3-Bromo-4-methoxy­benzaldehyde 4-nitro­phenyl­hydrazone

Zhang, C.-X.; Yin, Z.-G.; Qian, H.-Y.; Hu, J.; Feng, Y.-L.

doi:10.1107/S1600536807046533

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3-Bromo-4-methoxybenzaldehyde 4-nitrophenylhydrazone

C.-X. Zhang, Z.-G. Yin, H.-Y. Qian, J. Hu and Y.-L. Feng

In the title compound, C₁₄H₁₂BrN₃O₃, the two benzene rings are slightly twisted, making a dihedral angle of 9.9 (3)°. The crystal packing is stabilized by weak intermolecular N—H

O and C—H

O hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807046533/dn3064sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807046533/dn3064Isup2.hkl Contains datablock I

CCDC reference: 663839

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.008 Å
R factor = 0.091
wR factor = 0.176
Data-to-parameter ratio = 15.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       1.04
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          8

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 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
   1 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

Comment top

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 the synthesis and crystal structure of the title compound(I).

The 4-nitrophenyl group and the methyl benzene rings areslightly twisted making a dihedral angle of 9.9 (3)° (Fig. 1). The N1/O1/O2 nitro group is co-planar with its attached benzene ring [dihedral angle =1.4 (2)°].

The intermolecular N—H···O and C—H···O hydrogen bonds can help stabilizing the molecular structure·(Table 1, Fig.2)

Related literature top

For related literature, see: Okabe et al. (1993).

Experimental top

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 minitutes at 351 K, 3-Bromo-4-methoxybenzaldehyde (1 mmol 0.215 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 (I) was obtained after 1 d.

Structure description top

The intermolecular N—H···O and C—H···O hydrogen bonds can help stabilizing the molecular structure·(Table 1, Fig.2)

For related literature, see: Okabe et al. (1993).

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, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures top

	Fig. 1. Molecular view of (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Partial packing view of (I), showing the intermolecular hydrogen bonds as dashed lines.

3-Bromo-4-methoxybenzaldehyde 4-nitrophenylhydrazone top

Crystal data top

C₁₄H₁₂BrN₃O₃	F(000) = 1408
M_r = 350.18	D_x = 1.591 Mg m⁻³
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 1248 reflections
a = 7.2800 (15) Å	θ = 2.5–27.8°
b = 14.678 (3) Å	µ = 2.82 mm⁻¹
c = 27.368 (6) Å	T = 298 K
V = 2924.4 (10) Å³	Block, brown
Z = 8	0.27 × 0.25 × 0.20 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2980 independent reflections
Radiation source: fine-focus sealed tube	2456 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.060
ω scans	θ_max = 26.5°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→8
T_min = 0.486, T_max = 0.548	k = −18→18
30041 measured reflections	l = −34→34

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)] = 0.091	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.176	H-atom parameters constrained
S = 1.22	w = 1/[σ²(F_o²) + (0.045P)² + 6.3175P] where P = (F_o² + 2F_c²)/3
2980 reflections	(Δ/σ)_max < 0.001
191 parameters	Δρ_max = 0.93 e Å⁻³
0 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

