2-Eth­oxy-4-{[(2-nitro­phen­yl)hydrazono]meth­yl}phenol

Yin, Z.-G.; Qian, H.-Y.; Zhang, C.-X.; Zhu, X.-W.

doi:10.1107/S160053680903699X

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2575

doi:10.1107/S160053680903699X

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2-Ethoxy-4-{[(2-nitrophenyl)hydrazono]methyl}phenol

Zhi-Gang Yin,^a ^* Heng-Yu Qian,^a Chun-Xia Zhang ^a and Xue-Wen Zhu ^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 11 September 2009; accepted 12 September 2009; online 30 September 2009)

The title compound, C₁₅H₁₅N₃O₄, a Schiff base, was obtained from a condensation reaction of 3-ethoxy-4-hydroxybenzaldehyde and 2-nitrophenylhydrazine. The molecule is approximately planar, the largest deviation from the mean plane being 0.1449 (16) Å. An intramolecular N—H⋯O interaction is also present. In the crystal, intermolecular O—H⋯O hydrogen bonds link the molecules, forming chain parallel to the b axis.

Related literature

For the role played by Schiff bases in the development of various proteins and enzymes, see: Kahwa et al. (1986 ); Santos et al. (2001 ).

Experimental

Crystal data

C₁₅H₁₅N₃O₄
M_r = 301.30
Monoclinic, P 2₁ /c
a = 14.586 (3) Å
b = 5.002 (1) Å
c = 19.894 (4) Å
β = 102.40 (3)°
V = 1417.6 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.20 × 0.18 × 0.17 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.979, T_max = 0.982
5585 measured reflections
2762 independent reflections
1264 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.071
S = 0.72
2762 reflections
201 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.20 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	1.99	2.610 (2)	128
O4—H11⋯O4ⁱ	0.82	2.21	2.9842 (16)	159
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: 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, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680903699X/dn2485sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680903699X/dn2485Isup2.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 interest in the study of the coordination chemistry of Schiff bases, we synthesized the title compound and determined its crystal structure.

The whole molecule is roughly planar with the largest deviation from the mean plane being -0.1449 (16)Å at C15 (Fig. 1).

Intermolecular O—H···O hydrogen bonds link the molecule to form chain parallel to the b axis (Table 1, Fig. 2).

Related literature top

For the role played by Schiff bases in the development of various

proteins and enzymes, 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 mixture was stirred for several minitutes at 351k, 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 product was isolated and recrystallized from methanol, red single crystals of (I) was 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: 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, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular view of of (I) with the atom labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Partial packing view of (I) showing the formation of a chain through O-H···O hydrogen bonds. H atoms are represented as small spheres of arbitrary radii and H bonds are shown as dashed line. H atoms not involved in hydrogen bonding have been omitted for clarity.[Symmetry codes: (i) -x+1, y+1/2, -z-1/2]

