2,4-Dinitro­benzaldehyde hydrazone

Zhang, N.; Wang, R.; Tan, C.; Jiang, Y.; Zhao, Y.

doi:10.1107/S1600536808007514

organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page o745

doi:10.1107/S1600536808007514

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2,4-Dinitrobenzaldehyde hydrazone

Nan Zhang,^a Ruji Wang,^b Chunyan Tan,^c Yuyang Jiang ^d ^* and Yufen Zhao ^a

^aKey Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology, Ministry of Education, Department of Chemistry, Tsinghua University, Beijing 100084, People's Republic of China, ^bDepartment of Chemistry, Tsinghua University, Beijing 100084, People's Republic of China, ^cKey Laboratory of Chemical Biology, Guangdong Province, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055, People's Republic of China, and ^dSchool of Medicine, Tsinghua University, Beijing 100084, People's Republic of China
^*Correspondence e-mail: jiangyy@sz.tsinghua.edu.cn

(Received 17 March 2008; accepted 19 March 2008; online 29 March 2008)

The title compound, C₇H₆N₄O₄, plays an important role in the synthesis of biologically active compounds. The planar hydrazone group is oriented at a dihedral angle of 8.27 (3)° with respect to the benzene ring. In the crystal structure, intermolecular N—H⋯O and N—H⋯N hydrogen bonds link the molecules.

Related literature

For related literature, see: Allen et al. (1987 ); Chaulk et al. (2007 ); Kawakami et al. (2000 ); Moreno-Mañas et al. (2001 ).

Experimental

Crystal data

C₇H₆N₄O₄
M_r = 210.16
Triclinic, $[P \overline 1]$
a = 4.5839 (7) Å
b = 9.6840 (16) Å
c = 9.9287 (15) Å
α = 90.785 (12)°
β = 96.149 (11)°
γ = 98.955 (13)°
V = 432.66 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 295 (2) K
0.4 × 0.3 × 0.2 mm

Data collection

Bruker P4 diffractometer
Absorption correction: none
2238 measured reflections
1616 independent reflections
1160 reflections with I > 2σ(I)
R_int = 0.026
3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.116
S = 1.07
1616 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O1ⁱ	0.90	2.52	3.305 (3)	146
N1—H1C⋯N2ⁱⁱ	0.90	2.34	3.123 (4)	146
Symmetry codes: (i) -x+2, -y, -z+1; (ii) -x+2, -y, -z.

Data collection: XSCANS (Bruker, 1997 ); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808007514/fj2106sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808007514/fj2106Isup2.hkl

checkCIF report

Comment top

Benzaldehyde hydrazone and its analogues are important intermediates in heterocyclic chemistry, and they have been widely used for the synthesis of biologically active compounds such as [1,2,4]triazino[6,5-f]quinolines, pyrazolo[3,4-f]quinolines (Kawakami et al., 2000), 1,3-dithiol-2-ylidene derivatives (Moreno-Mañas et al., 2001), and oligo-RNAs with photocaged adenosine 2'-hydroxyls (Chaulk et al., 2007). Here we report the synthesis and crystal structure of a nitro-analogue: 2,4-dinitrobenzaldehyde hydrazone. The molecule of the title compound (Fig. 1) contains a benzene ring, a hydrazone chain and two nitryl groups. Most of the bond lengths and angles are within normal ranges (Allen et al., 1987). Because of the pi-pi conjugation and two nitryl groups electron withdrawing effect, the distance of C=N bond (1.282 (3) Å) is obviously shorter than that of the normal range (1.34–1.38 Å). The molecule is essentially planar, with a dihedral angle of 8.27° between the hydrazone group and the benzene ring. In the crystal structure, the molecules are linked by intermolecular N—H···O and N—H···N hydrogen bonds (Table 1, Fig. 2), which seem to be effective in the stabilization of the structure.

Related literature top

For related literature, see: Allen et al. (1987); Chaulk et al. (2007); Kawakami et al. (2000); Moreno-Mañas et al. (2001).

Experimental top

2,4-Dinitrobenzaldehyde (1.96 g, 10 mmol) was dissolved in 100 ml absolute ethanol, after which hydrazine hydrate (0.96 ml, 20 mmol) was added. The mixture was stirred at about 353 K for 5 h. The solution was cooled and kept at about 279 K overnight. Brown powder was collected by filtration (1.41 g, yield 67%) and then single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol.

