1-(Butan-2-yl­idene)-2-(2-nitro­phen­yl)hydrazine

Qian, H.; Yin, Z.; Yao, Z.

doi:10.1107/S1600536809031420

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2155

doi:10.1107/S1600536809031420

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1-(Butan-2-ylidene)-2-(2-nitrophenyl)hydrazine

Heng-yu Qian,^a Zhi-gang Yin ^a ^* and Zhi-qiang Yao ^a

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

(Received 6 August 2009; accepted 10 August 2009; online 15 August 2009)

Crystals of the title compound, C₁₀H₁₃N₃O₂, were obtained from a condensation reaction of butan-2-one and 1-(2-nitrophenyl)hydrazine. The molecule exhibits a nearly coplanar structure, except for the methyl and methylene H atoms, the largest deviations from the mean plane defined by all non-H atoms, except for the nitro group, being 0.120 (2) Å for one of the nitro O atoms. Intramolecular N—H⋯O hydrogen bonding helps to establish the molecular configuration.

Related literature

For applications of Schiff base compounds, see: Kahwa et al. (1986 ); Santos et al. (2001 ).

Experimental

Crystal data

C₁₀H₁₃N₃O₂
M_r = 207.23
Monoclinic, P 2₁ /c
a = 7.3079 (11) Å
b = 10.2150 (17) Å
c = 14.763 (2) Å
β = 100.058 (9)°
V = 1085.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.28 × 0.21 × 0.11 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
7304 measured reflections
2116 independent reflections
1099 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.159
S = 0.93
2116 reflections
141 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2	0.889 (16)	1.969 (16)	2.604 (3)	127.2 (14)

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: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809031420/xu2581sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809031420/xu2581Isup2.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 molecular structure of (I) is shown in Fig. 1. The molecules is roughly planar, with the largest deviations from the mean plane defined by all non-H atoms, except the nitro group, being -0.120 (2) for atom O2.

Intramolecular N—H···O hydrogen bond is observed in compound (I), and this helps to stabilize the configuration of the molecule.

Related literature top

For applications of Schiff base compounds, 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 min at 351 K, then butan-2-one (1 mmol, 0.72 g) in ethanol (8 ml) 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 were 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: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonding is shown in dashed line.

