2-Eth­oxy-4-[2-(3-nitro­phen­yl)­hydrazono­meth­yl]phenol

Chen, J.-Q.; Jiang, L.; Li, S.-M.; Chen, Y.-Z.

doi:10.1107/S1600536809037908

organic compounds

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Volume 65| Part 10| October 2009| Page o2536

doi:10.1107/S1600536809037908

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2-Ethoxy-4-[2-(3-nitrophenyl)hydrazonomethyl]phenol

Jun-Qiang Chen,^a ^* Ling Jiang,^b Shu-Mian Li ^b and Yu-Zhen Chen ^b

^aEnergy Research Institute Co. Ltd, Henan Academy of Sciences, Zhengzhou 450000, People's Republic of China, and ^bKey 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: junqiangchen2009@126.com

(Received 11 September 2009; accepted 18 September 2009; online 26 September 2009)

The title Schiff base compound, C₁₅H₁₅N₃O₄, was prepared from a condensation reaction of 3-ethoxy-4-hydroxybenzaldehyde and 3-nitrophenylhydrazine. The molecule is nearly planar; the dihedral angle between the hydroxybenzene ring and the nitrobenzene ring is 6.57 (7)°. O—H⋯O, O—H⋯N and C—H⋯O hydrogen bonding helps to stabilize the crystal structure.

Related literature

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

Experimental

Crystal data

C₁₅H₁₅N₃O₄
M_r = 301.30
Monoclinic, P 2₁ /n
a = 12.4160 (6) Å
b = 7.7429 (4) Å
c = 16.2249 (9) Å
β = 110.497 (6)°
V = 1461.04 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.20 × 0.16 × 0.13 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.979, T_max = 0.982
5606 measured reflections
2835 independent reflections
1558 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.077
S = 0.80
2835 reflections
203 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O1	0.89 (2)	2.14 (2)	2.6582 (16)	116.7 (18)
O2—H2A⋯N1ⁱ	0.89 (2)	2.32 (2)	3.0345 (19)	137.0 (15)
C11—H11A⋯O2ⁱⁱ	0.93	2.56	3.340 (2)	141
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; 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 global, I. DOI: 10.1107/S1600536809037908/xu2611sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809037908/xu2611Isup2.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 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 hydroxybenzene ring and the nitrobenzene ring is roughly co-planar, making a dihedral angle of 6.57 (7)°. Intramolecular O—H···O hydrogen bond and intermolecular O—H···N and C—H···O hydrogen bonds are observed (Table 1), they help to stabilize the crystal structure (Fig. 2).

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 solution was stirred for several min at 351 K, 3-ethoxy-4-hydroxybenzaldehyde (1 mmol, 0.166 g) in ethanol (8 mm l) was added dropwise and the mixture was stirred at refluxing temperature for 2 h. The solid 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: 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. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level, showing intramolecular hydrogen bonds as dashed line.
	Fig. 2. The unit cell packing diagram showing intermolecular hydrogen bonding as dashed lines.

2-Ethoxy-4-[2-(3-nitrophenyl)hydrazonomethyl]phenol top

Crystal data top

C₁₅H₁₅N₃O₄	F(000) = 632
M_r = 301.30	D_x = 1.370 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1850 reflections
a = 12.4160 (6) Å	θ = 3.2–28.2°
b = 7.7429 (4) Å	µ = 0.10 mm⁻¹
c = 16.2249 (9) Å	T = 296 K
β = 110.497 (6)°	Block, red
V = 1461.04 (13) Å³	0.20 × 0.16 × 0.13 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2835 independent reflections
Radiation source: fine-focus sealed tube	1558 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 26.0°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −15→15
T_min = 0.979, T_max = 0.982	k = −9→8
5606 measured reflections	l = −20→10

