But-2-enal 2,4-dinitro­phenyl­hydrazone

Yin, Z.-G.; Qian, H.-Y.; Chen, Y.-Z.; Hu, J.

doi:10.1107/S1600536808033254

organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2149

doi:10.1107/S1600536808033254

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But-2-enal 2,4-dinitrophenylhydrazone

Zhi-Gang Yin,^a ^* Heng-Yu Qian,^a Yu-Zhen Chen ^a and Jie Hu ^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 9 October 2008; accepted 13 October 2008; online 22 October 2008)

In the title compound, C₁₀H₁₀N₄O₄, the but-2-enal chain is almost planar, the largest deviation from the mean plane being 0.013 (1) Å, and this plane makes a dihedral angle of 9.95 (24)° with the benzene ring,. Of the two nitro groups, one is twisted with respect to the benzene ring, making a dihedral angle of 5.7 (1)°, whereas the other is nearly in the plane of the benzene ring, with a twist angle of only 0.7 (1)°. This difference is related to the occurence of an intramolecular N—H⋯O hydrogen bond with the O atom of the less twisted nitro group. The NH group is also involved in a weak interaction with the same O atom of a symmetry-related molecule, thus forming a pseudo inversion dimer.

Related literature

For general background, see: Okabe et al. (1993 ). For related structures, see: Bolte & Dill (1998 ); Ohba (1996 ).

Experimental

Crystal data

C₁₀H₁₀N₄O₄
M_r = 250.22
Monoclinic, P 2₁ /c
a = 4.6699 (8) Å
b = 13.188 (2) Å
c = 18.880 (3) Å
β = 92.565 (3)°
V = 1161.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 (2) K
0.27 × 0.23 × 0.23 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.972, T_max = 0.976
9152 measured reflections
2458 independent reflections
1326 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.111
S = 0.95
2458 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.16 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—H2⋯O1	0.86	2.02	2.6314 (18)	127
N2—H2⋯O1ⁱ	0.86	2.52	3.331 (2)	159
Symmetry code: (i) -x+1, -y+1, -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, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808033254/dn2390sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808033254/dn2390Isup2.hkl

checkCIF report

Comment top

2,4-Dinitrophenylhydrazine has applications in organic synthesis and some of its derivatives have been shown to be potentially DNA-damaging and mutagenic agents (Okabe et al., 1993). Some phenylhydrazone derivatives have been synthesized in our laboratory. As part of our work, we report the synthesis and crystal structure of the title compound(I).

In the title compound, the but-2-enal chain is planar with the largest deviation from the mean plane being 0.013 (1)Å at C1. This plane makes a dihedral angle of 9.95 (24)° with the benzene ring, so the whole molecule is roughly planar (Fig. 1). Of the the two nitro groups, one is twisted with respect to the benzene ring making a dihedral angle of 5.7 (1)° whereas the other is nearly in the plane of the benzene ring with a twist angle of only 0.7 (1)°. This difference is related to the occurence of an intramolecular hydrogen N-H···bond with the O atom of the less twisted nitro group (Table 1). The NH is also in weak intermolecular interaction with the same O atom of a symmetry related molecule building a pseudo dimer (Table 1, Fig. 2).

Bond lengths and bond angles are consistent with those of other dinitrophenylhydrazone derivatives(Ohba,1996; Bolte & Dill, 1998)

Related literature top

For general background, see: Okabe et al. (1993). For related structures, see: Bolte & Dill (1998); Ohba (1996).

Experimental top

2,4-Dinitrophenylhydrazine (1 mmol, 0.198 g) was dissolved in anhydrous methanol, H₂SO₄ (98% 0.5 ml) was added to this, the mixture was stirred for several minitutes at 351 K, but-2-enal (1 mmol 0.070 g) in methanol (8 ml) was added dropwise and the mixture was stirred at refluxing temperature for 2 h. The product was isolated and recrystallized in methanol, red single crystals of (I) was obtained after two weeks.

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, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular view of (I) with the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as small spheres of arbitrary radii. Intramolecular H bond is shown as dashed line.
	Fig. 2. Partial packing view showing the formation of pseudo dimer through weak intermolecular N-H···O hydrogen bonds which are shown as dashed lines. H atoms not involved in hydrogen bondings have been omitted for clarity.[Symmetry code: (i) -x+1, -y+1, -z]

But-2-enal 2,4-dinitrophenylhydrazone top

Crystal data top

C₁₀H₁₀N₄O₄	F(000) = 520
M_r = 250.22	D_x = 1.432 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1673 reflections
a = 4.6699 (8) Å	θ = 2.1–25.5°
b = 13.188 (2) Å	µ = 0.11 mm⁻¹
c = 18.880 (3) Å	T = 293 K
β = 92.565 (3)°	Block, red
V = 1161.6 (3) Å³	0.27 × 0.23 × 0.23 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2458 independent reflections
Radiation source: sealed tube	1326 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ϕ and ω scans	θ_max = 27.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −5→5
T_min = 0.972, T_max = 0.976	k = −16→16
9152 measured reflections	l = −24→24

