Synthesis, crystal structure and spectroscopic studies of 2-{(E)-[2-hydroxyphenyl)imino]methyl} phenol schiff base molecule

Article abstract of DOI:10.1007/s10870-009-9556-6

A new Schiff-base complex 2-{(E)-[2-hydroxyphenyl)imino]methyl}phenol has been synthesized and characterized by elemental analyses, UV-VIS and IR spectroscopy and single crystal X-ray determination. The structure comprises two independent and similar mole

Full text of DOI:10.1007/s10870-009-9556-6

J Chem Crystallogr (2009) 39:672–676
DOI 10.1007/s10870-009-9556-6
ORIGINAL PAPER
Synthesis, Crystal Structure and Spectroscopic Studies of 2-{(E)-
[2-Hydroxyphenyl)imino]methyl} Phenol Schiff Base Molecule
˘
Tuncay Tunc¸ Æ Musa Sarı Æ Murat Sadıkoglu Æ
¨
Orhan Bu¨yu¨kgu¨ngor
Received: 11 August 2008 / Accepted: 9 March 2009 / Published online: 21 March 2009
Ó The Author(s) 2009. This article is published with open access at Springerlink.com
Abstract
A
new Schiff-base complex 2-{(E)-[2-
Introduction
hydroxyphenyl)imino]methyl}phenol has been synthesized
and characterized by elemental analyses, UV–VIS and IR
spectroscopy and single crystal X-ray determination. The
structure comprises two independent and similar mole-
cules. The two independent molecules in the asymmetric
unit are hydrogen bonded and have different conforma-
tions. In each molecule, C13H11NO2, adopt an E configu-
ration about the azomethine C–N double bond. The
complex crystallized in the triclinic space group P-1. Two
benzene rings and azomethine group are practically
coplanar, as a result of intramolecular hydrogen bonds
involving the hydroxy O atom and azomethine N atom.
Also hydroxy group of the molecule is the presence
intermolecular O–HÁÁÁO hydrogen bonds with the hydroxy
group of the other molecule.
Schiff base complex have been playing an important role in
the development of coordination chemistry related to
catalysis and enzymatic reactions [1–5], magnetism and
molecular architectures [6, 7]. In particular salicylaldi-
mines are useful for the synthesis of transition metal
complexes. Schiff base ligands and their metal complexes
have been extensively studied over past few decades. Some
Schiff bases are used as ion-selective electrode [8]. Some
complexes containing nitrogen and oxygen donor atoms in
the complexes are effective as stereospecific catalysts for
oxidation, reduction, hydrolysis, biological activity and
other transformations of organic and inorganic chemistry
[9–12]. It is known that Schiff bases containing electro-
active imine group in non-aqueous media have two
reduction peaks corresponding to a one-electron transfer in
a cyclic voltammogram and the electrode reaction is an EC
mechanism [13]. The reduction behavior of some Schiff
bases was also studied on the glassy carbon electrodes
modified by the electrochemical reduction of diazonium
salts and the reduction behaviors of these molecules was
evaluated in connection with the role of the electron donor
or acceptor groups on the phenyl ring of the diazonium
salts [14, 15]. In addition, some Schiff base molecules were
also studied as electrochemical and quantum chemical the
effect on the corrosion of steel [16]. Aromatic Schiff bases
containing a hydroxyl group in the ortho position may have
two tautomeric forms, namely phenol-imine (O–HÁÁÁN) and
keto-amine (OÁÁÁH–N) structures [17]. Various studies were
carried out with these systems in order to establish the
existence of intramolecular hydrogen bonding, stabilizing
one of the tautomeric forms [18–20].
Keywords Crystal structure Á Schiff base Á
Hydroxypheny Á Phenol
T. Tunc¸
Education Faculty, Department of Science Education,
Aksaray University, 68100 Aksaray, Turkey
M. Sarı (&)
Education Faculty of Gazi, Department of Physics Education,
Gazi University, Besevler, 06500 Ankara, Turkey
e-mail: msari@gazi.edu.tr
˘
M. Sadıkoglu
Education Faculty, Department of Science Education,
Gaziosmanpas¸a University, 60100 Tokat, Turkey
¨
O. Bu¨yu¨kgu¨ngor
Faculty of Science and Literature, Department of Physics,
Ondokuz Mayıs University, 55139 Samsun, Turkey
In the present study, a new Schiff-base complex 2-
{(E)-[2-hydroxyphenyl)imino]methyl}phenol has been
123

