Crystal structure of (E)-4-hy­droxy-3-{1-[(4-hy­droxy­phen­yl)imino]­eth­yl}-6-methyl-2H-pyran-2-one

Amel Djedouani; Sihem Boufas; Franck Cleymand; Michel François; Solenne Fleutot

doi:10.1107/S2056989015012840

. 2015 Jul 11;71(Pt 8):o564–o565. doi: 10.1107/S2056989015012840

Crystal structure of (E)-4-hydroxy-3-{1-[(4-hydroxyphenyl)imino]ethyl}-6-methyl-2H-pyran-2-one

Amel Djedouani ^a, Sihem Boufas ^b,^*, Franck Cleymand ^c, Michel François ^c, Solenne Fleutot ^c

PMCID: PMC4571398 PMID: 26396798

Abstract

In the title Schiff base, C₁₄H₁₃NO₄, which adopts the phenol–imine tautomeric form, the dihedral angle between the planes of the benzene and heterocyclic (r.m.s. deviation = 0.037 Å) rings is 53.31 (11)°. An intramolecular O—H⋯N hydrogen bond closes an S(6) ring. In the crystal, molecules are linked by O—H⋯O hydrogen bonds to generate C(11) chains propagating in the [010] direction. A weak C—H⋯O link is also observed, leading to the formation of R ⁵ ₅(32) rings extending parallel to the (101) plane.

Keywords: crystal structure, hydroxy Schiff base, pyran-2-one, phenol–imine tautomer, hydrogen bonding, proton-transfer processes

Related literature

For photochromic and thermochromic properties of hydroxy Schiff bases, see: Garnovskii et al. (1993 ▸); Hadjoudis et al. (2004 ▸). For potential materials for optical memory and switch devices, see: Zhao et al. (2007 ▸). For proton-transfer processes, see: Lussier et al. (1987 ▸). For Schiff base structures, see: Djedouani et al. (2007 ▸, 2008 ▸). For Schiff base bond lengths and angles, see: Girija & Begum (2004 ▸); Girija et al. (2004 ▸); Bai & Jing (2007 ▸). graphic file with name e-71-0o564-scheme1.jpg

Experimental

Crystal data

C₁₄H₁₃NO₄
M _r = 259.26
Monoclinic,
a = 7.8730 (5) Å
b = 11.7930 (8) Å
c = 13.5330 (8) Å
β = 99.896 (2)°
V = 1237.79 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.10 × 0.06 × 0.03 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ▸) T _min = 0.875, T _max = 0.947
17976 measured reflections
2582 independent reflections
2061 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.148
S = 1.07
2582 reflections
173 parameters
All H-atom parameters refined
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Data collection: COLLECT (Nonius, 2002 ▸); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ▸); data reduction: EVALCCD (Duisenberg et al., 2003 ▸); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▸); program(s) used to refine structure: OLEX2.refine (Dolomanov et al., 2009 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and Mercury (Macrae et al., 2006 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸) and PARST (Nardelli, 1995 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015012840/hb7460sup1.cif

e-71-0o564-sup1.cif^{(14.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015012840/hb7460Isup2.hkl

e-71-0o564-Isup2.hkl^{(124.2KB, hkl)}

Click here for additional data file.^{(5.1KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015012840/hb7460Isup3.cml

Click here for additional data file.^{(1MB, tif)}

. DOI: 10.1107/S2056989015012840/hb7460fig1.tif

The structure of the title compound in 50% probability ellipsoids.

Click here for additional data file.^{(1.1MB, tif)}

S . DOI: 10.1107/S2056989015012840/hb7460fig2.tif

Part of the crystal structure of (I), showing the formation of S(6) rings with dashed red lines. N—H⋯O and O—H⋯O hydrogen bonds are shown as blue dashed lines.

CCDC reference: 1410367

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O1H1N1	0.82	1.83	2.560(2)	147
O2H2O1ⁱ	0.82	1.90	2.710(2)	169
C12H12BO3ⁱⁱ	0.96	2.55	3.137(3)	120

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

This work was supported by Université Constantine 1, DZ-25000, Constantine, Algeria.

supplementary crystallographic information

S1. Comment

Hydroxy Schiff bases have been extensively studied due to their biological, photochromic and thermochromic properties (Garnovskii et al., 1993; Hadjoudis et al., 2004). They are potential materials for optical memory and switch devices (Zhao et al., 2007). Proton transfer in these compounds forms the basis for an explanation of the mechanisms of various biological processes where proton transfer is the rate-determining step (Lussier et al., 1987). In general, O-hydroxy Schiff bases exhibit two possible tautomeric forms, the phenol-imine (or benzenoid) and ketoamine (or quinoid) forms. Depending on the tautomers, two types of intra-molecular hydrogen bonds are possible: O—H···N in benzenoid and N—H···O in quinoid tautomers.

As part of our ongoing studies of Schiff bases (Djedouani et al., 2007, 2008), we now describe the synthesis and the structure of the title compound, which takes the form phenol-imine and complete a six-membered pseudocycle via an intramolecular O—H····O hydrogen bond.

The dehydroacetic acid ring and phenyl ring are almost planer with r.m.s deviation for the mean plane are 0.0260 and 0.0027 respectively. The dihedral angle between the two rings is 53.30 (0.05) °. The two torsional angles τ1 (N1—C5—C14—C4) and τ2 (C5—N1—C1—C6) defining the confirmation of the molecule.

The N1—C5 distance of 1.324 (2) Å agree with similar bond in related compounds (Girija & Begum, 2004; Girija et al. 2004), slightly longer than a typical C=N bond (1.283 (4) Å) (Bai & Jing, 2007); but much shorter than the single carbon-nitrogen bond (Table. 1), N1—C1=1.432 (3) Å because of the resonance. The carbon-carbon bond connecting the phenol and imine groups exhibits intermediate distances between a single and a double bond and agree well with those observed in other azomethines. The C5—N1—C14 and C14—C5—N1 bond angle of 117.70 (2)° and 117.47 () ° respectively in the Schiff base ligand are smaller than typical hexagonal of 120°. This is due to the effect of substitution on O of pyron & OH of the DHA ring.

In the crystal, molecules are aligned head to foot along b axis, in columns along to [0 0 1] axis and the structure is stabilized by an O—H···O hydrogen bond and another weak C—H···O interaction, leading to the formation of R₅⁵(32) rings extending parallel to the (101) plane (Fig. 2, Table.1).

S2. Experimental

Compound (I) was prepared by refluxing a mixture of a solution containing dehydroacetic acid (0.01 mmol) and para-4-aminophenol (0.01 mmol) in ethanol (40 ml). The reaction mixture was stirred for 2 h under reflux and left to cool. Yellow crystals grew after a few days.