Computing details top

Data collection: XSCANS (Bruker, 1997); cell refinement: XSCANS (Bruker, 1997); data reduction: XSCANS (Bruker, 1997); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Perspective drawing of the title compound, with the atomic numbering scheme. Displacement ellipsoids are shown at the 35% probability level.
	Fig. 2. The unit cell packing of the title compound, viewed along the a direction.

2,4-Dinitrobenzaldehyde hydrazone top

Crystal data top

C₇H₆N₄O₄	Z = 2
M_r = 210.16	F(000) = 216
Triclinic, P1	D_x = 1.613 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.5839 (7) Å	Cell parameters from 39 reflections
b = 9.6840 (16) Å	θ = 5.9–12.5°
c = 9.9287 (15) Å	µ = 0.14 mm⁻¹
α = 90.785 (12)°	T = 295 K
β = 96.149 (11)°	Prism, yellow
γ = 98.955 (13)°	0.4 × 0.3 × 0.2 mm
V = 432.66 (12) Å³

Data collection top

Bruker P4 diffractometer	R_int = 0.027
Radiation source: fine-focus sealed tube	θ_max = 25.5°, θ_min = 2.1°
Graphite monochromator	h = −5→1
ω scans	k = −11→11
2238 measured reflections	l = −11→11
1616 independent reflections	3 standard reflections every 97 reflections
1160 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.001P)² + 0.38P] where P = (F_o² + 2F_c²)/3
1616 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₇H₆N₄O₄	γ = 98.955 (13)°
M_r = 210.16	V = 432.66 (12) Å³
Triclinic, P1	Z = 2
a = 4.5839 (7) Å	Mo Kα radiation
b = 9.6840 (16) Å	µ = 0.14 mm⁻¹
c = 9.9287 (15) Å	T = 295 K
α = 90.785 (12)°	0.4 × 0.3 × 0.2 mm
β = 96.149 (11)°

Data collection top

Bruker P4 diffractometer	R_int = 0.027
2238 measured reflections	3 standard reflections every 97 reflections
1616 independent reflections	intensity decay: none
1160 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.07	Δρ_max = 0.16 e Å⁻³
1616 reflections	Δρ_min = −0.18 e Å⁻³
136 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
O1	0.7840 (6)	0.1234 (3)	0.5319 (2)	0.0887 (8)
O2	0.4576 (6)	0.2314 (2)	0.6030 (2)	0.0798 (7)
O3	0.0003 (6)	0.5548 (2)	0.3362 (3)	0.0872 (8)
O4	0.1241 (6)	0.5961 (3)	0.1351 (3)	0.0946 (9)
N1	0.9783 (6)	−0.0870 (3)	0.1463 (3)	0.0758 (8)
H1B	1.0167	−0.1364	0.2204	0.091*
H1C	1.0581	−0.1043	0.0700	0.091*
N2	0.8489 (5)	0.0275 (2)	0.1456 (2)	0.0578 (6)
N3	0.5907 (6)	0.1955 (2)	0.5116 (2)	0.0569 (6)
N4	0.1273 (6)	0.5291 (3)	0.2381 (3)	0.0675 (7)
C1	0.7626 (6)	0.0654 (3)	0.2571 (3)	0.0520 (7)
H1A	0.7984	0.0169	0.3358	0.062*
C2	0.6075 (6)	0.1858 (3)	0.2585 (3)	0.0471 (6)
C3	0.5165 (6)	0.2445 (3)	0.3752 (3)	0.0470 (6)
C4	0.3552 (6)	0.3540 (3)	0.3687 (3)	0.0518 (7)
H4A	0.2918	0.3885	0.4466	0.062*
C5	0.2906 (6)	0.4105 (3)	0.2464 (3)	0.0534 (7)
C6	0.3755 (6)	0.3582 (3)	0.1277 (3)	0.0580 (7)
H6A	0.3302	0.3978	0.0448	0.070*
C7	0.5269 (6)	0.2473 (3)	0.1360 (3)	0.0561 (7)
H7A	0.5791	0.2108	0.0565	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.117 (2)	0.1053 (19)	0.0558 (13)	0.0634 (17)	−0.0041 (13)	−0.0040 (12)
O2	0.1006 (18)	0.0891 (16)	0.0580 (13)	0.0258 (14)	0.0307 (12)	0.0011 (11)
O3	0.0851 (17)	0.0709 (15)	0.115 (2)	0.0314 (13)	0.0264 (15)	−0.0126 (14)
O4	0.136 (2)	0.0714 (16)	0.0829 (17)	0.0524 (16)	−0.0107 (16)	0.0009 (13)
N1	0.109 (2)	0.0739 (17)	0.0583 (15)	0.0542 (17)	0.0153 (15)	0.0001 (13)
N2	0.0690 (15)	0.0583 (14)	0.0517 (14)	0.0267 (12)	0.0088 (11)	−0.0026 (11)
N3	0.0658 (15)	0.0538 (14)	0.0513 (14)	0.0095 (12)	0.0085 (12)	−0.0042 (11)
N4	0.0686 (17)	0.0521 (15)	0.083 (2)	0.0200 (13)	−0.0023 (15)	−0.0111 (14)
C1	0.0609 (17)	0.0507 (15)	0.0484 (15)	0.0176 (13)	0.0106 (13)	0.0035 (12)
C2	0.0447 (14)	0.0465 (14)	0.0510 (15)	0.0082 (11)	0.0085 (12)	−0.0016 (11)
C3	0.0482 (15)	0.0464 (14)	0.0459 (15)	0.0056 (12)	0.0063 (11)	−0.0001 (11)
C4	0.0494 (15)	0.0486 (15)	0.0578 (17)	0.0080 (12)	0.0091 (13)	−0.0096 (12)
C5	0.0505 (15)	0.0449 (15)	0.0661 (18)	0.0140 (12)	0.0029 (13)	−0.0031 (13)
C6	0.0649 (18)	0.0569 (17)	0.0542 (17)	0.0183 (14)	0.0027 (14)	0.0034 (13)
C7	0.0661 (18)	0.0586 (17)	0.0473 (15)	0.0211 (14)	0.0073 (13)	−0.0027 (12)