J Chem Crystallogr (2009) 39:672–676
673
Table 1. Diffraction measurements were made at room
temperature on a Stoe IPDS II CCD X-ray diffractometer
using graphite-monochromated MoKa radiation using x/
2h scan mode [21]. Unit-cell dimensions were determined
and refined by using the angular settings of 25 automat-
ically centered reflections in the 1.76 B h B 26.50 range.
The structure was solved by the direct methods using
SHELXS-97 and refined by full-matrix least-squares
techniques on F2 with SHELXL-97 [22, 23]. The empir-
ical absorption corrections were applied by the multi-scan
method via X-RED software. All non-hydrogen atoms
were refined with anisotropic displacement parameters
and hydrogen atoms were included in their idealized
positions and refined isotropically. ORTEP drawing [24]
of the molecule with 50% probability displacement ther-
mal ellipsoids and atom-labeling scheme are shown in
Fig. 1.
Scheme 1 Structure of 2-{(E)-[2-hydroxyphenyl)imino]methyl}phe-
nol Schiff-base
synthesized and its structure was determined using the
X-ray diffraction method and characterized with spectro-
scopic techniques. The structure of Schiff base molecule is
given in Scheme 1.
Experimental
General Procedures and Materials
Salicylaldehyde and 2-aminophenol were purchased from
Fluka and used without further purification. Ethanol and
chloroform were purchased from Carlo Erba. All other
chemical substances used were reagent-grade commercial
products. IR spectrum was recorded on a MATTSON 1000
FT-IR spectrophotometer with range 4,000–400 cm-1
using KBr pellets. The electronic spectra in the 200–
900 nm range were obtained on a Shimadzu UV-160A
spectrophotometer using chloroform as the solvent. Ele-
mental analyses for (C, H, N) were performed using a
LECO CHNS 932 elemental analyzer.
Table 1 Crystal data and structure refinement details for complex
CCDC no.
694516
C13H11NO2
Empirical formula
Formula weight
Temperature (K)
213.23
293(2)
˚
Radiation (k, A)
MoKa (0.71073)
Triclinic, P-1
Crystal system, space group
˚
Unit cell dimensions (A, °)
a
b
c
a
b
c
9.0479(7)
10.1564(8)
12.3659(10)
110.323(6)
89.940(6)
102.996(6)
1034.62(14)
4
Synthesis of 2-{(E)-[2-Hydroxyphenyl)imino]methyl}
Phenol
The title complex, 2-{(E)-[2-hydroxyphenyl)imino]methyl}
phenol, was synthesized by reacting an equimolar mixture of
salicylaldehyde (0.61 g, 5 mmol) and 2-aminophenol
(0.55 g, 5 mmol) in boiling ethanol (100 mL). Boiling was
continued for several minutes and the mixture was left aside
overnight. The precipitate formed was filtered and the resi-
due was dissolved in CHCl3-EtOH (3:1) and set aside for
crystallization. Analysis calculated for C13H11NO2 (%): C,
73.25; H, 5.22; N, 6.47. Found: C, 73.19; H, 5.16; N, 6.56.
Yield: 0.75 g, (70%) and m.p. [ 186 °C. Color: Brown.
UV–VIS (kmax, nm, CH2Cl2): 383, 258. FT-IR (KBr, cm-1):
1628 v(CH–N), 3062 v(C–H), 1530 v(C–C), 1310 v(C–O).
3
˚
Volume (A )
Z
Calculated density (Mg m-3
)
1.369
Absorption coefficient (mm-1
)
0.093
F(000)
448
Crystal size (mm)
0.480 9 0.380 9 0.220
1.76–27.56
h Range for data collection (°)
Index ranges
-11 B h B 11, -12 B k B 12,
-15 B l B 15
Reflections collected
Independent reflections
Data/parameters
4288
3227 {Rint = 0.0450}
3227/293
X-ray Structure Determinations of 2-{(E)-
[2-Hydroxyphenyl)imino]methyl}Phenol
Final R indices [I C 2r(I)]
Goodness of fit on F2
Largest difference peak and
R1 = 0.0493, wR2 = 0.1416
1.038
0.574 and -0.353
The crystal and instrumental parameters used in the unit-
cell determination and data collection are summarized in
-3
˚
hole (e A
)
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J Chem Crystallogr (2009) 39:672–676
3,062 cm-1
.
Furthermore, the v(C–C) and v(C–O)
-1
stretching frequencies were observed in 1,530 cm and
1,310 cm-1, respectively.
Description of the Crystal Structure of 2-{(E)-
[2-Hydroxyphenyl)imino]methyl}Phenol
The structure of 2-{(E)-[2-hydroxyphenyl)imino]methyl}
phenol, crystallizes into a triclinic lattice with space group
P-1. An ORTEP [24] view of the asymmetric unit is shown
in Fig. 1 and selected bond distances and angles are pre-
sented in Table 2. The asymmetric unit contains two
independent Schiff base molecules. The two independent
molecules are almost identical with one another. In each
