(E) 4 Meth­­oxy 2 [(4 nitro­phen­yl)imino­meth­yl]phenol

organic papers

o2106

14H12N2O4 doi:10.1107/S1600536805018155 Acta Cryst.(2005). E61, o2106–o2108

Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

(

E

)-4-Methoxy-2-[(4-nitrophenyl)iminomethyl]phenol

Ba˛sak Ko˛sar,aC¸ig˘dem Albayrak,b Mustafa Odabas¸og˘luband Orhan Bu¨yu¨kgu¨ngo¨ra*

a_{Department of Physics, Ondokuz Mayıs}

University, TR-55139, Samsun, Turkey, and b_{Department of Chemistry, Ondokuz Mayıs}

University, TR-55139, Samsun, Turkey

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 293 K

Mean(C–C) = 0.002 A˚

Rfactor = 0.042

wRfactor = 0.104

Data-to-parameter ratio = 16.8

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2005 International Union of Crystallography Printed in Great Britain – all rights reserved

The title compound, C14H12N2O4, exists as an enol–imine

tautomer, in which a strong intramolecular O—H N hydrogen bond is formed. This study verifies the preference of the enol–imine tautomeric form in the solid state.

Comment

o-Hydroxy Schiff bases derived from the reaction of o -hydroxyaldehydes with aniline have been examined exten-sively (Stewart & Lingafelter, 1959; Calligaris et al., 1972; Maslen & Waters, 1975). Schiff base compounds display interesting photochromic and thermochromic features and can be classified in terms of these (Cohenet al., 1964; Moustakali-Mavridis et al., 1980; Hadjoudis et al., 1987). Photo- and thermochromism ariseviaH-atom transfer from the hydroxy O atom to the N atom (Hadjoudiset al., 1987; Xuet al., 1994).

There are two possible types of intramolecular hydrogen bonds in Schiff bases, viz. the keto–amine (N—H O) and enol–imine (N H—O) tautomeric forms. X-ray investigation shows that (I) prefers the enol–imine tautomeric form.

o-Hydroxy Schiff bases have been found in the keto form (U¨ nver, Kabak et al., 2002; Odabas¸og˘lu, Albayrak, Bu¨yu¨k-gu¨ngo¨r & Goesmann, 2003; Ko˛sar et al., 2004; Ersanlı et al., 2004) or in the enol form (Karadayıet al., 2003; Leardiniet al.,

Received 2 June 2005 Accepted 8 June 2005 Online 17 June 2005

Figure 1

1998; U¨ nver, Yıldızet al., 2002; Elmalıet al., 1998) or as enol/ keto mixtures (Nazıret al., 2000).

The molecular structure of (I) is shown with the atom-numbering scheme in Fig. 1. Selected bond lengths and angles are listed in Table 1. The C13—O3 and C7—N2 bond lengths verify the presence of the enol–imine tautomeric form. These distances agree with the corresponding distances in N -(2-fluoro-3-methoxy)salicylaldimine [1.347 (3) and 1.280 (3) A˚ ; U¨ nver, Kendi et al., 2002] and N -[3,5-bis(trifluorometh-yl)phenyl]-3-methoxysalicylaldimine [1.352 (3) and 1.280 (4) A˚ ; Karadayıet al., 2003], which also show the enol– imine tautomeric form. The same bond distances can be compared with the corresponding distances in 2-{[tris- (hydroxymethyl)methyl]amino-methylene}cyclohexa-3,5-dien-1(2H)-one [1.3025 (16) and 1.2952 (18) A˚ ; Odabas¸og˘lu, Albayrak, Bu¨yu¨kgu¨ngo¨r & Lo¨nnecke, 2003] and 3-[(2-oxo-1-naphthylidene)methylamino]benzoic acid [1.290 (2) and 1.319 (3) A˚ ; Pavlovic´ & Sosa, 2000], which show the keto– amine tautomeric form. The C4—N1 bond length in the title compound is also in good agreement with the corresponding distances in the literature [1.4671 (18) A˚ (Zeller & Hunter, 2004) and 1.456 (4) A˚ (Glidewell et al., 2004)] for related compounds that contain a nitro group.