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 0.95	w = 1/[σ²(F_o²) + (0.0552P)²] where P = (F_o² + 2F_c²)/3
2458 reflections	(Δ/σ)_max < 0.001
164 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.11 e Å⁻³

Crystal data top

C₁₀H₁₀N₄O₄	V = 1161.6 (3) Å³
M_r = 250.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.6699 (8) Å	µ = 0.11 mm⁻¹
b = 13.188 (2) Å	T = 293 K
c = 18.880 (3) Å	0.27 × 0.23 × 0.23 mm
β = 92.565 (3)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2458 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1326 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.976	R_int = 0.039
9152 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 0.95	Δρ_max = 0.16 e Å⁻³
2458 reflections	Δρ_min = −0.11 e Å⁻³
164 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
N1	0.0380 (3)	0.35052 (10)	0.11439 (8)	0.0607 (4)
N2	0.1292 (3)	0.44685 (9)	0.09740 (8)	0.0563 (4)
H2	0.2613	0.4552	0.0676	0.068*
N3	0.2785 (3)	0.65667 (11)	0.05938 (8)	0.0554 (4)
N4	−0.3915 (4)	0.77803 (13)	0.22849 (9)	0.0673 (5)
O1	0.4042 (3)	0.58766 (9)	0.02881 (7)	0.0693 (4)
O2	0.3266 (3)	0.74610 (9)	0.04720 (8)	0.0761 (4)
O3	−0.5851 (3)	0.75891 (12)	0.26884 (9)	0.0872 (5)
O4	−0.3125 (3)	0.86398 (12)	0.21507 (9)	0.0909 (5)
C1	0.1822 (6)	−0.01443 (14)	0.09371 (14)	0.1054 (9)
H1A	0.0157	−0.0191	0.1216	0.158*
H1B	0.3428	−0.0449	0.1191	0.158*
H1C	0.1469	−0.0492	0.0495	0.158*
C2	0.2468 (5)	0.09525 (15)	0.07954 (12)	0.0770 (6)
H22	0.4003	0.1089	0.0513	0.092*
C3	0.1060 (5)	0.17380 (13)	0.10341 (10)	0.0651 (5)
H3	−0.0512	0.1615	0.1307	0.078*
C4	0.1811 (4)	0.27691 (12)	0.08969 (10)	0.0585 (5)
H4	0.3370	0.2906	0.0623	0.070*
C5	0.0079 (4)	0.52752 (12)	0.12821 (9)	0.0497 (4)
C6	0.0733 (4)	0.63020 (12)	0.11150 (9)	0.0506 (4)
C7	−0.0580 (4)	0.71065 (13)	0.14479 (10)	0.0539 (5)
H7	−0.0131	0.7771	0.1330	0.065*
C8	−0.2534 (4)	0.69186 (13)	0.19495 (10)	0.0556 (5)
C9	−0.3232 (4)	0.59241 (15)	0.21334 (10)	0.0603 (5)
H9	−0.4562	0.5806	0.2476	0.072*
C10	−0.1960 (4)	0.51299 (13)	0.18104 (10)	0.0582 (5)
H10	−0.2439	0.4473	0.1939	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0727 (10)	0.0384 (8)	0.0716 (10)	−0.0054 (7)	0.0084 (8)	0.0014 (7)
N2	0.0651 (9)	0.0405 (8)	0.0639 (9)	−0.0042 (7)	0.0116 (7)	0.0008 (7)
N3	0.0681 (10)	0.0380 (8)	0.0602 (9)	0.0009 (7)	0.0032 (8)	0.0008 (7)
N4	0.0677 (11)	0.0668 (12)	0.0670 (11)	0.0122 (9)	−0.0015 (9)	−0.0095 (9)
O1	0.0902 (10)	0.0448 (7)	0.0747 (9)	0.0027 (7)	0.0259 (7)	−0.0002 (6)
O2	0.1022 (11)	0.0386 (7)	0.0894 (10)	−0.0035 (7)	0.0259 (8)	0.0066 (6)
O3	0.0782 (10)	0.0913 (11)	0.0937 (11)	0.0151 (8)	0.0195 (9)	−0.0164 (8)
O4	0.1150 (13)	0.0545 (9)	0.1047 (12)	0.0163 (9)	0.0220 (10)	−0.0058 (8)
C1	0.162 (2)	0.0418 (11)	0.110 (2)	0.0019 (14)	−0.0186 (17)	0.0004 (12)
C2	0.1028 (17)	0.0469 (11)	0.0809 (14)	0.0004 (11)	0.0013 (12)	−0.0004 (10)
C3	0.0838 (14)	0.0428 (10)	0.0687 (12)	−0.0059 (9)	0.0057 (10)	0.0026 (9)
C4	0.0724 (12)	0.0427 (10)	0.0606 (11)	−0.0040 (9)	0.0060 (9)	0.0011 (8)
C5	0.0527 (10)	0.0394 (9)	0.0564 (11)	−0.0010 (8)	−0.0037 (8)	−0.0010 (7)
C6	0.0528 (10)	0.0445 (9)	0.0543 (10)	−0.0006 (8)	−0.0001 (9)	0.0012 (8)
C7	0.0572 (11)	0.0406 (9)	0.0632 (11)	0.0014 (8)	−0.0062 (9)	−0.0002 (8)
C8	0.0548 (11)	0.0519 (11)	0.0596 (11)	0.0098 (9)	−0.0014 (9)	−0.0042 (9)
C9	0.0545 (11)	0.0661 (12)	0.0605 (12)	0.0025 (9)	0.0051 (9)	−0.0002 (9)
C10	0.0622 (11)	0.0474 (10)	0.0649 (12)	−0.0042 (9)	0.0039 (9)	0.0056 (9)

