.68
No. of reflections	1758
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.11

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2	0.86	2.00	2.615 (3)	127.4
N2—H2A···O2ⁱ	0.86	2.53	3.353 (3)	159.9

Symmetry code: (i) −x+2, −y, −z.

Acknowledgements

The authors would like to express their deep appreciation to the PhD startup fund of the Fund for Natural Scientific Research of Zhengzhou University of Light Industry (grant No. 2005001) and the Fund for Natural Scientific Research of Zhengzhou University of Light Industry (grant No. 000455).

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