molecule, the two benzene rings and azomethine group are
Fig. 1 The molecular structure and atomic labeling scheme of the
compound. Displacement ellipsoids are drawn at the 50% probability
level. Hydrogen bonds are indicated by dashed lines
Results and Discussion
UV–VIS and IR Spectra of 2-{(E)-
[2-Hydroxyphenyl)imino]methyl}Phenol
The UV–VIS spectra of Schiff base complexe have been
obtained in 10-2 M in chloroform at room temperature.
This molecule exhibit the absorption peaks due to the
localized p–p* transition at 258 nm. The shoulder peak in
383 nm is tentatively attributed to the n–p* transition of
imino group. A strong absorption band at 1,628 cm-1 in
the IR spectra of the complex is assigned to azomethine
group, v(CH–N) mode [25]. The weak band of the aromatic
v(C–H) stretching frequency of ligand was observed in
˚
Table 2 Selected bond distances (A) and angles (°) for complex
C7–N1
1.301(2)
C20–N2
1.307(2)
C9–O2
1.356(2)
C22–O4
1.346(2)
C2–O1
1.294(2)
C15–O3
1.298(2)
C8–N1
1.416(2)
C21–N2
1.414(2)
C9–O2
1.356(2)
C22–O4
1.346(2)
C7–N1–C8
N1–C7–C1
O1–C2–C1
O2–C9–C8
126.95(14)
123.27(15)
121.66(16)
117.23(16)
C20–N2–C21
N2–C20–C14
O3–C15–C14
O4–C22–C21
126.82(14)
123.12(15)
120.84(15)
117.67(15)
Fig. 2 The molecular structure of compound, showing the intra- and
intermolecular hydrogen bonding. Intra-intermolecular O–HÁÁÁN and
O–HÁÁÁO hydrogen bonds are shown as dashed lines
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J Chem Crystallogr (2009) 39:672–676
675
Fig. 3 The crystal packing of compound viewed along the a axis. Intra-intermolecular O–HÁÁÁN and OHÁÁÁO hydrogen bonds are shown as
dashed lines
practically coplanar. The both molecules adopts an (E)-
configuration about the C7–N1 and C20–N2 bonds with the
azomethine nitrogen atoms. The C7–N1 and C20–N2 bond
˚
distances [1.301(2), 1.307(2) A] are appreciably close to
˚
that of a C–N double bond (1.28 A) [26–28]. The dihedral
O–HÁÁÁO hydrogen bonds with the hydroxy group of the
other molecule (Fig. 2). The bond distances, bond angles
and hydrogen bonding are comparable with the literature
[29]. As shown in Fig. 2, interesting feature of this struc-
ture is the presence of one intra-molecular and one
intermolecular O–HÁÁÁN and O–HÁÁÁO hydrogen bonds
which stabilise this conformation, respectively, [O(1)–
H(1)ÁÁÁN(1)] and [O(4)–H(4)ÁÁÁO(1)] in hydroxy group of
molecule. But other hydroxy group of the molecule is the
presence only intermolecular O–HÁÁÁO hydrogen bonds
which stabilise [O(2)–H(2)ÁÁÁO(3)] and [O(3)–H(3)ÁÁÁO(2)]
(Fig. 3). Intra-intermolecular hydrogen bond distances and
bond angles are listed in Table 3.
angle between of each molecule is 80.84(11)°. All the bond
distances in the molecule are within normal ranges com-
parable to those of the similar compounds [26–28]. The
both independent molecule is essentially coplanar. The two
independent molecules in the asymmetric unit are hydro-
gen bonded and have different conformation. In the
structure, the intramolecular hydrogen bonds involving the
hydroxy O atom and azomethine N atom. Also hydroxy
group of the molecule is the presence intermolecular
Supplementary Material
Table 3 Intra-intermolecular hydrogen bond distances and bond
angles
Crystallographic data for the structural analysis has been
deposited with the Cambridge Crystallographic Data Centre
as supplementary publication No. CCDC 694516. Copies of
this data can be obtained free of charge via www.ccdc.
cam.ac.uk/data_request/cif, by emailing data_request@
ccdc.cam.ac.uk, or by contacting. The Cambridge Crystallo-
graphic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
UK; Fax: ?44 1223 336033.
˚
˚
˚
D–HÁÁÁA
d(D–H)(A) d(HÁÁÁA)(A) d(DÁÁÁA))(A) D–HÁÁÁA (°)
O2–H2ÁÁÁO3a 0.82
O3–H3ÁÁÁO2b 0.82
O4–H4ÁÁÁO1 0.82
O1–H1ÁÁÁN1 0.82
a
1.76
2.22
1.77
1.87
2.5794(18)
2.5794(19)
2.5837(19)
2.599(2)
175
107
172
148
b
Symmetry codes: -1 ? x, y, z; 1 ? x, y, z
123

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J Chem Crystallogr (2009) 39:672–676
Acknowledgments The authors thank to acknowledge the Faculty
of Arts and Sciences, Ondokuz Mayıs University, Turkey, for use of
the Stoe IPDS-2 diffractometer purchased under grant F.279 of the
University Research Fund.
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