As a common feature ofo-hydroxysalicylidene systems, (I) displays a strong hydrogen bond between atoms N2 and O3 (Filarowskiet al., 2003; Yıldız et al., 1998). The bond lengths and angles of this hydrogen bond are listed in Table 2.

For a closely related compound, (E )-2-ethoxy-6-[(4-nitro-phenylimino)methyl]phenol, see Ko˛saret al.(2005).

Experimental

Compound (I) was prepared by refluxing a mixture of a solution containing 5-methoxysalicylaldehyde (3.5 mmol) in ethyl alcohol (10 ml) and a solution containing 4-nitroaniline (3.5 mmol) in ethyl alcohol (10 ml). The reaction mixture was stirred for 1 h under reflux. The solution was left to cool. The powder product was recrystallized from ethyl alcohol. Appropriate single crystals were grown from methyl alcohol (yield 70%, m.p. 461–462 K).

Crystal data

C14H12N2O4 Mr= 272.26

Monoclinic,P21=n a= 8.9769 (9) A˚

b= 14.3789 (13) A˚

c= 10.0589 (10) A˚ = 101.755 (8)

V= 1271.2 (2) A˚3

Z= 4

Dx= 1.423 Mg m

3

MoKradiation Cell parameters from 9989

reflections = 1.4–27.8

= 0.11 mm1 T= 293 (2) K Prism, red

0.270.180.11 mm

Data collection

Stoe IPDS-II diffractometer !rotation scans

Absorption correction: integration (X-RED32; Stoe & Cie, 2002)

Tmin= 0.977,Tmax= 0.989

19135 measured reflections 3049 independent reflections

1230 reflections withI> 2(I)

Rint= 0.072

max= 28.1

h=11!11

k=18!18

l=13!13

Refinement

Refinement onF2 R[F2> 2(F2)] = 0.042

wR(F2_{) = 0.104} S= 0.82 3049 reflections 181 parameters

H-atom parameters constrained

w= 1/[2

(Fo 2

) + (0.05P)2] whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.11 e A˚

3

min=0.14 e A˚

3

Table 1

Selected geometric parameters (A˚ ,_).

N2—C7 1.277 (2) O3—C13 1.351 (2) C4—N1 1.465 (2)

N1—O2 1.214 (2) N1—O1 1.223 (2)

O2—N1—O1 123.43 (18)

Table 2

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

O3—H33 N2 0.82 1.89 2.6102 (19) 146

All H atoms were refined using a riding model, with C—H = 0.96 A˚ (for CH3), C—H = 0.93 A˚ (for other CH), O—H = 0.82 A˚ and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl,O).

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement:

X-AREA; data reduction:X-RED32(Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:ORTEP-3 for Windows(Farrugia, 1997); software used to prepare material for publication:WinGX(Farrugia, 1999).

The authors thank the staff of the X-ray Laboratory of the Department of Physics, Ondokuz Mayis University, for their help and advice.

References

Calligaris, M., Nardin, G. & Randaccio, L. (1972).Coord. Chem. Rev.7, 385– 403.

Cohen, M. D., Schmidt, G. M. J. & Flavian, S. (1964).J. Chem. Soc.pp. 2041– 2051.

organic papers

Acta Cryst.(2005). E61, o2106–o2108 Ko˛saret al. _C

14H12N2O4

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Elmalı, A., Elerman, Y. & Zeyrek, C. T. (1998).J. Mol. Struct.443, 123–130. Ersanlı, C. C., Albayrak, C¸ ., Odaba˛sogˇlu, M., Tho¨ne, C. & Erdo¨nmez, A.

(2004).Acta Cryst.C60, o133–o135. Farrugia, L. J. (1997).J. Appl. Cryst.30, 565. Farrugia, L. J. (1999).J. Appl. Cryst.32, 837–838.

Filarowski, A., Koll, A. & Glowiaka, T. (2003).J. Mol. Struct.644, 187–195. Glidewell, C., Low, J. N., Skakle, M. S. J. & Wardell, J. L. (2004).Acta Cryst.

C60, o33–o34.

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Acta Cryst.E59, o851–o853.

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Maslen, H. S. & Waters, T. N. (1975).Coord. Chem. Rev.17, 137–176. Moustakali-Mavridis, I., Hadjoudis, E. & Mavridis A. (1980).Acta Cryst.B36,

1126–1130.

