58 2-Hydroxy-6- (2-methoxyphenyl)aminomethylen cyclohexa-2,

Please download to get full document.

View again

of 4
12 views
PDF
All materials on our website are shared by users. If you have any questions about copyright issues, please report us to resolve them. We are always happy to assist you.
Document Description
58 2-Hydroxy-6- (2-methoxyphenyl)aminomethylen cyclohexa-2,
Document Share
Document Tags
Document Transcript
  electronic reprint Acta Crystallographica Section E Structure ReportsOnline ISSN 1600-5368 Editors: W. Clegg and D. G. Watson 2-Hydroxy-6-[(2-methoxyphenyl)aminomethylene]cyclohexa-2,4-dienone Onur S¸ahin, Orhan B¨uy¨ukg¨ung  ¨or, C¸i ˇgdem Albayrak and Mustafa Odabas¸o ˇglu Copyright © International Union of CrystallographyAuthor(s) of this paper may load this reprint on their own web site provided that this cover page is retained. Republication of this article or itsstorage in electronic databases or the like is not permitted without prior permission in writing from the IUCr. Acta Cryst. (2005). E 61 , o1579–o1581 S¸ahin et al. ¯ C 14 H 13 NO 3  organic papers Acta Cryst. (2005). E 61 , o1579–o1581 doi:10.1107/S160053680501319X S¸ahin et al.  C 14 H 13 NO 3 o1579 Acta Crystallographica Section E Structure ReportsOnline ISSN 1600-5368 2-Hydroxy-6-[(2-methoxyphenyl)amino-methylene]cyclohexa-2,4-dienone Onur S¸ahin, a OrhanBu¨yu¨kgu¨ngo¨r, a C¸ig˘demAlbayrak b and MustafaOdabas¸ogˇlu b * a Department of Physics, Ondokuz MayısUniversity, TR-55139, Samsun, Turkey, and b Department of Chemistry, Ondokuz MayısUniversity, TR-55139, Samsun, TurkeyCorrespondence e-mail: onurs@omu.edu.tr Key indicators Single-crystal X-ray study T  = 296 KMean   (C–C) = 0.002 A˚ R factor = 0.038 wR factor = 0.096Data-to-parameter ratio = 16.4For details of how these key indicators wereautomatically derived from the article, seehttp://journals.iucr.org/e. # 2005 International Union of CrystallographyPrinted in Great Britain – all rights reserved The molecule of the title compound, C 14 H 13 NO 3 , adopts theketo–amine tautomeric form. An intramolecular N—H ÁÁÁ Ohydrogen bond dictates the essentially planar moleculargeometry; the two benzene rings make a dihedral angle of 7.93 (7)  . The crystal packing is stabilized by intermolecularO—H ÁÁÁ O and C—H ÁÁÁ O hydrogen bonds. Comment It is known that the thermo- and photochromism observed inN-substituted ortho -hydroxyimines in the solid state arepossibly due to H-atom transfer from the hydroxy O atom tothe N atom (Hadjoudis et al. , 1987; Xu et al. , 1994). It is alsoknown that the chemical conductivity of Schiff basescontaining ortho -hydroxyphenyl fragments is strongly influ-enced by an H-atom transfer reaction between the phenol–imine and keto–amine tautomers (Yu ¨ ce et al. , 2004). Thephenol–imine form is dominant in salicylaldimine, while theketo–amine form is preferred in ortho -hydroxy-naphthaldimine Schiff bases. It has also been observed that, inthe solid state, the keto–amine form is present in hydroxy-naphthaldimine, while the phenol–imine form exists in sali-cylaldimine Schiff bases (Kaitner & Pavlovic etal. , 1996; Yıldı zet al. , 1998). The title compound, (I) (Fig. 1), is in the keto–amine tautomeric form.In the molecule of (I), the C10 O2 and N1—C8 bondlengths of 1.2931 (17) and 1.3043 (19) A˚, respectively(Table 1), are in good agreement with those observed in 