C₁₄H₁₂BrN₃O₃	V = 2924.4 (10) Å³
M_r = 350.18	Z = 8
Orthorhombic, Pccn	Mo Kα radiation
a = 7.2800 (15) Å	µ = 2.82 mm⁻¹
b = 14.678 (3) Å	T = 298 K
c = 27.368 (6) Å	0.27 × 0.25 × 0.20 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2980 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2456 reflections with I > 2σ(I)
T_min = 0.486, T_max = 0.548	R_int = 0.060
30041 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.091	0 restraints
wR(F²) = 0.176	H-atom parameters constrained
S = 1.22	Δρ_max = 0.93 e Å⁻³
2980 reflections	Δρ_min = −0.58 e Å⁻³
191 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
Br1	0.11817 (15)	0.97770 (5)	0.17684 (2)	0.1058 (4)
O1	0.3606 (7)	1.1359 (3)	0.58357 (17)	0.0930 (14)
O2	0.4495 (6)	1.2106 (3)	0.51958 (19)	0.0857 (13)
O3	0.0204 (7)	0.7930 (3)	0.14235 (15)	0.0887 (14)
N1	0.3772 (7)	1.1431 (3)	0.5392 (2)	0.0687 (13)
N2	0.1160 (7)	0.8638 (3)	0.42050 (15)	0.0642 (12)
H2	0.0786	0.8142	0.4340	0.077*
N3	0.1076 (6)	0.8735 (3)	0.37049 (16)	0.0630 (12)
C1	0.3092 (7)	1.0709 (4)	0.50809 (19)	0.0556 (13)
C2	0.2439 (8)	0.9916 (4)	0.5293 (2)	0.0602 (13)
H2A	0.2421	0.9849	0.5630	0.072*
C3	0.1816 (7)	0.9227 (4)	0.49932 (18)	0.0573 (13)
H3	0.1378	0.8690	0.5131	0.069*
C4	0.1836 (7)	0.9327 (3)	0.44878 (18)	0.0509 (12)
C5	0.2542 (8)	1.0125 (4)	0.42843 (19)	0.0591 (13)
H5	0.2577	1.0196	0.3947	0.071*
C6	0.3184 (8)	1.0802 (4)	0.4581 (2)	0.0615 (14)
H6	0.3683	1.1328	0.4445	0.074*
C7	0.0422 (8)	0.8060 (4)	0.3473 (2)	0.0666 (15)
H7	0.0015	0.7557	0.3648	0.080*
C8	0.0284 (8)	0.8046 (4)	0.2942 (2)	0.0622 (14)
C9	0.0654 (8)	0.8806 (4)	0.2657 (2)	0.0621 (14)
H9	0.0943	0.9358	0.2805	0.075*
C10	0.0594 (8)	0.8745 (4)	0.2153 (2)	0.0648 (15)
C11	0.0189 (8)	0.7920 (4)	0.1923 (2)	0.0656 (15)
C12	−0.0173 (9)	0.7173 (4)	0.2203 (3)	0.0802 (19)
H12	−0.0449	0.6620	0.2055	0.096*
C13	−0.0130 (9)	0.7237 (4)	0.2705 (2)	0.0745 (17)
H13	−0.0388	0.6722	0.2891	0.089*
C14	−0.0039 (13)	0.7075 (5)	0.1180 (3)	0.112 (3)
H14A	0.0900	0.6658	0.1284	0.167*
H14B	0.0044	0.7163	0.0833	0.167*
H14C	−0.1224	0.6830	0.1260	0.167*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.1924 (10)	0.0635 (4)	0.0616 (4)	0.0057 (5)	−0.0070 (5)	−0.0025 (3)
O1	0.119 (4)	0.090 (3)	0.069 (3)	−0.005 (3)	−0.008 (3)	−0.017 (2)
O2	0.091 (3)	0.057 (2)	0.108 (3)	−0.012 (2)	−0.009 (3)	−0.005 (2)
O3	0.126 (4)	0.075 (3)	0.064 (2)	0.023 (3)	−0.029 (3)	−0.030 (2)
N1	0.063 (3)	0.061 (3)	0.082 (4)	0.008 (3)	−0.007 (3)	−0.009 (3)
N2	0.082 (3)	0.059 (3)	0.052 (2)	−0.010 (3)	−0.002 (2)	0.008 (2)
N3	0.071 (3)	0.067 (3)	0.051 (2)	−0.003 (2)	−0.003 (2)	0.002 (2)
C1	0.053 (3)	0.052 (3)	0.062 (3)	0.006 (2)	−0.011 (3)	−0.002 (2)
C2	0.063 (3)	0.066 (3)	0.052 (3)	0.009 (3)	−0.001 (3)	0.006 (3)
C3	0.062 (3)	0.054 (3)	0.055 (3)	0.000 (3)	−0.003 (3)	0.009 (2)
C4	0.045 (3)	0.053 (3)	0.055 (3)	0.002 (2)	−0.003 (2)	0.002 (2)
C5	0.066 (3)	0.060 (3)	0.050 (3)	−0.009 (3)	−0.003 (3)	0.009 (2)
C6	0.062 (3)	0.050 (3)	0.072 (4)	−0.003 (3)	−0.004 (3)	0.014 (3)
C7	0.071 (4)	0.057 (3)	0.071 (4)	−0.006 (3)	−0.010 (3)	−0.002 (3)
C8	0.056 (3)	0.065 (4)	0.065 (3)	−0.004 (3)	−0.007 (3)	−0.010 (3)
C9	0.075 (4)	0.053 (3)	0.059 (3)	0.006 (3)	−0.015 (3)	−0.012 (3)
C10	0.083 (4)	0.052 (3)	0.060 (3)	0.016 (3)	−0.013 (3)	−0.012 (3)
C11	0.065 (4)	0.066 (4)	0.066 (3)	0.014 (3)	−0.019 (3)	−0.019 (3)
C12	0.088 (5)	0.055 (3)	0.098 (5)	−0.005 (3)	−0.023 (4)	−0.028 (3)
C13	0.083 (4)	0.062 (4)	0.078 (4)	−0.010 (3)	−0.012 (3)	−0.004 (3)
C14	0.161 (8)	0.086 (5)	0.088 (5)	0.034 (5)	−0.040 (5)	−0.044 (4)

