(E)-4-[(3,5-Dimethyl­phen­yl)imino­meth­yl]-2-meth­oxy-3-nitro­phenol

Yang, Z.-M.; Su, D.-C.; Zhu, H.-L.

doi:10.1107/S1600536811054407

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o220

doi:10.1107/S1600536811054407

Open

access

(E)-4-[(3,5-Dimethylphenyl)iminomethyl]-2-methoxy-3-nitrophenol

Zhong-Ming Yang,^a ^* Deng-Cheng Su ^a and Hai-Liang Zhu ^a

^aSchool of Life Sciences, Shangdong University of Technology, Zibo 255000, People's Republic of China
^*Correspondence e-mail: hailiang_zhu@163.com

(Received 14 December 2011; accepted 18 December 2011; online 23 December 2011)

The molecule of the title compound, C₁₆H₁₆N₂O₄, exists in the E configuration with respect to the central C=N double bond. The dihedral angle between the two benzene rings is 2.17 (9) Å. In the crystal, molecules are linked via O—H⋯N hydrogen bonds into chains that propagate along the b-axis direction. There is also π–π stacking of inversion-related molecules, with interplanar spacings of 3.479 (5) Å and ring centroid–centroid distances of 3.876 (4) Å.

Related literature

The title compound is an imine derivative of 4-hydroxy-3-methoxy-2-nitrobenzaldehyde, a vanillin-like compound. For background to the biological activity of vanillin derivatives, see: Javiya et al. (2008 ); Cordano et al. (2002 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₆H₁₆N₂O₄
M_r = 300.31
Monoclinic, P 2₁ /c
a = 8.616 (9) Å
b = 9.690 (11) Å
c = 18.29 (2) Å
β = 97.631 (11)°
V = 1513 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.23 × 0.21 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.978, T_max = 0.989
8085 measured reflections
2935 independent reflections
1699 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.140
S = 1.04
2935 reflections
203 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N2ⁱ	0.82	1.95	2.755 (3)	169
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811054407/pk2377sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811054407/pk2377Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811054407/pk2377Isup3.cml

checkCIF report

Comment top

The Schiff base adducts of vanillin with various primary amines show an observable effect on tumours. Amine derivatives of vanillin present similar effects, such as acting as oxidative phosphorylation inhibitors, which prevent ATP sythesis (Cordano et al., 2002). There has been much research interest in vanillin derivatives due to its biological activities (Javiya et al. 2008). In this work, we report here the crystal structure of the title compound, (E)-4-((3,5-dimethylphenylimino)methyl)-2-methoxy-3-nitrophenol, (I). In (I), all bond lengths are within normal ranges (Allen et al., 1987) (Fig. 1).

Related literature top

The title compound is an imine derivative of 4-hydroxy-3-methoxy-2-nitrobenzaldehyde, a vanillin-like compound. For background to the biological activity of vanillin derivatives, see: Javiya et al. (2008); Cordano et al. (2002). For standard bond lengths, see: Allen et al. (1987).

Experimental top

An equimolar ratio of 4-hydroxy-3-methoxy-2-nitrobenzaldehyde (2 mmol, 394 mg) and 3,5-dimethylaniline (2 mmol, 242 mg) were dissolved in methanol (25 ml). The mixture was stirred for 3 h under a gentle reflux. After allowing the solution to stand in air for two days with methanol slowly evaporating, yellow crystals were deposited, isolated, washed with methanol three times, and dried under vacuum with CaCl₂ as desiccant.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (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 (I) showing 30% probability displacement ellipsoids.

