(E)-1,3-Benzodioxole-5-carbaldehyde 4-nitro­phenyl­hydrazone

In the title compound, C₁₄H₁₁N₃O₄, the two benzene rings are nearly coplanar, making a dihedral angle of 5.2 (16)°. The crystal packing is consolidated by inter­molecular N—H...O hydrogen bonding.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.051
• wR factor = 0.088
• Data-to-parameter ratio = 8.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.43
           From the CIF: _reflns_number_total               1687
           Count of symmetry unique reflns         1721
           Completeness (_total/calc)             98.02%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

4-Nitrophenylhydrazine 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). As a continuation of this work, we report here the crystal structure of the title compound.

The structure of the title compound is shown in Fig. 1, Selected bond lengths and angles are listed in Table 1. The C6—C1 and C6—C5 bond, close to the imino group, are longer than other aromatic C—C bonds in the same benzene ring, which are consistent with the reported by Shan et al. (2002, 2003).

The title molecule crystallizes in the E conformation, with an N2—N1—C7—C1 torsion angle of -176.6 (3)°. The two benzene rings make a dihedral angle of 5.2 (16)°.

The intermolecular N—H···O hydrogen bonding (Table 2) helps to stabilize the crystal structure (Fig. 2).

Related literature

For general background, see: Okabe et al. (1993). For related structures, see: Shan et al. (2002, 2003).

S2. Experimental

4-Nitrophenylhydrazine (1 mmol, 0.153 g) was dissolved in anhydrous methanol, H₂SO₄ (98% 0.5 ml) was added to this, the mixture was stirred for several minutes at 351 K, 1,3-Benzodioxole-5-carbaldehyde (1 mmol, 0.150 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 dichloromethane, brown single crystals of the title compound were obtained after 2 d.

S3. Refinement

Imino H atom was located in a difference Fourier map and positional parameters were refined, U_iso(H) = 1.2U_eq(N). Other H atoms were placed in calculated positions with C—H = 0.93 Å (aromatic) and 0.97 Å (methylene), and refined in riding mode with U_iso(H)=1.2U_eq(C). Friedel pairs were merged.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radii.
	Fig. 2. Packing of (I), showing the intermolecular hydrogen bonds as dashed lines.