Geometric parameters (Å, º) top

Br1—C10	1.893 (6)	C5—C6	1.366 (7)
O1—N1	1.226 (6)	C5—H5	0.9300
O2—N1	1.244 (6)	C6—H6	0.9300
O3—C11	1.367 (7)	C7—C8	1.456 (8)
O3—C14	1.432 (7)	C7—H7	0.9300
N1—C1	1.447 (7)	C8—C13	1.385 (8)
N2—C4	1.364 (6)	C8—C9	1.389 (8)
N2—N3	1.377 (6)	C9—C10	1.382 (7)
N2—H2	0.8600	C9—H9	0.9300
N3—C7	1.269 (7)	C10—C11	1.398 (7)
C1—C6	1.376 (7)	C11—C12	1.363 (9)
C1—C2	1.384 (7)	C12—C13	1.379 (9)
C2—C3	1.379 (7)	C12—H12	0.9300
C2—H2A	0.9300	C13—H13	0.9300
C3—C4	1.391 (7)	C14—H14A	0.9600
C3—H3	0.9300	C14—H14B	0.9600
C4—C5	1.396 (7)	C14—H14C	0.9600

C11—O3—C14	117.0 (5)	N3—C7—H7	118.8
O1—N1—O2	122.5 (5)	C8—C7—H7	118.8
O1—N1—C1	119.1 (5)	C13—C8—C9	117.8 (5)
O2—N1—C1	118.4 (5)	C13—C8—C7	119.6 (6)
C4—N2—N3	120.3 (4)	C9—C8—C7	122.4 (5)
C4—N2—H2	119.9	C10—C9—C8	120.2 (5)
N3—N2—H2	119.9	C10—C9—H9	119.9
C7—N3—N2	115.7 (5)	C8—C9—H9	119.9
C6—C1—C2	121.1 (5)	C9—C10—C11	120.8 (6)
C6—C1—N1	119.7 (5)	C9—C10—Br1	119.7 (4)
C2—C1—N1	119.2 (5)	C11—C10—Br1	119.4 (4)
C3—C2—C1	118.8 (5)	C12—C11—O3	125.0 (5)
C3—C2—H2A	120.6	C12—C11—C10	118.9 (5)
C1—C2—H2A	120.6	O3—C11—C10	116.1 (6)
C2—C3—C4	120.7 (5)	C11—C12—C13	120.1 (5)
C2—C3—H3	119.7	C11—C12—H12	119.9
C4—C3—H3	119.7	C13—C12—H12	119.9
N2—C4—C3	118.8 (5)	C12—C13—C8	122.0 (6)
N2—C4—C5	121.9 (5)	C12—C13—H13	119.0
C3—C4—C5	119.3 (5)	C8—C13—H13	119.0
C6—C5—C4	120.0 (5)	O3—C14—H14A	109.5
C6—C5—H5	120.0	O3—C14—H14B	109.5
C4—C5—H5	120.0	H14A—C14—H14B	109.5
C5—C6—C1	120.2 (5)	O3—C14—H14C	109.5
C5—C6—H6	119.9	H14A—C14—H14C	109.5
C1—C6—H6	119.9	H14B—C14—H14C	109.5
N3—C7—C8	122.5 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱ	0.86	2.19	3.035 (6)	166
C7—H7···O1ⁱ	0.93	2.48	3.400 (8)	172

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂BrN₃O₃
M_r	350.18
Crystal system, space group	Orthorhombic, Pccn
Temperature (K)	298
a, b, c (Å)	7.2800 (15), 14.678 (3), 27.368 (6)
V (Å³)	2924.4 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	2.82
Crystal size (mm)	0.27 × 0.25 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.486, 0.548
No. of measured, independent and observed [I > 2σ(I)] reflections	30041, 2980, 2456
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.091, 0.176, 1.22
No. of reflections	2980
No. of parameters	191
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.93, −0.58

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱ	0.86	2.19	3.035 (6)	166.1
C7—H7···O1ⁱ	0.93	2.48	3.400 (8)	172.0

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

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