(E)-4-[(3,5-Dimethylphenyl)iminomethyl]-2-methoxy-3-nitrophenol top

Crystal data top

C₁₆H₁₆N₂O₄	F(000) = 632
M_r = 300.31	D_x = 1.318 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2115 reflections
a = 8.616 (9) Å	θ = 2.4–26.4°
b = 9.690 (11) Å	µ = 0.10 mm⁻¹
c = 18.29 (2) Å	T = 296 K
β = 97.631 (11)°	Column, yellow
V = 1513 (3) Å³	0.23 × 0.21 × 0.12 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2935 independent reflections
Radiation source: fine-focus sealed tube	1699 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −8→10
T_min = 0.978, T_max = 0.989	k = −11→11
8085 measured reflections	l = −16→22

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.140	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0684P)² + 0.080P] where P = (F_o² + 2F_c²)/3
2935 reflections	(Δ/σ)_max < 0.001
203 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₆H₁₆N₂O₄	V = 1513 (3) Å³
M_r = 300.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.616 (9) Å	µ = 0.10 mm⁻¹
b = 9.690 (11) Å	T = 296 K
c = 18.29 (2) Å	0.23 × 0.21 × 0.12 mm
β = 97.631 (11)°

Data collection top

Bruker APEXII CCD diffractometer	2935 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1699 reflections with I > 2σ(I)
T_min = 0.978, T_max = 0.989	R_int = 0.032
8085 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.140	H-atom parameters constrained
S = 1.04	Δρ_max = 0.24 e Å⁻³
2935 reflections	Δρ_min = −0.17 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
N1	0.9369 (2)	0.4869 (2)	0.39259 (10)	0.0569 (5)
N2	0.50451 (19)	0.63346 (16)	0.41616 (8)	0.0416 (4)
O1	0.98163 (17)	0.29564 (16)	0.28424 (8)	0.0592 (4)
O2	0.73798 (16)	0.18585 (15)	0.19443 (8)	0.0542 (4)
H2	0.6585	0.1695	0.1658	0.081*
O3	1.0325 (2)	0.4118 (2)	0.42663 (10)	0.0972 (7)
O4	0.9417 (2)	0.61258 (19)	0.39560 (10)	0.0811 (6)
C1	0.8322 (2)	0.33311 (19)	0.29183 (11)	0.0410 (5)
C2	0.7044 (2)	0.27628 (19)	0.24588 (10)	0.0401 (5)
C3	0.5541 (2)	0.3148 (2)	0.25587 (11)	0.0441 (5)
H3	0.4693	0.2778	0.2254	0.053*
C4	0.5275 (2)	0.4069 (2)	0.31015 (11)	0.0428 (5)
H4	0.4251	0.4309	0.3155	0.051*
C5	0.6504 (2)	0.46491 (19)	0.35722 (10)	0.0395 (5)
C6	0.8019 (2)	0.42449 (19)	0.34604 (10)	0.0404 (5)
C7	0.6243 (2)	0.5559 (2)	0.41790 (11)	0.0427 (5)
H7	0.6985	0.5573	0.4598	0.051*
C8	0.4898 (2)	0.72319 (19)	0.47734 (10)	0.0389 (5)
C9	0.3404 (2)	0.7652 (2)	0.48727 (11)	0.0452 (5)
H9	0.2545	0.7324	0.4559	0.054*
C10	0.3177 (2)	0.8561 (2)	0.54361 (12)	0.0473 (6)
C11	0.4476 (3)	0.9040 (2)	0.58903 (11)	0.0492 (6)
H11	0.4334	0.9655	0.6266	0.059*
C12	0.5983 (2)	0.86339 (19)	0.58038 (11)	0.0452 (5)
C13	0.6190 (2)	0.77377 (19)	0.52390 (11)	0.0409 (5)
H13	0.7195	0.7469	0.5168	0.049*
C14	0.1558 (3)	0.9054 (3)	0.55369 (15)	0.0742 (8)
H14A	0.0792	0.8536	0.5220	0.111*