(E)-1,3-Benzodioxole-5-carbaldehyde 4-nitrophenylhydrazone

Crystal data

C14H11N3O4	F(000) = 592
Mr = 285.26	Dx = 1.318 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 1143 reflections
a = 23.719 (3) Å	θ = 2.1–25.6°
b = 4.9052 (18) Å	µ = 0.10 mm^−1
c = 12.353 (2) Å	T = 291 K
V = 1437.2 (6) Å^3	Block, brown
Z = 4	0.30 × 0.26 × 0.24 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	1316 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.062
Graphite monochromator	θmax = 27.4°, θmin = 2.4°
φ and ω scans	h = −30→29
14432 measured reflections	k = −6→6
1687 independent reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.04P)^2] where P = (Fo^2 + 2Fc^2)/3
1687 reflections	(Δ/σ)max < 0.001
194 parameters	Δρmax = 0.14 e Å^−3
1 restraint	Δρmin = −0.14 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.97237 (14)	−0.2533 (5)	0.2885 (3)	0.0355 (7)
H1	0.9499	−0.2448	0.3502	0.043*
C2	1.01832 (13)	−0.4287 (7)	0.2850 (3)	0.0405 (8)
H2	1.0268	−0.5372	0.3446	0.049*
C3	1.05156 (14)	−0.4423 (7)	0.1928 (3)	0.0422 (8)
C4	1.03942 (13)	−0.2802 (7)	0.1041 (3)	0.0443 (8)
C5	0.99349 (14)	−0.1041 (7)	0.1062 (3)	0.0427 (8)
H5	0.9851	0.0034	0.0463	0.051*
C6	0.95999 (13)	−0.0902 (6)	0.1992 (3)	0.0350 (7)
C7	0.91205 (14)	0.0874 (7)	0.2049 (3)	0.0452 (8)
H7	0.8909	0.0741	0.2680	0.054*
C8	1.11926 (16)	−0.5179 (8)	0.0645 (3)	0.0512 (9)
H8A	1.1557	−0.4302	0.0722	0.061*
H8B	1.1232	−0.6724	0.0161	0.061*
C9	0.82653 (14)	0.6057 (7)	0.0746 (3)	0.0415 (8)
C10	0.85405 (17)	0.6553 (7)	−0.0236 (3)	0.0464 (9)
H10	0.8865	0.5586	−0.0414	0.056*
C11	0.83259 (14)	0.8510 (6)	−0.0950 (3)	0.0410 (8)
H11	0.8513	0.8880	−0.1596	0.049*
C12	0.78322 (13)	0.9903 (7)	−0.0692 (3)	0.0392 (8)
C13	0.75576 (14)	0.9381 (6)	0.0283 (3)	0.0360 (7)
H13	0.7229	1.0317	0.0456	0.043*
C14	0.77741 (13)	0.7470 (8)	0.0995 (3)	0.0473 (9)
H14	0.7590	0.7129	0.1646	0.057*
N1	0.89330 (11)	0.2693 (6)	0.1327 (2)	0.0411 (7)
N2	0.84735 (12)	0.4281 (5)	0.1523 (2)	0.0346 (6)
H2A	0.8303 (14)	0.416 (7)	0.210 (3)	0.042*
N3	0.76391 (11)	1.2097 (5)	−0.1526 (2)	0.0377 (6)
O1	1.09794 (10)	−0.6063 (5)	0.1701 (2)	0.0479 (6)
O2	1.07755 (9)	−0.3256 (4)	0.0227 (2)	0.0419 (5)
O3	0.78600 (10)	1.2221 (4)	−0.23909 (18)	0.0416 (6)
O4	0.71404 (9)	1.3080 (5)	−0.1304 (2)	0.0454 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0421 (19)	0.0279 (13)	0.0365 (17)	−0.0115 (12)	−0.0002 (14)	−0.0008 (13)
C2	0.0315 (17)	0.0506 (19)	0.039 (2)	−0.0092 (15)	−0.0065 (14)	0.0090 (15)
C3	0.0454 (19)	0.0382 (18)	0.043 (2)	0.0026 (14)	−0.0013 (16)	0.0078 (16)
C4	0.0420 (19)	0.0357 (17)	0.055 (2)	−0.0038 (14)	0.0117 (17)	0.0213 (16)
C5	0.0334 (19)	0.053 (2)	0.042 (2)	−0.0006 (14)	−0.0035 (15)	0.0153 (17)
C6	0.0373 (17)	0.0304 (14)	0.0372 (18)	−0.0116 (12)	−0.0058 (15)	−0.0018 (14)
C7	0.0354 (18)	0.056 (2)	0.044 (2)	−0.0034 (15)	−0.0021 (16)	0.0095 (17)
C8	0.054 (2)	0.0439 (19)	0.056 (2)	0.0059 (17)	0.0079 (17)	0.0071 (17)
C9	0.0350 (17)	0.0442 (18)	0.045 (2)	−0.0027 (14)	0.0084 (15)	0.0062 (16)
C10	0.067 (2)	0.0361 (16)	0.037 (2)	0.0120 (16)	0.0168 (18)	−0.0051 (15)
C11	0.0433 (18)	0.0350 (17)	0.045 (2)	−0.0080 (14)	0.0096 (15)	0.0024 (15)
C12	0.0322 (16)	0.0409 (17)	0.0444 (19)	−0.0121 (14)	−0.0005 (16)	0.0025 (14)
C13	0.0408 (18)	0.0266 (13)	0.0407 (19)	−0.0054 (13)	0.0035 (15)	−0.0078 (15)
C14	0.0349 (18)	0.048 (2)	0.059 (2)	−0.0019 (14)	0.0173 (16)	0.0171 (17)
N1	0.0356 (14)	0.0468 (15)	0.0409 (16)	−0.0009 (13)	0.0149 (12)	0.0120 (13)
N2	0.0391 (16)	0.0358 (13)	0.0290 (14)	−0.0037 (12)	0.0019 (11)	−0.0101 (12)
N3	0.0377 (16)	0.0385 (14)	0.0369 (17)	−0.0112 (11)	−0.0082 (14)	−0.0055 (12)
O1	0.0472 (15)	0.0455 (13)	0.0509 (16)	0.0054 (10)	−0.0010 (12)	0.0072 (11)
O2	0.0417 (13)	0.0405 (12)	0.0436 (13)	−0.0056 (10)	0.0021 (11)	0.0026 (11)
O3	0.0494 (13)	0.0406 (12)	0.0346 (14)	0.0218 (10)	−0.0060 (12)	−0.0059 (10)
O4	0.0431 (13)	0.0433 (12)	0.0497 (15)	−0.0070 (10)	0.0105 (12)	0.0169 (12)