2-ethoxy-4-{[(2-nitrophenyl)hydrazono]methyl}phenol top

Crystal data top

C₁₅H₁₅N₃O₄	F(000) = 632
M_r = 301.30	D_x = 1.412 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1993 reflections
a = 14.586 (3) Å	θ = 3.1–28.2°
b = 5.002 (1) Å	µ = 0.11 mm⁻¹
c = 19.894 (4) Å	T = 296 K
β = 102.40 (3)°	Block, red
V = 1417.6 (5) Å³	0.20 × 0.18 × 0.17 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2762 independent reflections
Radiation source: fine-focus sealed tube	1264 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ω scans	θ_max = 26.0°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −17→16
T_min = 0.979, T_max = 0.982	k = −6→5
5585 measured reflections	l = −17→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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.071	H-atom parameters constrained
S = 0.72	w = 1/[σ²(F_o²) + (0.0305P)²] where P = (F_o² + 2F_c²)/3
2762 reflections	(Δ/σ)_max < 0.001
201 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₅H₁₅N₃O₄	V = 1417.6 (5) Å³
M_r = 301.30	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.586 (3) Å	µ = 0.11 mm⁻¹
b = 5.002 (1) Å	T = 296 K
c = 19.894 (4) Å	0.20 × 0.18 × 0.17 mm
β = 102.40 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2762 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1264 reflections with I > 2σ(I)
T_min = 0.979, T_max = 0.982	R_int = 0.040
5585 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.071	H-atom parameters constrained
S = 0.72	Δρ_max = 0.13 e Å⁻³
2762 reflections	Δρ_min = −0.20 e Å⁻³
201 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
C1	0.06946 (14)	0.4950 (3)	0.12464 (9)	0.0311 (5)
C2	0.07330 (15)	0.6553 (4)	0.18267 (10)	0.0385 (5)
H2A	0.0301	0.6290	0.2103	0.046*
C3	0.13985 (16)	0.8501 (4)	0.19918 (10)	0.0435 (6)
H3	0.1428	0.9562	0.2380	0.052*
C4	0.20308 (15)	0.8864 (4)	0.15677 (10)	0.0431 (6)
H4	0.2483	1.0197	0.1674	0.052*
C5	0.20040 (15)	0.7316 (4)	0.10010 (10)	0.0404 (6)
H5	0.2439	0.7620	0.0729	0.049*
C6	0.13368 (14)	0.5272 (3)	0.08161 (10)	0.0309 (5)
C7	0.19806 (14)	0.2628 (4)	−0.06428 (9)	0.0350 (5)
H7	0.1510	0.1341	−0.0737	0.042*
C8	0.26434 (14)	0.2814 (3)	−0.10903 (9)	0.0320 (5)
C9	0.33800 (14)	0.4669 (3)	−0.09704 (9)	0.0320 (5)
H9	0.3455	0.5822	−0.0596	0.038*
C10	0.39910 (14)	0.4781 (3)	−0.14074 (10)	0.0315 (5)
C11	0.38746 (14)	0.3060 (4)	−0.19732 (9)	0.0310 (5)
C12	0.31578 (15)	0.1243 (4)	−0.20896 (10)	0.0369 (5)
H12	0.3082	0.0102	−0.2467	0.044*
C13	0.25466 (15)	0.1098 (4)	−0.16481 (10)	0.0375 (5)
H13	0.2066	−0.0161	−0.1726	0.045*
C14	0.49775 (15)	0.8147 (4)	−0.07617 (10)	0.0397 (5)
H14A	0.5067	0.7107	−0.0341	0.048*
H14B	0.4476	0.9422	−0.0764	0.048*
C15	0.58674 (16)	0.9580 (4)	−0.08049 (11)	0.0557 (7)
H15A	0.6358	0.8298	−0.0802	0.084*
H15B	0.6044	1.0757	−0.0417	0.084*
H15C	0.5769	1.0602	−0.1223	0.084*
N1	−0.00228 (12)	0.2929 (3)	0.11143 (9)	0.0380 (4)
N2	0.13414 (11)	0.3742 (3)	0.02520 (8)	0.0365 (4)
H2	0.0924	0.2519	0.0131	0.044*
N3	0.20184 (11)	0.4161 (3)	−0.01266 (8)	0.0345 (4)
O1	−0.00973 (10)	0.1463 (3)	0.06016 (7)	0.0466 (4)
O2	−0.05468 (11)	0.2664 (3)	0.15192 (7)	0.0572 (5)
O3	0.47481 (10)	0.6437 (2)	−0.13471 (7)	0.0433 (4)
O4	0.44797 (11)	0.3159 (2)	−0.24127 (7)	0.0462 (4)
H11	0.4789	0.4540	−0.2346	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0301 (13)	0.0326 (11)	0.0327 (12)	−0.0013 (10)	0.0117 (10)	0.0023 (9)
C2	0.0433 (15)	0.0418 (12)	0.0346 (12)	0.0052 (12)	0.0179 (11)	0.0040 (10)
C3	0.0542 (16)	0.0416 (13)	0.0356 (13)	0.0044 (12)	0.0119 (12)	−0.0022 (10)
C4	0.0453 (16)	0.0383 (12)	0.0458 (14)	−0.0061 (11)	0.0099 (12)	−0.0029 (11)
C5	0.0400 (15)	0.0406 (12)	0.0456 (14)	−0.0100 (11)	0.0201 (12)	0.0002 (10)
C6	0.0321 (13)	0.0320 (11)	0.0296 (12)	0.0000 (10)	0.0090 (10)	0.0023 (9)
C7	0.0316 (13)	0.0389 (11)	0.0371 (12)	−0.0088 (10)	0.0131 (11)	−0.0003 (10)
C8	0.0311 (13)	0.0342 (11)	0.0343 (12)	−0.0021 (10)	0.0151 (10)	−0.0006 (10)
C9	0.0372 (14)	0.0326 (11)	0.0306 (12)	−0.0039 (10)	0.0173 (11)	−0.0038 (9)
C10	0.0332 (13)	0.0286 (11)	0.0363 (12)	−0.0039 (10)	0.0156 (10)	−0.0011 (9)
C11	0.0349 (13)	0.0348 (12)	0.0276 (11)	0.0034 (10)	0.0163 (10)	0.0018 (9)
C12	0.0450 (14)	0.0373 (12)	0.0305 (12)	−0.0057 (11)	0.0128 (11)	−0.0082 (9)
C13	0.0382 (14)	0.0388 (12)	0.0378 (13)	−0.0110 (10)	0.0132 (11)	−0.0044 (10)
C14	0.0448 (14)	0.0419 (11)	0.0345 (12)	−0.0099 (11)	0.0134 (11)	−0.0002 (10)
C15	0.0494 (16)	0.0683 (15)	0.0527 (15)	−0.0233 (13)	0.0186 (13)	−0.0084 (12)
N1	0.0358 (12)	0.0444 (10)	0.0388 (10)	−0.0033 (9)	0.0187 (9)	0.0033 (9)
N2	0.0353 (11)	0.0403 (9)	0.0398 (11)	−0.0130 (8)	0.0213 (9)	−0.0045 (8)
N3	0.0310 (11)	0.0416 (10)	0.0355 (10)	−0.0039 (8)	0.0173 (9)	0.0014 (8)
O1	0.0463 (10)	0.0544 (9)	0.0444 (10)	−0.0174 (8)	0.0215 (8)	−0.0101 (7)
O2	0.0517 (11)	0.0749 (10)	0.0563 (10)	−0.0173 (9)	0.0363 (9)	−0.0046 (8)
O3	0.0441 (9)	0.0484 (8)	0.0459 (9)	−0.0189 (8)	0.0284 (8)	−0.0145 (7)
O4	0.0547 (11)	0.0470 (9)	0.0472 (9)	−0.0078 (8)	0.0339 (8)	−0.0069 (7)