2-[(2-hydroxy-4-nitrophenyl)aminomethylene]cyclohexa-3,5-dien-1(2 H  )-one [1.298 (2) and 1.308 (2) A˚; Ersanlı et al. , 2003] and1-[(4-nitrophenylamino)methylene]naphthalen-2(1 H  )-one[1.289 (3) and 1.306 (3) A˚; O ¨ zek et al. , 2004]. The C1—N1bond length is 1.4135 (18) A˚, corresponding to 1.4155 (18) A˚in 3-(4-acetylphenyliminomethyl)-1,2-dihydroxybenzene(Yu ¨ ce et al. , 2004). The C8 C9 bond length and C8—N1—C1bond angle are 1.404 (2) A˚and 127.29 (13)  , respectively,compared with 1.396 (3) A˚and 126.35 (19)  , respectively, in 1-[(4-nitrophenylamino)methylene]naphthalen-2(1 H  )-one(O ¨ zek et al. , 2004). Received 15 April 2005Accepted 26 April 2005Online 7 May 2005 electronic reprint  There is a strong intramolecular N1—H1 ÁÁÁ O2 hydrogenbond (Table 2), with the H atom transferred from the O to theN atom. The N1 ÁÁÁ O2 distance [2.5870 (16) A˚] is shorter thanthe sum of the van der Waals radii of O and N [3.07 A˚; Bondi et al. , 1964], and comparable with those observed in 2-{[tris-(hydroxymethyl)methyl]aminomethylene}cyclohexa-3,5-dien-1(2 H  )-one and its 6-hydroxy and 6-methoxy derivatives[2.5851 (16) A˚; Odabas¸og ˇ lu et al. , 2003]. This intramolecularN—H ÁÁÁ O hydrogen bond dictates the essentially planarmolecular geometry; the two benzene rings make a dihedralangle of 7.93 (7)  .In the crystal structure of (I), there is an intermolecular O—H ÁÁÁ O hydrogen bond with an O ÁÁÁ O distance of 2.7160 A˚(Table 2); this may be compared with the sum of the van derWaals radii of two O atoms [3.04 A˚; Pizzala et al. , 2000]. Thearrangement of O—H ÁÁÁ O hydrogen bonds can be describedby the graph-set notation R 22 (10), and this generates acentrosymmetric dimer with an S (6) motif (Bernstein et al. ,1995). The crystal packing (Fig. 2) is further stabilized by weakintermolecular C—H ÁÁÁ O hydrogen bonds (Table 2). Experimental The title compound was prepared by refluxing a solution containing3-hydroxysalicylaldehyde (3.5 mmol) in ethanol (10 ml) and a solu-tion containing 2-methoxyaniline (3.5 mmol) in ethanol (10 ml). Thereaction mixture was stirred for 1 h under reflux and then allowed tocool. The powder product, (I), was recrystallized from ethanol.Suitable single crystals were obtained from methanol (yield 83%;m.p. 478–479 K). Crystal data C 14 H 13 NO 3 M  r  = 243.25Monoclinic, P 2 1 = na = 7.5517 (7) A˚ b = 11.3022 (12) A˚ c = 13.4646 (13) A˚  = 95.186 (8)  V  = 1144.5 (2) A˚ 3 Z  = 4 D  x = 1.412 Mg m À 3 Mo K   radiationCell parameters from 5462reflections   = 2.4–27.9   = 0.10 mm À 1 T  = 296 KPrism, red0.30 Â 0.21 Â 0.15 mm Data collection Stoe IPDS-II diffractometerRotation ! scansAbsorption correction: integration(  X-RED ; Stoe & Cie, 2002) T  min = 0.973, T  max = 0.99313 408 measured reflections2724 independent reflections1551 reflections with I  > 2   (  I  ) R int = 0.070   max = 27.9  h = À 9 ! 9 k = À 14 ! 14 l  = À 17 ! 