Synthesis and crystal structure of 2-(2,3,4-Trimethoxy-6- methylbenzylideneamino)phenol

Article abstract of DOI:10.1007/s10870-009-9543-y

The title compound 2-(2,3,4-trimethoxy-6-methylbenzylideneamino)phenol (C₁₇H₁₉NO₄, M _r = 301.33) was synthesised and characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. The crys

Full text of DOI:10.1007/s10870-009-9543-y

J Chem Crystallogr (2009) 39:708–710
DOI 10.1007/s10870-009-9543-y
ORIGINAL PAPER
Synthesis and Crystal Structure of 2-(2,3,4-Trimethoxy-6-
Methylbenzylideneamino)phenol
Zu-Pei Liang Æ Jian Li Æ Cheng-Yun Wang Æ
Xi-Shi Tai
Received: 24 August 2008 / Accepted: 2 March 2009 / Published online: 27 March 2009
Ó Springer Science+Business Media, LLC 2009
Abstract The title compound 2-(2,3,4-trimethoxy-6-meth-
ylbenzylideneamino)phenol (C17H19NO4, Mr = 301.33) was
synthesised and characterized by elemental analysis, IR spectra
and single crystal X-ray diffraction. The crystal belongs to
monoclinic, space group P21/c, with a = 10.4458(14), b =
form metal complexes [7–9], which are very intreresting in
many fields, such as catalysis and enzymatic reactions [10,
11] and magnetism [12]. Recently, a few Schiff base
compounds with antibacterial activity have been investi-
gated [4, 13–15]. However, to the best of our knowledge,
the Schiff base 2-(2,3,4-trimethoxy-6-methylbenzylide-
neamino)phenol and the complexes derived from it have
never been reported so far. Investigation on the structure of
the Schiff base compound may be helpful to design and
synthesise new metal complexes. In this paper, the title
compound was synthesised and its molecular structure was
investigated by elemental analysis, FT-IR. and X-ray
crystallographic techniques.
°
˚
8.3870(10), c = 17.780(2) A, b = 91.102(2) , V = 1557.4(3)
3
3
˚
˚
A , Z = 4, Dc = 1.285 g/cm , k = 0.71073 A, l(Mo Ka) =
0.092 mm-1, F(000) = 640. The final refinement gave
R = 0.0452, wR(F2) = 0.1065 for 2,743 observed reflections
with I [ 2r(I). X-ray diffraction analysis reveals that the
molecule adopts an E configuration at the C=N functional
bond. The dihedral angle between the two phenyl rings
is 38.3(3)°. The crystal structure is stabilized by C–HÁÁÁO,
O–HÁÁÁO and O–HÁÁÁN hydrogen bonds and p–p stacking
interactions.
Experimental Procedures
Keywords 2-(2,3,4-Trimethoxy-6-
methylbenzylideneamino)phenol Á Synthesis Á
Crystal structure
Reagents and Techniques
Infrared absorption spectra were obtained from a Nicolet
NEXUS 670 FT-IR spectrometer in KBr discs and were
reported in cm-1 units. Carbon, nitrogen and hydrogen
analyzes were performed on an Elemental Analysensteme
GmbH Vario EL analyzer. 2,3,4-Trimethoxy-6-methyl-
benzaldehyde, 2-aminophenol and ethylalcohol were
purchased from Weifang Runze (China).
Introduction
Schiff bases are used as substrates in the preparation of a
number of industrial and biologically active compounds via
ring closure, cycloaddition and replacement reactions [1].
Schiff bases are known to have biological activities such as
antimicrobial [2–4], antitumor [5], and herbicidal proper-
ties [6]. They have also been widely used as versatile
ligands involved in various metal chelation reactions to
The Synthesis of 2-(2,3,4-Trimethoxy-6-
Methylbenzylideneamino)phenol
A mixture of 2-aminophenol (0.695 g, 5 mmol) and 2,3,4-
trimethoxy-6-methylbenzaldehyde (1.04 g, 5 mmol) in
ethanol (30 mL) was refluxed for 2 h. After cooling the
precipitate was filtered and dried. The product was
recrystallized in ethanol. Yield: 91%. A 20 mg of the
Z.-P. Liang (&) Á J. Li Á C.-Y. Wang Á X.-S. Tai
Department of Chemistry and Chemical Engineering,
Weifang University, 261061 Weifang, China
e-mail: zupeiliang@163.com
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J Chem Crystallogr (2009) 39:708–710
709
˚
product was dissolved in ethanol of 20 mL. The solution
was filtered to remove impurities, and then left for crys-
tallization at room temperature. Anal. Calcd. (%) for
C17H19NO4: C 67.77, H 6.31, N 4.65. Found (%): C 67.86,
H 6.54, N 4.56. Selected IR data (cm-1): 1,636 cm-1 (s,
–C=N), 1,200 cm-1 (s, Ar–O).
Table 2 Selected bond lengths (A) and bond angles (°)
N(1)–C(1)
1.261(3)
1.370(3)
1.385(3)
1.361(3)
1.360(3)
120.6(2)
116.1(2)
126.7(2)
117.0(2)
120.2(2)
115.5(2)
116.0(3)