Nazır, H., Yıldız, M., Yılmaz, H., Tahir, M. N. & U¨ lku¨, D. (2000).J. Mol. Struct. 524, 241–250.

Odabas¸og˘lu, M., Albayrak, C¸ ., Bu¨yu¨kgu¨ngo¨r, O. & Goesmann, H. (2003).Acta Cryst.C59, o234–o236.

Odabas¸og˘lu, M., Albayrak, C¸ ., Bu¨yu¨kgu¨ngo¨r, O. & Lo¨nnecke, P. (2003).Acta Cryst.C59, o616–o619.

Pavlovic´, G. & Sosa J.-M. (2000).Acta Cryst.C56, 1117–1119.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Go¨ttingen, Germany.

Stewart, J. M. & Lingafelter, E. C. (1959).Acta Cryst.12, 842–845.

Stoe & Cie (2002).X-AREAandX-RED32. Stoe & Cie, Darmstadt, Germany. U¨ nver, H., Kabak, M., Zengin, D. M. & Durlu, T. N. (2002). J. Chem.

Crystallogr.31, 203–209.

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organic papers

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supporting information

sup-1 Acta Cryst. (2005). E61, o2106–o2108

supporting information

Acta Cryst. (2005). E61, o2106–o2108 [https://doi.org/10.1107/S1600536805018155]

(

E

)-4-Methoxy-2-[(4-nitrophenyl)iminomethyl]phenol

B

ą

sak Ko

˛

sar,

Ç

i

ğ

dem Albayrak, Mustafa Odaba

ş

o

ğ

lu and Orhan B

ü

y

ü

kg

ü

ng

ö

r

(E)-4-Methoxy-2-[(4-nitrophenyl)iminomethyl]phenol

Crystal data

C14H12N2O4

Mr = 272.26 Monoclinic, P21/n

Hall symbol: -P 2yn

a = 8.9769 (9) Å

b = 14.3789 (13) Å

c = 10.0589 (10) Å

β = 101.755 (8)°

V = 1271.2 (2) Å3

Z = 4

F(000) = 568

Dx = 1.423 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 9989 reflections

θ = 1.4–27.8°

µ = 0.11 mm−1

T = 293 K Prism, red

0.27 × 0.18 × 0.11 mm

Data collection

Stoe IPDS-II diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

Detector resolution: 6.67 pixels mm-1

rotation method scans

Absorption correction: integration (X-RED; Stoe & Cie, 2002)

Tmin = 0.977, Tmax = 0.989

19135 measured reflections 3049 independent reflections 1230 reflections with I > 2σ(I)

Rint = 0.072

θmax = 28.1°, θmin = 2.5°

h = −11→11

k = −18→18

l = −13→13

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.042}

wR(F2_{) = 0.104}

S = 0.82 3049 reflections 181 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2_(F

o2) + (0.05P)2]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.11 e Å−3

Δρmin = −0.14 e Å−3

Special details

supporting information

sup-2 Acta Cryst. (2005). E61, o2106–o2108

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

C1 0.08289 (19) 0.47916 (11) 0.36339 (18) 0.0524 (5) N2 0.18738 (15) 0.55222 (9) 0.40484 (15) 0.0557 (4) O3 0.45960 (14) 0.60752 (9) 0.52155 (15) 0.0799 (5)

H33 0.3921 0.5699 0.4928 0.120*

C7 0.1500 (2) 0.63745 (12) 0.38352 (18) 0.0561 (5)

H7 0.0511 0.6518 0.3399 0.067*

C12 0.5036 (2) 0.76916 (13) 0.5333 (2) 0.0649 (5)

H12 0.6032 0.7582 0.5783 0.078*

C13 0.4064 (2) 0.69466 (12) 0.49318 (19) 0.0587 (5) C4 −0.09738 (19) 0.32643 (12) 0.28793 (19) 0.0567 (5) C2 0.1359 (2) 0.39074 (11) 0.4000 (2) 0.0603 (5)

H2 0.2339 0.3830 0.4509 0.072*

C6 −0.0646 (2) 0.48993 (13) 0.2897 (2) 0.0629 (5)