H14B	0.1460	1.0016	0.5414	0.111*
H14C	0.1392	0.8924	0.6041	0.111*
C15	0.7379 (3)	0.9183 (2)	0.63073 (13)	0.0659 (7)
H15A	0.8273	0.8609	0.6269	0.099*
H15B	0.7153	0.9180	0.6807	0.099*
H15C	0.7599	1.0109	0.6165	0.099*
C16	1.0488 (3)	0.3650 (3)	0.22692 (16)	0.0830 (8)
H16A	0.9857	0.3485	0.1804	0.124*
H16B	1.1528	0.3308	0.2251	0.124*
H16C	1.0531	0.4624	0.2368	0.124*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0502 (12)	0.0687 (13)	0.0484 (12)	0.0024 (10)	−0.0067 (9)	−0.0119 (10)
N2	0.0453 (10)	0.0436 (9)	0.0355 (10)	0.0019 (8)	0.0038 (8)	0.0029 (8)
O1	0.0433 (9)	0.0764 (11)	0.0564 (10)	0.0165 (8)	0.0017 (7)	−0.0015 (8)
O2	0.0520 (9)	0.0614 (9)	0.0468 (10)	0.0059 (8)	−0.0026 (7)	−0.0146 (8)
O3	0.0803 (14)	0.1037 (15)	0.0914 (14)	0.0299 (11)	−0.0490 (11)	−0.0251 (12)
O4	0.0812 (13)	0.0707 (12)	0.0860 (14)	−0.0246 (10)	−0.0088 (10)	−0.0067 (10)
C1	0.0394 (12)	0.0467 (11)	0.0355 (12)	0.0061 (9)	−0.0004 (9)	0.0031 (9)
C2	0.0482 (13)	0.0393 (10)	0.0317 (11)	0.0046 (9)	0.0012 (9)	−0.0001 (9)
C3	0.0433 (12)	0.0484 (12)	0.0390 (12)	−0.0026 (9)	−0.0005 (9)	−0.0031 (10)
C4	0.0380 (12)	0.0462 (11)	0.0436 (13)	0.0011 (9)	0.0029 (10)	0.0034 (10)
C5	0.0449 (13)	0.0393 (10)	0.0332 (11)	0.0033 (9)	0.0016 (9)	0.0023 (9)
C6	0.0415 (12)	0.0442 (11)	0.0324 (11)	0.0007 (9)	−0.0067 (9)	0.0010 (9)
C7	0.0474 (13)	0.0447 (11)	0.0342 (12)	0.0026 (10)	−0.0010 (9)	0.0020 (9)
C8	0.0443 (12)	0.0382 (10)	0.0339 (12)	0.0043 (9)	0.0037 (9)	0.0060 (9)
C9	0.0410 (13)	0.0492 (12)	0.0436 (13)	0.0058 (9)	−0.0014 (10)	0.0100 (10)
C10	0.0481 (13)	0.0490 (12)	0.0460 (13)	0.0147 (10)	0.0102 (11)	0.0100 (11)
C11	0.0618 (16)	0.0423 (11)	0.0438 (13)	0.0138 (10)	0.0080 (11)	−0.0011 (10)
C12	0.0502 (13)	0.0399 (11)	0.0434 (13)	0.0099 (9)	−0.0009 (10)	−0.0005 (10)
C13	0.0362 (12)	0.0418 (10)	0.0443 (12)	0.0075 (8)	0.0039 (9)	0.0000 (9)
C14	0.0547 (16)	0.0839 (18)	0.085 (2)	0.0269 (13)	0.0137 (14)	0.0051 (15)
C15	0.0650 (16)	0.0637 (15)	0.0644 (16)	0.0076 (12)	−0.0091 (13)	−0.0172 (12)
C16	0.0587 (17)	0.101 (2)	0.093 (2)	0.0072 (15)	0.0242 (16)	0.0017 (18)

Geometric parameters (Å, º) top

N1—O3	1.208 (2)	C8—C13	1.398 (3)
N1—O4	1.219 (3)	C9—C10	1.389 (3)
N1—C6	1.476 (3)	C9—H9	0.9300
N2—C7	1.274 (3)	C10—C11	1.383 (3)
N2—C8	1.436 (3)	C10—C14	1.509 (3)
O1—C1	1.362 (3)	C11—C12	1.385 (3)
O1—C16	1.431 (3)	C11—H11	0.9300
O2—C2	1.345 (2)	C12—C13	1.379 (3)
O2—H2	0.8200	C12—C15	1.512 (3)
C1—C6	1.380 (3)	C13—H13	0.9300
C1—C2	1.406 (3)	C14—H14A	0.9600
C2—C3	1.383 (3)	C14—H14B	0.9600
C3—C4	1.377 (3)	C14—H14C	0.9600
C3—H3	0.9300	C15—H15A	0.9600
C4—C5	1.392 (3)	C15—H15B	0.9600
C4—H4	0.9300	C15—H15C	0.9600
C5—C6	1.404 (3)	C16—H16A	0.9600
C5—C7	1.458 (3)	C16—H16B	0.9600
C7—H7	0.9300	C16—H16C	0.9600
C8—C9	1.385 (3)