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 0.80	w = 1/[σ²(F_o²) + (0.0412P)²] where P = (F_o² + 2F_c²)/3
2835 reflections	(Δ/σ)_max < 0.001
203 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₅H₁₅N₃O₄	V = 1461.04 (13) Å³
M_r = 301.30	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.4160 (6) Å	µ = 0.10 mm⁻¹
b = 7.7429 (4) Å	T = 296 K
c = 16.2249 (9) Å	0.20 × 0.16 × 0.13 mm
β = 110.497 (6)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2835 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1558 reflections with I > 2σ(I)
T_min = 0.979, T_max = 0.982	R_int = 0.022
5606 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 0.80	Δρ_max = 0.13 e Å⁻³
2835 reflections	Δρ_min = −0.16 e Å⁻³
203 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	0.13682 (9)	0.87732 (14)	0.23604 (7)	0.0531 (3)
O2	0.22167 (11)	0.78440 (15)	0.40430 (8)	0.0574 (3)
N1	0.50471 (10)	1.09280 (16)	0.17334 (8)	0.0449 (3)
C6	0.44686 (13)	0.95951 (18)	0.28540 (10)	0.0400 (4)
C10	0.58320 (12)	1.20825 (19)	0.06891 (10)	0.0408 (4)
C11	0.47700 (12)	1.22659 (19)	0.00284 (10)	0.0424 (4)
H11A	0.4099	1.1937	0.0117	0.051*
N3	0.36075 (12)	1.31235 (19)	−0.14578 (10)	0.0586 (4)
C2	0.25328 (13)	0.89131 (18)	0.27554 (10)	0.0403 (4)
C4	0.40865 (14)	0.86218 (19)	0.41319 (10)	0.0498 (4)
H4A	0.4353	0.8353	0.4728	0.060*
C5	0.48479 (13)	0.91857 (19)	0.37376 (10)	0.0467 (4)
H5A	0.5625	0.9290	0.4072	0.056*
N2	0.59659 (11)	1.14119 (17)	0.15028 (9)	0.0566 (4)
H2B	0.6649	1.1291	0.1881	0.068*
C9	0.53084 (13)	1.02074 (18)	0.24853 (10)	0.0449 (4)
H9A	0.6083	1.0066	0.2817	0.054*
C1	0.32963 (13)	0.94411 (18)	0.23613 (10)	0.0415 (4)
H1B	0.3030	0.9697	0.1763	0.050*
C12	0.47362 (12)	1.29476 (19)	−0.07618 (10)	0.0418 (4)
C3	0.29426 (14)	0.84598 (18)	0.36459 (10)	0.0424 (4)
C15	0.68158 (13)	1.2571 (2)	0.05225 (11)	0.0525 (4)
H15A	0.7534	1.2441	0.0959	0.063*
O3	0.27636 (11)	1.2634 (2)	−0.13242 (10)	0.1076 (6)
C13	0.56883 (14)	1.3452 (2)	−0.09402 (11)	0.0545 (5)
H13A	0.5630	1.3915	−0.1483	0.065*
O4	0.35438 (11)	1.3746 (2)	−0.21577 (9)	0.0961 (5)
C7	0.08594 (14)	0.9091 (2)	0.14407 (11)	0.0570 (5)
H7A	0.1026	0.8145	0.1112	0.068*
H7B	0.1167	1.0146	0.1288	0.068*
C14	0.67357 (14)	1.3242 (2)	−0.02778 (12)	0.0627 (5)
H14A	0.7403	1.3562	−0.0376	0.075*
C8	−0.04114 (14)	0.9256 (2)	0.12228 (12)	0.0676 (5)
H8A	−0.0776	0.9469	0.0604	0.101*
H8B	−0.0567	1.0200	0.1549	0.101*
H8C	−0.0707	0.8206	0.1376	0.101*
H2A	0.1526 (18)	0.777 (2)	0.3624 (14)	0.100 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0394 (6)	0.0719 (8)	0.0458 (7)	−0.0045 (5)	0.0122 (5)	0.0102 (6)
O2	0.0559 (8)	0.0773 (8)	0.0446 (8)	−0.0088 (7)	0.0246 (7)	0.0017 (6)
N1	0.0349 (7)	0.0587 (8)	0.0418 (8)	−0.0058 (6)	0.0142 (6)	0.0001 (7)
C6	0.0386 (9)	0.0409 (9)	0.0397 (10)	−0.0013 (7)	0.0127 (8)	−0.0005 (7)
C10	0.0327 (9)	0.0507 (9)	0.0379 (10)	−0.0041 (7)	0.0112 (7)	−0.0017 (7)
C11	0.0310 (9)	0.0550 (10)	0.0429 (10)	−0.0045 (7)	0.0152 (8)	−0.0059 (8)
N3	0.0406 (9)	0.0810 (10)	0.0471 (10)	0.0004 (8)	0.0064 (8)	0.0040 (8)
C2	0.0376 (9)	0.0406 (9)	0.0416 (10)	−0.0012 (7)	0.0125 (8)	0.0015 (7)
C4	0.0519 (11)	0.0609 (11)	0.0333 (10)	−0.0019 (9)	0.0107 (8)	0.0043 (8)
C5	0.0395 (9)	0.0525 (10)	0.0420 (10)	−0.0015 (8)	0.0065 (8)	0.0020 (8)
N2	0.0293 (7)	0.0921 (11)	0.0443 (9)	−0.0077 (7)	0.0078 (6)	0.0119 (8)
C9	0.0349 (9)	0.0529 (10)	0.0421 (11)	−0.0007 (8)	0.0074 (8)	−0.0006 (8)
C1	0.0428 (9)	0.0441 (9)	0.0345 (9)	−0.0022 (7)	0.0098 (7)	0.0017 (7)
C12	0.0338 (9)	0.0508 (10)	0.0387 (10)	−0.0019 (7)	0.0101 (7)	−0.0044 (7)
C3	0.0469 (10)	0.0445 (9)	0.0391 (10)	−0.0024 (8)	0.0193 (8)	−0.0002 (7)
C15	0.0301 (9)	0.0729 (12)	0.0501 (11)	−0.0061 (8)	0.0087 (8)	0.0071 (9)
O3	0.0362 (8)	0.1872 (16)	0.0859 (11)	−0.0113 (9)	0.0045 (7)	0.0440 (10)
C13	0.0493 (11)	0.0695 (12)	0.0447 (11)	−0.0089 (9)	0.0165 (9)	0.0063 (8)
O4	0.0645 (9)	0.1613 (15)	0.0501 (9)	−0.0042 (8)	0.0043 (7)	0.0324 (9)
C7	0.0453 (10)	0.0696 (11)	0.0488 (11)	−0.0090 (9)	0.0071 (9)	0.0076 (9)
C14	0.0378 (10)	0.0927 (14)	0.0594 (13)	−0.0133 (9)	0.0192 (9)	0.0098 (10)
C8	0.0471 (11)	0.0812 (12)	0.0652 (13)	0.0020 (10)	0.0081 (9)	0.0044 (10)