120.7(3)
N(1)–C(12)
O(1)–C(8)
O(2)–C(9)
O(3)–C(10)
1.411(3)
1.385(4)
1.437(3)
1.417(3)
O(1)–C(3)
O(2)–C(4)
O(3)–C(5)
O(4)–C(13)
C(1)–N(1)–C(12)
C(4)–O(2)–C(9)
N(1)–C(1)–C(2)
O(1)–C(3)–C(2)
O(2)–C(4)–C(5)
O(3)–C(5)–C(4)
C(13)–C(12)–N(1)
O(4)–C(13)–C(12)
C(3)–O(1)–C(8)
C(5)–O(3)–C(10)
O(1)–C(3)–C(4)
C(3)–C(4)–O(2)
O(3)–C(5)–C(6)
C(17)–C(12)–N(1)
O(4)–C(13)–C(14)
118.0(2)
118.4(2)
121.1(2)
120.1(2)
124.7(2)
125.6(2)
118.8(3)
X-ray Structure Determination
The single crystal X-ray data of title compound was col-
lected on a Bruker SMART diffractometer with a graphite
˚
monochromatized Mo–Ka radiation (k = 0.71073 A). The
structure was solved by SHELXS-97 and refined with
SHELXL-97 [16]. The positions of the H atoms bonded to
˚
C atoms were calculated (C–H distance 0.96 A), and
refined using a riding model. All the H atoms were placed
in geometrically idealized positions and constrained to ride
on their parent atoms, with O–H and C–H distances of 0.82
and structure refinements are given in Table 1. Some
selected bond distances and angles are listed in Table 2.
The molecular structures with the atom-numbering scheme
are shown in Fig. 2. Crystallographic data (excluding
structure factors) for the structures reported in this paper
have been deposited with the Cambridge Crystallographic
Data Centre as supplementary publication no. 698899.
˚
and 0.96 A, respectively, and Uiso(H) = 1.2–1.5Ueq(C)
and Uiso(H) = 1.5Ueq(O). The details of the X-ray data
collection, experimental conditions, and structure solution
Table 1 Crystal and experimental data for the title compound
Compound
C17H19NO4
Light yellow/block
301.33
Results and Discussion
Color/shape
Formula weight
CCDC deposit no.
Crystal system
Space group
The Schiff reaction of 2,3,4-trimethoxy-6-methylbenzal-
dehyde with 2-aminophenol in a 1:1 ratio which was
confirmed by the elemental analysis and IR spectra.
The title compound consists of benzylidenimin and
o-hydroxyl phenyl groups, and they do not share a common
plane (Fig. 1). The benzene ring (C2–C7) is nearly planar
698899
Monoclinic
P21/c
˚
a = 10.4458(14) A
Unit cell dimensions
˚
b = 8.387(1) A
˚
c = 17.780(2) A
˚
to within 0.003(2) A, the displacements of C8, C9 and C10
˚
are -0.918(3), -0.984(2) and 0.169(3) A, respectively,
b = 91.102(2)°
3
˚
Volume
1557.4(3) A
from this plane. The another one (C12–C17) is nearly
˚
planar to within 0.005(3) A. The dihedral angle between
Z
4
Density (calculated)
Absorption coefficient
F(000)
1.285 g cm-3
0.092 mm-1
640
the two benzene ring planes is 38.3(3)°. The bond lengths
and bond angles are as expected. C1–N1 is a double bond
Crystal size
0.50 9 0.46 9 0.35 mm3
h range for data collection
Index ranges
1.95–25.01°
-10 B h B 12; -9 B k B 9;
-20 B l B 21
Reflections collected
Independent reflections
Reflections observed (I [ 2r(I))
Refinement method
7,524
2,743
1,531
Full-matrix least-squares on F2
Data/parameters
2,743/204
Goodness-of-fit on F2
R indices [I [ 2r (I)]
R indices (all data)
1.040
R1 = 0.0452; wR2 = 0.1065
R1 = 0.0998; wR2 = 0.1444
-3
˚
0.157 and -0.186 e. A
Largest diff. peak and hole
Fig. 1 The molecular structure of the title compound
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J Chem Crystallogr (2009) 39:708–710
molecule forms hydrogen bonded dimers (Fig. 2; Table 3).
The existence of two benzene rings is very helpful to form
a strong p–p stacking interactions [18].
Acknowledgments This work was supported by the Natural Sci-
ence Foundation of Shandong Province (No. Y2007B61).
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Table 3 Hydrogen bond schemes (A, )
˚
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D–HÁÁÁA
O4–H4ÁÁÁO2i
C9–H9CÁÁÁO3
D–H
HÁÁÁA
D–A
D–HÁÁÁA
0.82
0.96
2.482
2.438
3.068
3.069
129
136
Symmetry codes: (i) 1-x, 2-y, -z
˚
˚
[1.261(3) A] [15]. While the N1–C12 bond [1.411(3) A] is
found to have normal single-bond length. Bond lengths
˚
C3–O1 [1.370(3) A], C4–O2 [1.385(3) A] and C5–O3
˚
[1.361(3) A] are in good agreement with the values
˚
17. Zhang WJ, Lu M, Li CB, Zhou WY (2005) Acta Cryst E61:o3222
18. Su BQ (2007) J Chem Crystallogr 37:87. doi:10.1007/s10870-
006-9134-0
reported in the literature [17].
The crystal structure is stabilized by intermolecular
hydrogen bonds C–HÁÁÁO and O–HÁÁÁO, and the title
123