1-(Butan-2-ylidene)-2-(2-nitrophenyl)hydrazine top

Crystal data top

C₁₀H₁₃N₃O₂	F(000) = 440
M_r = 207.23	D_x = 1.268 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1572 reflections
a = 7.3079 (11) Å	θ = 2.4–26.0°
b = 10.2150 (17) Å	µ = 0.09 mm⁻¹
c = 14.763 (2) Å	T = 296 K
β = 100.058 (9)°	Block, red
V = 1085.1 (3) Å³	0.28 × 0.21 × 0.11 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1099 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.024
Graphite monochromator	θ_max = 26.0°, θ_min = 2.4°
ω scans	h = −9→8
7304 measured reflections	k = −11→12
2116 independent reflections	l = −13→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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.159	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	w = 1/[σ²(F_o²) + (0.0917P)²] where P = (F_o² + 2F_c²)/3
2116 reflections	(Δ/σ)_max = 0.010
141 parameters	Δρ_max = 0.17 e Å⁻³
1 restraint	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₁₀H₁₃N₃O₂	V = 1085.1 (3) Å³
M_r = 207.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.3079 (11) Å	µ = 0.09 mm⁻¹
b = 10.2150 (17) Å	T = 296 K
c = 14.763 (2) Å	0.28 × 0.21 × 0.11 mm
β = 100.058 (9)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1099 reflections with I > 2σ(I)
7304 measured reflections	R_int = 0.024
2116 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	1 restraint
wR(F²) = 0.159	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	Δρ_max = 0.17 e Å⁻³
2116 reflections	Δρ_min = −0.15 e Å⁻³
141 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	0.3024 (2)	1.04656 (17)	0.09960 (11)	0.0674 (5)
C1	0.2088 (2)	0.89169 (19)	−0.01835 (13)	0.0551 (5)
N2	0.2496 (2)	1.01728 (17)	0.00803 (12)	0.0678 (5)
C2	0.2183 (3)	0.79113 (19)	0.04780 (12)	0.0621 (6)
H2	0.2495	0.8122	0.1099	0.075*
C6	0.1570 (2)	0.85236 (19)	−0.11104 (12)	0.0587 (5)
C5	0.1221 (3)	0.7221 (2)	−0.13432 (14)	0.0690 (6)
H5	0.0889	0.6985	−0.1959	0.083*
N3	0.1382 (3)	0.9459 (2)	−0.18488 (14)	0.0817 (6)
C3	0.1830 (3)	0.66460 (19)	0.02310 (14)	0.0698 (6)
H3	0.1907	0.6007	0.0685	0.084*
C4	0.1358 (3)	0.6288 (2)	−0.06817 (15)	0.0732 (6)
H4	0.1136	0.5415	−0.0841	0.088*
O2	0.1590 (3)	1.0630 (2)	−0.16759 (12)	0.1089 (7)
C7	0.3445 (3)	1.1663 (2)	0.11902 (16)	0.0713 (6)
O1	0.1019 (3)	0.90665 (19)	−0.26427 (11)	0.1204 (7)
C8	0.4002 (3)	1.2013 (2)	0.21782 (18)	0.0938 (8)
H8A	0.5240	1.2387	0.2266	0.113*
H8B	0.3166	1.2687	0.2325	0.113*
C10	0.3419 (3)	1.2749 (2)	0.05076 (18)	0.0974 (8)
H10A	0.4223	1.2531	0.0080	0.146*
H10B	0.3843	1.3543	0.0824	0.146*
H10C	0.2175	1.2869	0.0180	0.146*
C9	0.4004 (4)	1.0931 (3)	0.28360 (19)	0.1200 (10)
H9A	0.2803	1.0523	0.2740	0.180*
H9B	0.4286	1.1266	0.3452	0.180*
H9C	0.4926	1.0298	0.2745	0.180*
H2A	0.240 (3)	1.0806 (15)	−0.0338 (11)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0685 (11)	0.0696 (12)	0.0636 (12)	−0.0003 (9)	0.0106 (8)	−0.0109 (9)
C1	0.0509 (11)	0.0590 (12)	0.0556 (12)	0.0053 (9)	0.0102 (8)	0.0030 (10)
N2	0.0764 (12)	0.0608 (12)	0.0652 (13)	0.0025 (9)	0.0095 (9)	0.0037 (8)
C2	0.0672 (13)	0.0693 (14)	0.0485 (11)	0.0010 (10)	0.0062 (9)	0.0024 (10)
C6	0.0557 (11)	0.0734 (14)	0.0468 (11)	0.0076 (10)	0.0081 (8)	0.0083 (10)
C5	0.0601 (13)	0.0917 (17)	0.0549 (12)	−0.0007 (11)	0.0087 (10)	−0.0156 (12)
N3	0.0826 (13)	0.1009 (16)	0.0613 (13)	0.0115 (11)	0.0116 (9)	0.0134 (12)
C3	0.0758 (15)	0.0658 (14)	0.0680 (14)	−0.0028 (11)	0.0126 (11)	0.0065 (11)
C4	0.0764 (15)	0.0667 (14)	0.0777 (16)	−0.0052 (11)	0.0169 (12)	−0.0077 (12)
O2	0.1446 (17)	0.0932 (13)	0.0870 (13)	0.0062 (12)	0.0148 (11)	0.0327 (10)
C7	0.0523 (12)	0.0700 (15)	0.0934 (17)	0.0034 (11)	0.0173 (11)	−0.0162 (13)
O1	0.1572 (18)	0.1516 (17)	0.0490 (11)	0.0180 (13)	0.0086 (10)	0.0100 (10)
C8	0.0826 (16)	0.0953 (18)	0.106 (2)	−0.0056 (13)	0.0236 (14)	−0.0338 (16)
C10	0.0861 (18)	0.0704 (16)	0.136 (2)	0.0024 (13)	0.0191 (15)	0.0039 (15)
C9	0.135 (2)	0.144 (3)	0.0799 (17)	−0.036 (2)	0.0144 (16)	−0.0224 (18)