O3—N1—O4	124.1 (2)	C10—C9—H9	119.7
O3—N1—C6	118.8 (2)	C11—C10—C9	118.4 (2)
O4—N1—C6	117.06 (19)	C11—C10—C14	120.5 (2)
C7—N2—C8	119.54 (17)	C9—C10—C14	121.0 (2)
C1—O1—C16	115.41 (18)	C10—C11—C12	122.2 (2)
C2—O2—H2	109.5	C10—C11—H11	118.9
O1—C1—C6	121.05 (17)	C12—C11—H11	118.9
O1—C1—C2	120.70 (19)	C13—C12—C11	118.75 (19)
C6—C1—C2	118.22 (19)	C13—C12—C15	120.4 (2)
O2—C2—C3	124.08 (18)	C11—C12—C15	120.8 (2)
O2—C2—C1	116.69 (19)	C12—C13—C8	120.32 (19)
C3—C2—C1	119.23 (19)	C12—C13—H13	119.8
C4—C3—C2	121.24 (18)	C8—C13—H13	119.8
C4—C3—H3	119.4	C10—C14—H14A	109.5
C2—C3—H3	119.4	C10—C14—H14B	109.5
C3—C4—C5	121.47 (19)	H14A—C14—H14B	109.5
C3—C4—H4	119.3	C10—C14—H14C	109.5
C5—C4—H4	119.3	H14A—C14—H14C	109.5
C4—C5—C6	116.32 (19)	H14B—C14—H14C	109.5
C4—C5—C7	122.25 (19)	C12—C15—H15A	109.5
C6—C5—C7	121.32 (18)	C12—C15—H15B	109.5
C1—C6—C5	123.51 (18)	H15A—C15—H15B	109.5
C1—C6—N1	117.89 (19)	C12—C15—H15C	109.5
C5—C6—N1	118.56 (19)	H15A—C15—H15C	109.5
N2—C7—C5	122.96 (18)	H15B—C15—H15C	109.5
N2—C7—H7	118.5	O1—C16—H16A	109.5
C5—C7—H7	118.5	O1—C16—H16B	109.5
C9—C8—C13	119.75 (19)	H16A—C16—H16B	109.5
C9—C8—N2	117.40 (18)	O1—C16—H16C	109.5
C13—C8—N2	122.77 (18)	H16A—C16—H16C	109.5
C8—C9—C10	120.6 (2)	H16B—C16—H16C	109.5
C8—C9—H9	119.7

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N2ⁱ	0.82	1.95	2.755 (3)	169

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₆N₂O₄
M_r	300.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.616 (9), 9.690 (11), 18.29 (2)
β (°)	97.631 (11)
V (Å³)	1513 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.23 × 0.21 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.978, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	8085, 2935, 1699
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.140, 1.04
No. of reflections	2935
No. of parameters	203
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.17

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N2ⁱ	0.82	1.95	2.755 (3)	169.3

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

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cordano, G., Pezoa, J., Munoz, S., Rivera, E., Medina, J., Nunez-Vergara, L. J., Pavani, M., Guerrero, A. & Ferreira, J. (2002). Eur. J. Pharm. Sci. 16, 255–263. Web of Science CrossRef PubMed CAS Google Scholar
Javiya, J., Godvani, N., Baluja, S., Parekh, J. & Chanda, S. (2008). Acta Cienc. Indica Chem. 34, 413–417. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o220

doi:10.1107/S1600536811054407

Open

access