17 Refinement  Refinement on F  2 R [ F  2 > 2   ( F  2 )] = 0.038 wR ( F  2 ) = 0.096 S = 0.852724 reflections166 parametersH-atom parameters constrained w = 1/[   2 ( F  o2 ) + (0.0515 P ) 2 ]where P = ( F  o2 + 2 F  c2 )/3( Á /   ) max < 0.001 Á  max = 0.15 e A˚ À 3 Á  min = À 0.17 e A˚ À 3 Extinction correction: SHELXL97  (Sheldrick, 1997)Extinction coefficient: 0.017 (2) Table 1 Selected geometric parameters (A˚,  ). C1—N1 1.4135 (18)C8—N1 1.3043 (19)C8—C9 1.404 (2)C9—C10 1.425 (2)C10—O2 1.2931 (17)C11—O3 1.3673 (18)C2—C1—N1 123.54 (14)N1—C8—C9 123.20 (13)C8—C9—C10 120.11 (13)O2—C10—C9 122.59 (13)O3—C11—C10 119.47 (14)C8—N1—C1 127.29 (13)N1—C8—C9—C10 0.7 (2) C2—C1—N1—C8 6.0 (2) Table 2 Hydrogen-bond geometry (A˚,  ). D —H ÁÁÁ  A D —H H ÁÁÁ  A D ÁÁÁ  A D —H ÁÁÁ  A N1—H1 ÁÁÁ O2 0.86 1.89 2.5870 (16) 137O3—H3  A ÁÁÁ O2 i 0.82 1.95 2.7160 (16) 154C8—H8 ÁÁÁ O3 ii 0.93 2.59 3.3597 (19) 141 Symmetry codes: (i) À  x þ 2 ; À  y þ 1 ; À z þ 1; (ii) x À 1 ;  y ; z . After their location in a difference Fourier map, all H atoms werepositioned geometrically and refined using a riding model, with C—Hdistances in the range 0.93–0.96 A˚, O—H = 0.82 A˚and N—H =0.86 A˚, and with U  iso (H) = 1.2–1.5 U  eq of the parent atom.Data collection: X-AREA (Stoe & Cie, 2002); cell refinement:  X-AREA ; data reduction: X-RED (Stoe & Cie, 2002); program(s) organic papers o1580 S¸ahin et al.  C 14 H 13 NO 3 Acta Cryst. (2005). E 61 , o1579–o1581 Figure 1 A view of (I), with the atom-numbering scheme and 50% probabilitydisplacement ellipsoids. The dashed line indicates a hydrogen bond. Figure 2 A packing diagram for (I). Dashed lines indicate hydrogen bonds. OtherH atoms have been omitted for clarity. electronic reprint  used to solve structure: SHELXS97  (Sheldrick, 1997); program(s)used to refine structure: SHELXL97  (Sheldrick, 1997); moleculargraphics: ORTEP3 for Windows (Farrugia, 1997); software used toprepare material for publication: WinGX  (Farrugia, 1999). The authors acknowledge the Faculty of Arts and Sciences,Ondokuz Mayıs University, Turkey, for the use of the StoeIPDS-II diffractometer (purchased under grant No. F279 of the University Research Fund). References Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34 , 1555–1573.Bondi, A. (1964). J. Phys. Chem. 68 , 441–451.Ersanlı, C. C., Albayrak, C¸., Odabas¸og ˇ lu, M. & Erdo ¨ nmez, A. (2003). ActaCryst. C 59 , o601–o602.Farrugia, L. J. (1997). J. Appl. Cryst. 30 , 565.Farrugia, L. J. (1999). J. Appl. Cryst. 32 , 837–838.Hadjoudis, E., Vittorakis, M. & Mavridis, I. M. (1987). Tetrahedron , 43 , 1345–1360.Kaitner, B. & Pavlovic, G. (1996). Acta Cryst. C 52 , 2573–2575.Odabas¸og ˇ lu, M., Albayrak, C¸., Bu ¨ yu ¨ kgu ¨ ngo ¨ r, O. & Lo ¨ nnecke, P. (2003). ActaCryst. C 59 , o616–o619.O ¨ zek, A., Yu ¨ ce, S., Albayrak, C¸., Odabas¸og ˇ lu, M. & Bu ¨ yu ¨ kgu ¨ ngo ¨ r, O. (2004).  Acta Cryst. E 60 , o826–o827.Pizzala, H., Carles, M., Stone, W. E. E. & Thevand, A. (2000). J. Chem. Soc.Perkin Trans. 2 , pp. 935–939.Sheldrick, G. M. (1997). SHELXS97  and SHELXL97  . University of Go ¨ ttingen, Germany.Stoe & Cie (2002). X-RED and X-AREA . Stoe & Cie, Darmstadt, Germany.Xu, X., You, X., Sun, Z., Wang, X. & Liu, H. (1994). Acta Cryst. C 50 , 1169–1171.Yıldız, M., Kılı c¸, Z. & Ho ¨ kelek, T. (1998). J. Mol. Struct. 441 , 1–10.Yu ¨ ce, S., O ¨ zek, A., Albayrak, C¸., Odabas¸og ˇ lu, M. & Bu ¨ yu ¨ kgu ¨ ngo ¨ r, O. (2004).  Acta Cryst. E 60 , o810–o812. organic papers Acta Cryst. (2005). E 61 , o1579–o1581 S¸ahin et al.  C 14 H 13 NO 3 o1581 electronic reprint
Search Related
We Need Your Support
Thank you for visiting our website and your interest in our free products and services. We are nonprofit website to share and download documents. To the running of this website, we need your help to support us.

Thanks to everyone for your continued support.

No, Thanks