Geometric parameters (Å, º) top

O1—C2	1.3654 (16)	C4—C3	1.368 (2)
O1—C7	1.4234 (18)	C4—C5	1.385 (2)
O2—C3	1.3643 (18)	C4—H4A	0.9300
O2—H2A	0.89 (2)	C5—H5A	0.9300
N1—C9	1.2759 (17)	N2—H2B	0.8600
N1—N2	1.3713 (16)	C9—H9A	0.9300
C6—C5	1.380 (2)	C1—H1B	0.9300
C6—C1	1.3989 (19)	C12—C13	1.369 (2)
C6—C9	1.451 (2)	C15—C14	1.369 (2)
C10—N2	1.3735 (19)	C15—H15A	0.9300
C10—C11	1.385 (2)	C13—C14	1.376 (2)
C10—C15	1.393 (2)	C13—H13A	0.9300
C11—C12	1.374 (2)	C7—C8	1.497 (2)
C11—H11A	0.9300	C7—H7A	0.9700
N3—O3	1.2031 (17)	C7—H7B	0.9700
N3—O4	1.2105 (17)	C14—H14A	0.9300
N3—C12	1.4660 (19)	C8—H8A	0.9600
C2—C1	1.3782 (19)	C8—H8B	0.9600
C2—C3	1.398 (2)	C8—H8C	0.9600