Geometric parameters (Å, º) top

N1—C4	1.278 (2)	C2—C3	1.317 (3)
N1—N2	1.3821 (17)	C2—H22	0.9300
N2—C5	1.349 (2)	C3—C4	1.431 (2)
N2—H2	0.8600	C3—H3	0.9300
N3—O2	1.2245 (17)	C4—H4	0.9300
N3—O1	1.2396 (17)	C5—C10	1.422 (3)
N3—C6	1.446 (2)	C5—C6	1.427 (2)
N4—O4	1.2221 (19)	C6—C7	1.390 (2)
N4—O3	1.234 (2)	C7—C8	1.367 (3)
N4—C8	1.465 (2)	C7—H7	0.9300
C1—C2	1.504 (3)	C8—C9	1.399 (3)
C1—H1A	0.9600	C9—C10	1.362 (2)
C1—H1B	0.9600	C9—H9	0.9300
C1—H1C	0.9600	C10—H10	0.9300

C4—N1—N2	116.23 (15)	N1—C4—C3	121.30 (18)
C5—N2—N1	119.02 (14)	N1—C4—H4	119.4
C5—N2—H2	120.5	C3—C4—H4	119.4
N1—N2—H2	120.5	N2—C5—C10	120.21 (15)
O2—N3—O1	121.65 (15)	N2—C5—C6	123.70 (16)
O2—N3—C6	119.54 (15)	C10—C5—C6	116.08 (16)
O1—N3—C6	118.80 (14)	C7—C6—C5	121.43 (16)
O4—N4—O3	123.62 (17)	C7—C6—N3	116.26 (15)
O4—N4—C8	119.16 (19)	C5—C6—N3	122.30 (15)
O3—N4—C8	117.21 (17)	C8—C7—C6	119.78 (16)
C2—C1—H1A	109.5	C8—C7—H7	120.1
C2—C1—H1B	109.5	C6—C7—H7	120.1
H1A—C1—H1B	109.5	C7—C8—C9	120.80 (17)
C2—C1—H1C	109.5	C7—C8—N4	118.64 (17)
H1A—C1—H1C	109.5	C9—C8—N4	120.55 (18)
H1B—C1—H1C	109.5	C10—C9—C8	119.93 (18)
C3—C2—C1	126.1 (2)	C10—C9—H9	120.0
C3—C2—H22	117.0	C8—C9—H9	120.0
C1—C2—H22	117.0	C9—C10—C5	121.97 (16)
C2—C3—C4	123.7 (2)	C9—C10—H10	119.0
C2—C3—H3	118.1	C5—C10—H10	119.0
C4—C3—H3	118.1

C5—N2—N1—C4	−172.68 (16)	N1—C4—C3—C2	−179.7 (2)
N2—N1—C4—C3	−179.67 (15)	C4—C3—C2—C1	178.41 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.86	2.02	2.6314 (18)	127
N2—H2···O1ⁱ	0.86	2.52	3.331 (2)	159

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀N₄O₄
M_r	250.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	4.6699 (8), 13.188 (2), 18.880 (3)
β (°)	92.565 (3)
V (Å³)	1161.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.27 × 0.23 × 0.23

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.972, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	9152, 2458, 1326
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.111, 0.95
No. of reflections	2458
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −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, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.86	2.02	2.6314 (18)	127.4
N2—H2···O1ⁱ	0.86	2.52	3.331 (2)	158.5

Symmetry code: (i) −x+1, −y+1, −z.

Acknowledgements

The authors express their deep appreciation to the Outstanding Youth Fund for Henan Natural Scientific Research (grant No. 0512001100) and the Fund for Scientific and Technical Emphasis (grant No. 072102270006)

References

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