Home The crystal structure of (E)-4-(3-ethoxy-2-hydroxybenzylideneamino)benzoic acid, C16H15NO4
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The crystal structure of (E)-4-(3-ethoxy-2-hydroxybenzylideneamino)benzoic acid, C16H15NO4

  • Başak Koşar Kirca EMAIL logo
Published/Copyright: December 5, 2017

Abstract

C16H15NO4, triclinic, P1̅ (no. 2), a = 4.9960(4) Å, b = 6.9139(5) Å, c = 20.7650(15) Å, α = 83.718(6)°, β = 84.805(6)°, γ = 78.648(6)°, V = 697.25(9) Å3, Z = 2, Rgt(F) = 0.0480, wRref(F2) = 0.0988, T = 296 K.

CCDC no.: 942110

The asymmetric unit of the title crystal structure is shown in the figure. Tables 1 and 2 contain details of the measurement method and a list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:Brown needle
Size:0.76 × 0.30 × 0.03 mm
Wavelength:Mo radiation (0.71073 Å)
μ:1.0 cm−1
Diffractometer, scan mode:STOE IPDS 2, ω scans
2θmax, completeness:52°, 98.8%
N(hkl)measured, N(hkl)unique, Rint:7346, 2710, 0.141
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 1509
N(param)refined:198
Programs:Stoe programs [1], SHELX [2], ORTEP-3 [3], WinGX [4]
Table 2:

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).

AtomxyzUiso*/Ueq
C1−0.0486(4)0.5847(3)0.28544(10)0.0414(5)
C2−0.1998(4)0.4428(3)0.31452(10)0.0416(5)
C3−0.4125(4)0.4952(3)0.36158(10)0.0437(5)
C4−0.4763(5)0.6873(3)0.37826(11)0.0488(6)
H4−0.61980.72290.40900.059*
C5−0.3276(5)0.8288(3)0.34940(11)0.0528(6)
H5−0.37220.95810.36090.063*
C6−0.1167(5)0.7773(3)0.30435(10)0.0500(6)
H6−0.01640.87190.28590.060*
C7−0.7522(5)0.3840(3)0.43814(11)0.0516(6)
H7A−0.89950.48810.42310.062*
H7B−0.67880.42610.47480.062*
C8−0.8560(5)0.1955(4)0.45762(12)0.0664(7)
H8A−0.70840.09360.47230.080*
H8B−0.92900.15580.42100.080*
H8C−0.99720.21620.49210.080*
C90.1799(5)0.5306(3)0.23893(10)0.0466(6)
H90.28360.62520.22250.056*
C100.4725(4)0.3035(3)0.17547(10)0.0458(6)
C110.5881(5)0.4351(4)0.13141(11)0.0609(7)
H110.51240.56950.12890.073*
C120.8139(5)0.3671(3)0.09157(11)0.0599(7)
H120.89130.45640.06250.072*
C130.9279(5)0.1666(3)0.09416(10)0.0488(6)
C140.8084(5)0.0359(3)0.13666(11)0.0537(6)
H140.8811−0.09900.13820.064*
C150.5821(5)0.1029(3)0.17687(11)0.0515(6)
H150.50240.01290.20510.062*
C161.1746(5)0.0938(4)0.05226(10)0.0500(6)
N10.2443(4)0.3570(3)0.21973(8)0.0471(5)
O1−0.1432(4)0.2540(2)0.29939(8)0.0572(5)
O2−0.5430(3)0.3452(2)0.38719(7)0.0551(5)
O31.2797(4)0.2190(3)0.01362(8)0.0686(5)
O41.2701(4)−0.0897(3)0.05632(9)0.0663(5)
H1A−0.013(5)0.249(4)0.2681(11)0.089(10)*
H4A1.423(6)−0.129(6)0.0302(18)0.19(2)*

Source of materials

The title compound was prepared by refluxing a mixture of a solution containing 3-ethoxy-2-hydroxybenzaldehyde (0.5 g; 3.01 mmol) in 20 mL ethanol and a solution containing 4-aminobenzoic acid (0.41 g; 3.01 mmol) in 20 mL ethanol. The reaction mixture was stirred for 1 h under reflux. The crystals for the crystal structure determination were obtained from acetone by slow evaporation (yield 72%, m.p. 488–490 K).

Experimental details

All H atoms except for H1A and H4A were refined using riding models, with C—H distances of 0.96 Å for CH3 group, 0.97 Å for CH2 group and 0.93 Å for aromatic groups. The displacement parameters of these H atoms were fixed at 1.2Ueq of their parent carbon atom for aromatic groups and methylene, 1.5Ueq of their parent atoms for methyl group.

Comment

The reaction of an aldehyde and a primary amine forms the Schiff base compounds having a −C=N− double bond. These compounds have a wide range of application in the fields of coordination chemistry, biochemistry, pharmacy, nanotechnology, optical devices and textile industries [5], [6], [7]. Particularly the o-hydroxy Schiff base class is more attractive for physicists and chemists because of its interesting photo-, solvato- and thermochromic features which are caused by an intramolecular proton transfer from the hydroxyl O atom to the imine N atom with a change in the π-electronic system in the solid state. o-Hydroxy Schiff base compounds adopt OH (enol-imine/benzenoid) [8] or NH (keto-amine/quinoid) [9] tautomeric forms with reference to the location of the transferred proton.

The title compound adopts enol-imine tautomeric form and has E configuration around the C=N double bond. The bond lengths and angles are in the expected ranges and comparable with those of similar compounds in literature [10, 11] . The compound displays a strong intramolecular hydrogen bond including the atoms O1 and N1 (O⋯N = 2.588(2) Å) as a common feature of o-hydroxysalicylidene systems. As can be seen from the figure, this strong hydrogen bond constitutes a S(6) ring. In three dimensional network, the crystal structure is stabilized by an intermolecular O—H⋯O hydrogen bond and weak van der Waals interactions. The donor-acceptor distance of this intermolecular O4—H4A⋯O3′ hydrogen bond is 2.621(2) Å [symmetry code (’) = 3−x, −y, −z].

References

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Received: 2017-9-16
Accepted: 2017-11-10
Published Online: 2017-12-5
Published in Print: 2018-1-26

©2018 Başak Koşar Kirca, published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 License.

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