Geometric parameters (Å, º) top

C1—C2	1.397 (2)	C10—O3	1.365 (2)
C1—C6	1.407 (3)	C10—C11	1.398 (2)
C1—N1	1.438 (2)	C11—C12	1.367 (2)
C2—C3	1.365 (3)	C11—O4	1.370 (2)
C2—H2A	0.9300	C12—C13	1.381 (3)
C3—C4	1.389 (3)	C12—H12	0.9300
C3—H3	0.9300	C13—H13	0.9300
C4—C5	1.361 (2)	C14—O3	1.426 (2)
C4—H4	0.9300	C14—C15	1.501 (3)
C5—C6	1.405 (2)	C14—H14A	0.9700
C5—H5	0.9300	C14—H14B	0.9700
C6—N2	1.359 (2)	C15—H15A	0.9600
C7—N3	1.273 (2)	C15—H15B	0.9600
C7—C8	1.451 (3)	C15—H15C	0.9600
C7—H7	0.9300	N1—O2	1.2308 (19)
C8—C13	1.386 (2)	N1—O1	1.2417 (18)
C8—C9	1.401 (2)	N2—N3	1.380 (2)
C9—C10	1.373 (3)	N2—H2	0.8600
C9—H9	0.9300	O4—H11	0.8200

C2—C1—C6	121.55 (18)	C12—C11—O4	119.34 (17)
C2—C1—N1	116.94 (18)	C12—C11—C10	120.12 (17)
C6—C1—N1	121.50 (17)	O4—C11—C10	120.54 (18)
C3—C2—C1	120.59 (19)	C11—C12—C13	120.11 (18)
C3—C2—H2A	119.7	C11—C12—H12	119.9
C1—C2—H2A	119.7	C13—C12—H12	119.9
C2—C3—C4	118.55 (19)	C12—C13—C8	120.53 (19)
C2—C3—H3	120.7	C12—C13—H13	119.7
C4—C3—H3	120.7	C8—C13—H13	119.7
C5—C4—C3	121.6 (2)	O3—C14—C15	107.09 (16)
C5—C4—H4	119.2	O3—C14—H14A	110.3
C3—C4—H4	119.2	C15—C14—H14A	110.3
C4—C5—C6	121.73 (19)	O3—C14—H14B	110.3
C4—C5—H5	119.1	C15—C14—H14B	110.3
C6—C5—H5	119.1	H14A—C14—H14B	108.6
N2—C6—C5	119.98 (17)	C14—C15—H15A	109.5
N2—C6—C1	124.03 (18)	C14—C15—H15B	109.5
C5—C6—C1	115.98 (17)	H15A—C15—H15B	109.5
N3—C7—C8	122.48 (18)	C14—C15—H15C	109.5
N3—C7—H7	118.8	H15A—C15—H15C	109.5
C8—C7—H7	118.8	H15B—C15—H15C	109.5
C13—C8—C9	119.29 (18)	O2—N1—O1	121.13 (17)
C13—C8—C7	118.99 (18)	O2—N1—C1	119.06 (16)
C9—C8—C7	121.72 (17)	O1—N1—C1	119.80 (16)
C10—C9—C8	119.83 (17)	C6—N2—N3	119.74 (16)
C10—C9—H9	120.1	C6—N2—H2	120.1
C8—C9—H9	120.1	N3—N2—H2	120.1
O3—C10—C9	126.29 (18)	C7—N3—N2	115.88 (16)
O3—C10—C11	113.60 (16)	C10—O3—C14	118.65 (14)
C9—C10—C11	120.11 (19)	C11—O4—H11	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.86	1.99	2.610 (2)	128
O4—H11···O4ⁱ	0.82	2.21	2.9842 (16)	159

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₅N₃O₄
M_r	301.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	14.586 (3), 5.002 (1), 19.894 (4)
β (°)	102.40 (3)
V (Å³)	1417.6 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.20 × 0.18 × 0.17

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	5585, 2762, 1264
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.071, 0.72
No. of reflections	2762
No. of parameters	201
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.20

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, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.86	1.99	2.610 (2)	127.8
O4—H11···O4ⁱ	0.82	2.21	2.9842 (16)	158.5

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

Acknowledgements

The authors would like to express their deep appreciation to the startup fund for PhDs of the Natural Scientific Research of Zhengzhou University of Light Industry (No. 2005001) and the Fund for Natural Scientific Research of Zhengzhou University of Light Industry (000455).

References

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