H6 −0.1023 0.5492 0.2661 0.075*

C8 0.25691 (19) 0.71214 (11) 0.42517 (18) 0.0549 (5) C5 −0.1552 (2) 0.41352 (12) 0.2515 (2) 0.0647 (5)

H5 −0.2539 0.4206 0.2018 0.078*

O4 0.26926 (16) 0.96910 (8) 0.42188 (15) 0.0771 (4) C9 0.2084 (2) 0.80430 (11) 0.39989 (19) 0.0593 (5)

H9 0.1092 0.8164 0.3547 0.071*

N1 −0.1926 (2) 0.24483 (12) 0.24440 (19) 0.0727 (5) C11 0.4543 (2) 0.85820 (13) 0.5074 (2) 0.0644 (5)

H11 0.5211 0.9073 0.5346 0.077*

C3 0.0461 (2) 0.31393 (12) 0.3623 (2) 0.0638 (5)

H3 0.0824 0.2545 0.3871 0.077*

O2 −0.1413 (2) 0.16804 (11) 0.27642 (19) 0.1014 (6) C10 0.3065 (2) 0.87682 (12) 0.4414 (2) 0.0599 (5) O1 −0.31999 (18) 0.25807 (11) 0.17620 (18) 0.1002 (6) C14 0.1203 (2) 0.99100 (14) 0.3516 (3) 0.0868 (7)

H14A 0.1090 1.0573 0.3445 0.130*

H14B 0.0477 0.9663 0.4004 0.130*

H14C 0.1031 0.9643 0.2624 0.130*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

supporting information

sup-3 Acta Cryst. (2005). E61, o2106–o2108

C12 0.0555 (11) 0.0621 (12) 0.0731 (14) −0.0071 (9) 0.0038 (10) −0.0024 (10) C13 0.0564 (11) 0.0514 (10) 0.0655 (13) −0.0044 (9) 0.0058 (9) 0.0007 (9) C4 0.0555 (11) 0.0550 (11) 0.0598 (12) −0.0123 (8) 0.0124 (9) −0.0064 (9) C2 0.0509 (10) 0.0507 (10) 0.0753 (14) −0.0025 (8) 0.0030 (10) 0.0014 (9) C6 0.0562 (11) 0.0545 (11) 0.0733 (14) −0.0016 (8) 0.0022 (10) 0.0035 (9) C8 0.0524 (10) 0.0515 (10) 0.0596 (13) −0.0065 (8) 0.0083 (9) −0.0026 (9) C5 0.0531 (10) 0.0681 (12) 0.0684 (14) −0.0072 (9) 0.0021 (10) −0.0013 (10) O4 0.0788 (9) 0.0463 (7) 0.1007 (12) −0.0046 (7) 0.0049 (8) −0.0034 (7) C9 0.0561 (10) 0.0531 (10) 0.0662 (13) −0.0025 (9) 0.0063 (9) −0.0015 (9) N1 0.0705 (12) 0.0702 (12) 0.0782 (13) −0.0204 (9) 0.0170 (10) −0.0165 (9) C11 0.0623 (13) 0.0613 (12) 0.0679 (14) −0.0163 (9) 0.0093 (10) −0.0065 (9) C3 0.0631 (12) 0.0497 (10) 0.0766 (14) −0.0025 (9) 0.0098 (10) 0.0012 (9) O2 0.1045 (12) 0.0571 (9) 0.1369 (15) −0.0202 (9) 0.0115 (10) −0.0114 (9) C10 0.0676 (13) 0.0452 (10) 0.0665 (13) −0.0073 (9) 0.0129 (10) −0.0032 (9) O1 0.0714 (10) 0.0991 (11) 0.1209 (14) −0.0267 (8) −0.0021 (10) −0.0226 (10) C14 0.0827 (15) 0.0618 (13) 0.112 (2) 0.0076 (11) 0.0117 (14) 0.0020 (12)

Geometric parameters (Å, º)

C1—C2 1.381 (2) C6—C5 1.374 (2)

C1—C6 1.388 (2) C6—H6 0.9300

C1—N2 1.413 (2) C8—C9 1.402 (2)

N2—C7 1.277 (2) C5—H5 0.9300

O3—C13 1.351 (2) O4—C10 1.373 (2)

O3—H33 0.8200 O4—C14 1.415 (2)