Geometric parameters (Å, º) top

N1—C7	1.282 (2)	C3—C4	1.380 (3)
N1—N2	1.372 (2)	C3—H3	0.9300
C1—N2	1.359 (2)	C4—H4	0.9300
C1—C6	1.413 (3)	C7—C10	1.496 (3)
C1—C2	1.411 (2)	C7—C8	1.488 (3)
N2—H2A	0.888 (9)	C8—C9	1.471 (3)
C2—C3	1.355 (2)	C8—H8A	0.9700
C2—H2	0.9300	C8—H8B	0.9700
C6—C5	1.387 (3)	C10—H10A	0.9600
C6—N3	1.438 (2)	C10—H10B	0.9600
C5—C4	1.356 (3)	C10—H10C	0.9600
C5—H5	0.9300	C9—H9A	0.9600
N3—O1	1.223 (2)	C9—H9B	0.9600
N3—O2	1.227 (2)	C9—H9C	0.9600

C7—N1—N2	116.33 (18)	C5—C4—H4	120.3
N2—C1—C6	123.67 (17)	C3—C4—H4	120.3
N2—C1—C2	120.49 (18)	N1—C7—C10	125.6 (2)
C6—C1—C2	115.84 (18)	N1—C7—C8	117.5 (2)
C1—N2—N1	119.87 (16)	C10—C7—C8	116.8 (2)
C1—N2—H2A	120.1 (14)	C9—C8—C7	115.8 (2)
N1—N2—H2A	120.0 (14)	C9—C8—H8A	108.3
C3—C2—C1	121.61 (18)	C7—C8—H8A	108.3
C3—C2—H2	119.2	C9—C8—H8B	108.3
C1—C2—H2	119.2	C7—C8—H8B	108.3
C5—C6—C1	121.30 (17)	H8A—C8—H8B	107.4
C5—C6—N3	117.42 (19)	C7—C10—H10A	109.5
C1—C6—N3	121.28 (19)	C7—C10—H10B	109.5
C4—C5—C6	120.57 (19)	H10A—C10—H10B	109.5
C4—C5—H5	119.7	C7—C10—H10C	109.5
C6—C5—H5	119.7	H10A—C10—H10C	109.5
O1—N3—O2	121.1 (2)	H10B—C10—H10C	109.5
O1—N3—C6	119.0 (2)	C8—C9—H9A	109.5
O2—N3—C6	119.9 (2)	C8—C9—H9B	109.5
C2—C3—C4	121.22 (18)	H9A—C9—H9B	109.5
C2—C3—H3	119.4	C8—C9—H9C	109.5
C4—C3—H3	119.4	H9A—C9—H9C	109.5
C5—C4—C3	119.5 (2)	H9B—C9—H9C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2	0.89 (2)	1.97 (2)	2.604 (3)	127 (1)

Experimental details

Crystal data
Chemical formula	C₁₀H₁₃N₃O₂
M_r	207.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	7.3079 (11), 10.2150 (17), 14.763 (2)
β (°)	100.058 (9)
V (Å³)	1085.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.28 × 0.21 × 0.11

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7304, 2116, 1099
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.159, 0.93
No. of reflections	2116
No. of parameters	141
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)	0.17, −0.15

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2	0.889 (16)	1.969 (16)	2.604 (3)	127.2 (14)

Acknowledgements

The authors would like to express their deep appreciation to the start-up Fund for PhDs of the Natural Scientific Research of Zhengzhou University of Light Industry (No. 2005001) and the Fund for Natural Scientific Research of Zhengzhou University of Light Industry, China (000455).

References

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