Geometric parameters (Å, º)

C1—C2	1.389 (5)	C8—H8B	0.9700
C1—C6	1.394 (5)	C9—N2	1.388 (4)
C1—H1	0.9300	C9—C14	1.390 (5)
C2—C3	1.387 (5)	C9—C10	1.399 (5)
C2—H2	0.9300	C10—C11	1.399 (5)
C3—C4	1.385 (5)	C10—H10	0.9300
C3—O1	1.392 (4)	C11—C12	1.393 (5)
C4—O2	1.371 (4)	C11—H11	0.9300
C4—C5	1.391 (5)	C12—C13	1.393 (4)
C5—C6	1.399 (5)	C12—N3	1.558 (4)
C5—H5	0.9300	C13—C14	1.384 (5)
C6—C7	1.434 (4)	C13—H13	0.9300
C7—N1	1.338 (4)	C14—H14	0.9300
C7—H7	0.9300	N1—N2	1.361 (4)
C8—O2	1.461 (4)	N2—H2A	0.82 (4)
C8—O1	1.464 (5)	N3—O3	1.192 (4)
C8—H8A	0.9700	N3—O4	1.307 (3)
C2—C1—C6	119.8 (3)	N2—C9—C14	117.2 (3)
C2—C1—H1	120.1	N2—C9—C10	122.9 (3)
C6—C1—H1	120.1	C14—C9—C10	119.8 (3)
C3—C2—C1	120.1 (3)	C9—C10—C11	119.7 (3)
C3—C2—H2	120.0	C9—C10—H10	120.1
C1—C2—H2	120.0	C11—C10—H10	120.1
C4—C3—C2	120.3 (3)	C12—C11—C10	119.9 (3)
C4—C3—O1	109.7 (3)	C12—C11—H11	120.1
C2—C3—O1	130.0 (3)	C10—C11—H11	120.1
O2—C4—C3	110.5 (3)	C11—C12—C13	120.1 (3)
O2—C4—C5	129.1 (3)	C11—C12—N3	115.8 (3)
C3—C4—C5	120.3 (3)	C13—C12—N3	124.1 (3)
C4—C5—C6	119.4 (3)	C14—C13—C12	120.0 (3)
C4—C5—H5	120.3	C14—C13—H13	120.0
C6—C5—H5	120.3	C12—C13—H13	120.0
C1—C6—C5	120.2 (3)	C13—C14—C9	120.5 (3)
C1—C6—C7	118.5 (3)	C13—C14—H14	119.8
C5—C6—C7	121.3 (3)	C9—C14—H14	119.8
N1—C7—C6	129.5 (3)	C7—N1—N2	121.9 (3)
N1—C7—H7	115.2	N1—N2—C9	121.4 (3)
C6—C7—H7	115.2	N1—N2—H2A	121 (2)
O2—C8—O1	105.8 (3)	C9—N2—H2A	118 (2)
O2—C8—H8A	110.6	O3—N3—O4	124.6 (3)
O1—C8—H8A	110.6	O3—N3—C12	119.9 (3)
O2—C8—H8B	110.6	O4—N3—C12	112.5 (2)
O1—C8—H8B	110.6	C3—O1—C8	106.4 (2)
H8A—C8—H8B	108.7	C4—O2—C8	107.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O4^i	0.82 (4)	2.30 (4)	3.110 (4)	171 (3)

Symmetry code: (i) −x+3/2, y−1, z+1/2.