C7—C8 1.444 (2) C9—C10 1.374 (2)

C7—H7 0.9300 C9—H9 0.9300

C12—C11 1.362 (2) N1—O2 1.214 (2)

C12—C13 1.389 (2) N1—O1 1.223 (2)

C12—H12 0.9300 C11—C10 1.384 (2)

C13—C8 1.399 (2) C11—H11 0.9300

C4—C3 1.363 (2) C3—H3 0.9300

C4—C5 1.376 (2) C14—H14A 0.9600

C4—N1 1.465 (2) C14—H14B 0.9600

C2—C3 1.375 (2) C14—H14C 0.9600

C2—H2 0.9300

C2—C1—C6 118.99 (16) C6—C5—C4 118.90 (17)

C2—C1—N2 115.69 (15) C6—C5—H5 120.6

C6—C1—N2 125.32 (16) C4—C5—H5 120.6

C7—N2—C1 121.86 (15) C10—O4—C14 117.67 (15)

C13—O3—H33 109.5 C10—C9—C8 120.43 (16)

N2—C7—C8 121.92 (16) C10—C9—H9 119.8

N2—C7—H7 119.0 C8—C9—H9 119.8

C8—C7—H7 119.0 O2—N1—O1 123.43 (18)

C11—C12—C13 120.61 (17) O2—N1—C4 118.85 (18)

C11—C12—H12 119.7 O1—N1—C4 117.72 (18)

supporting information

sup-4 Acta Cryst. (2005). E61, o2106–o2108

O3—C13—C12 118.68 (16) C12—C11—H11 119.5

O3—C13—C8 122.19 (16) C10—C11—H11 119.5

C12—C13—C8 119.12 (17) C4—C3—C2 118.76 (17)

C3—C4—C5 121.93 (17) C4—C3—H3 120.6

C3—C4—N1 119.13 (17) C2—C3—H3 120.6

C5—C4—N1 118.93 (16) O4—C10—C9 124.62 (17)

C3—C2—C1 120.99 (16) O4—C10—C11 115.94 (15)

C3—C2—H2 119.5 C9—C10—C11 119.44 (16)

C1—C2—H2 119.5 O4—C14—H14A 109.5

C5—C6—C1 120.40 (17) O4—C14—H14B 109.5

C5—C6—H6 119.8 H14A—C14—H14B 109.5

C1—C6—H6 119.8 O4—C14—H14C 109.5

C13—C8—C9 119.34 (16) H14A—C14—H14C 109.5 C13—C8—C7 121.50 (16) H14B—C14—H14C 109.5 C9—C8—C7 119.15 (15)

C2—C1—N2—C7 −176.33 (18) N1—C4—C5—C6 −178.54 (18) C6—C1—N2—C7 4.2 (3) C13—C8—C9—C10 0.0 (3) C1—N2—C7—C8 −179.66 (17) C7—C8—C9—C10 178.35 (18) C11—C12—C13—O3 −179.64 (19) C3—C4—N1—O2 0.4 (3) C11—C12—C13—C8 0.2 (3) C5—C4—N1—O2 179.9 (2)

C6—C1—C2—C3 1.3 (3) C3—C4—N1—O1 −179.0 (2)

N2—C1—C2—C3 −178.27 (18) C5—C4—N1—O1 0.5 (3) C2—C1—C6—C5 −1.3 (3) C13—C12—C11—C10 0.4 (3) N2—C1—C6—C5 178.15 (19) C5—C4—C3—C2 −1.0 (3) O3—C13—C8—C9 179.45 (18) N1—C4—C3—C2 178.47 (18) C12—C13—C8—C9 −0.4 (3) C1—C2—C3—C4 −0.1 (3) O3—C13—C8—C7 1.1 (3) C14—O4—C10—C9 −1.3 (3) C12—C13—C8—C7 −178.72 (17) C14—O4—C10—C11 178.41 (19) N2—C7—C8—C13 −1.1 (3) C8—C9—C10—O4 −179.67 (19) N2—C7—C8—C9 −179.43 (19) C8—C9—C10—C11 0.6 (3) C1—C6—C5—C4 0.3 (3) C12—C11—C10—O4 179.45 (19) C3—C4—C5—C6 0.9 (3) C12—C11—C10—C9 −0.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A