C2—O1—C7	119.12 (12)	C2—C1—C6	120.48 (14)
C3—O2—H2A	106.4 (14)	C2—C1—H1B	119.8
C9—N1—N2	115.03 (13)	C6—C1—H1B	119.8
C5—C6—C1	118.84 (14)	C13—C12—C11	124.11 (15)
C5—C6—C9	118.04 (14)	C13—C12—N3	118.29 (15)
C1—C6—C9	123.11 (14)	C11—C12—N3	117.60 (14)
N2—C10—C11	123.01 (14)	O2—C3—C4	118.96 (15)
N2—C10—C15	118.04 (14)	O2—C3—C2	120.94 (14)
C11—C10—C15	118.94 (14)	C4—C3—C2	120.09 (14)
C12—C11—C10	118.13 (14)	C14—C15—C10	120.65 (15)
C12—C11—H11A	120.9	C14—C15—H15A	119.7
C10—C11—H11A	120.9	C10—C15—H15A	119.7
O3—N3—O4	121.30 (16)	C12—C13—C14	116.81 (15)
O3—N3—C12	119.33 (15)	C12—C13—H13A	121.6
O4—N3—C12	119.37 (15)	C14—C13—H13A	121.6
O1—C2—C1	126.38 (14)	O1—C7—C8	107.85 (14)
O1—C2—C3	114.05 (13)	O1—C7—H7A	110.1
C1—C2—C3	119.57 (14)	C8—C7—H7A	110.1
C3—C4—C5	120.11 (15)	O1—C7—H7B	110.1
C3—C4—H4A	119.9	C8—C7—H7B	110.1
C5—C4—H4A	119.9	H7A—C7—H7B	108.4
C6—C5—C4	120.84 (15)	C15—C14—C13	121.35 (15)
C6—C5—H5A	119.6	C15—C14—H14A	119.3
C4—C5—H5A	119.6	C13—C14—H14A	119.3
N1—N2—C10	122.22 (13)	C7—C8—H8A	109.5
N1—N2—H2B	118.9	C7—C8—H8B	109.5
C10—N2—H2B	118.9	H8A—C8—H8B	109.5
N1—C9—C6	123.92 (14)	C7—C8—H8C	109.5
N1—C9—H9A	118.0	H8A—C8—H8C	109.5
C6—C9—H9A	118.0	H8B—C8—H8C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1	0.89 (2)	2.14 (2)	2.6582 (16)	116.7 (18)
O2—H2A···N1ⁱ	0.89 (2)	2.32 (2)	3.0345 (19)	137.0 (15)
C11—H11A···O2ⁱⁱ	0.93	2.56	3.340 (2)	141

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₅N₃O₄
M_r	301.30
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	12.4160 (6), 7.7429 (4), 16.2249 (9)
β (°)	110.497 (6)
V (Å³)	1461.04 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.16 × 0.13

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.979, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	5606, 2835, 1558
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.077, 0.80
No. of reflections	2835
No. of parameters	203
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.16

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1	0.89 (2)	2.14 (2)	2.6582 (16)	116.7 (18)
O2—H2A···N1ⁱ	0.89 (2)	2.32 (2)	3.0345 (19)	137.0 (15)
C11—H11A···O2ⁱⁱ	0.93	2.56	3.340 (2)	141

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

References

Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kahwa, I. A., Selbin, I., Hsieh, T. C. Y. & Laine, R. A. (1986). Inorg. Chim. Acta, 118, 179–185. CrossRef CAS Web of Science Google Scholar
Santos, M. L. P., Bagatin, I. A., Pereira, E. M. & Ferreira, A. M. D. C. (2001). J. Chem. Soc. Dalton Trans. pp. 838–844. Web of Science CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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