Geometric parameters (Å, º) top

O1—N3	1.214 (3)	C1—H1A	0.9300
O2—N3	1.221 (3)	C2—C7	1.400 (4)
O3—N4	1.229 (3)	C2—C3	1.414 (3)
O4—N4	1.219 (3)	C3—C4	1.382 (3)
N1—N2	1.336 (3)	C4—C5	1.361 (4)
N1—H1B	0.8999	C4—H4A	0.9300
N1—H1C	0.9000	C5—C6	1.393 (4)
N2—C1	1.282 (3)	C6—C7	1.365 (4)
N3—C3	1.464 (3)	C6—H6A	0.9300
N4—C5	1.463 (3)	C7—H7A	0.9300
C1—C2	1.458 (3)

N2—N1—H1B	124.3	C4—C3—C2	122.2 (2)
N2—N1—H1C	115.3	C4—C3—N3	115.3 (2)
H1B—N1—H1C	119.5	C2—C3—N3	122.5 (2)
C1—N2—N1	117.5 (2)	C5—C4—C3	118.9 (2)
O1—N3—O2	121.8 (3)	C5—C4—H4A	120.6
O1—N3—C3	119.9 (2)	C3—C4—H4A	120.6
O2—N3—C3	118.3 (2)	C4—C5—C6	121.7 (3)
O4—N4—O3	123.8 (3)	C4—C5—N4	119.6 (3)
O4—N4—C5	118.6 (3)	C6—C5—N4	118.7 (3)
O3—N4—C5	117.6 (3)	C7—C6—C5	118.4 (3)
N2—C1—C2	118.9 (2)	C7—C6—H6A	120.8
N2—C1—H1A	120.5	C5—C6—H6A	120.8
C2—C1—H1A	120.5	C6—C7—C2	123.2 (3)
C7—C2—C3	115.5 (2)	C6—C7—H7A	118.4
C7—C2—C1	119.4 (2)	C2—C7—H7A	118.4
C3—C2—C1	125.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1ⁱ	0.90	2.52	3.305 (3)	146
N1—H1C···N2ⁱⁱ	0.90	2.34	3.123 (4)	146

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

Experimental details

Crystal data
Chemical formula	C₇H₆N₄O₄
M_r	210.16
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	4.5839 (7), 9.6840 (16), 9.9287 (15)
α, β, γ (°)	90.785 (12), 96.149 (11), 98.955 (13)
V (Å³)	432.66 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.4 × 0.3 × 0.2

Data collection
Diffractometer	Bruker P4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2238, 1616, 1160
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.116, 1.07
No. of reflections	1616
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.18

Computer programs: XSCANS (Bruker, 1997), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1ⁱ	0.90	2.52	3.305 (3)	145.5
N1—H1C···N2ⁱⁱ	0.90	2.34	3.123 (4)	145.9

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

Acknowledgements

The authors acknowledge financial support from the Ministry of Science and Technology of China (2005CCA03400, 2007 A A02Z160), the Chinese National Natural Science Foundation (20572060, 20472043), and the Department of Science and Technology of Guangdong Province (2005 A11601008).

References

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