Synthesis and structural characterization of 4-hydroxyanilinium 3,4,5,6-tetrachloro-2-(methoxycarbonyl)benzoate methanol monosolvate

Article abstract of DOI:10.14233/ajchem.2013.12906b

The compound 4-hydroxyanilinium 3,4,5,6-tetrachloro-2-(methoxycarbonyl) benzoate methanol monosolvate (C₁₆H₁₅Cl₄NO ₆, M_r = 459.09) was synthesized and characterized by single crystal X-ray diffraction

Full text of DOI:10.14233/ajchem.2013.12906b

Asian Journal of Chemistry; Vol. 25, No. 2 (2013), 780-782
http://dx.doi.org/10.14233/ajchem.2013.12906B
Synthesis and Structural Characterization of 4-Hydroxyanilinium
3,4,5,6-Tetrachloro-2-(methoxycarbonyl)benzoate Methanol Monosolvate
JIAN LI
Department of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, P.R. China
Corresponding author: Tel: +86 536 8877561; E-mail: ljwfu@163.com
(Received: 20 October 2011;
Accepted: 20 August 2012)
AJC-11977
The compound 4-hydroxyanilinium 3,4,5,6-tetrachloro-2-(methoxycarbonyl)benzoate methanol monosolvate (C16H15Cl4NO6, Mr = 459.09)
was synthesized and characterized by single crystal X-ray diffraction. The crystal belongs to triclinic, space group P-1, with a = 6.9729(7),
b = 10.7860(11), c = 13.5101(15) Å, β = 83.105(2)º, V = 979.49(18) Å3, Z = 2, Dc = 1.557 g/cm3, λ = 0.71073 Å, µ(MoKα) = 0.637 mm-1,
F(000) = 468. The final refinement gave R = 0.0991, wR(F2) = 0.2400 for 3,338 observed reflections with I > 2σ(I). The asymmetric unit of
the title compound contains one 4-hydroxyanilinium cation, one 3,4,5,6-tetrachloro-2-(methoxycarbonyl)benzoate anion and one methanol
molecule. The two benzene rings are approximately parallel with a dihedral angle of 0.8 (2)º. The components of the crystal are connected,
via the intermolecular N-H···O and O-H···O hydrogen bonds interactions, to form network.
Key Words: 4-Hydroxyanilinium 3,4,5,6-tetrachloro-2-(methoxycarbonyl)benzoate, Monosolvate, Synthesis, Structure characterization.
diffractometer. The reflection data were measured at 298 K,
using a graphite monochromator MoKα (λ = 0.71073 Å)
radiation with an ω-2θ scan mode. The total reflections were
4,959 with 3,338 independent ones (Rint = 0.0462), of which
247 were observed with I > 2σ(I). Intensities were corrected
for Lorentz and polarization effects and empirical absorption
and all data were corrected using SADABB8 program.
The structure was solved by direct methods using
SHELXS-979 program. All the non-hydrogen atoms were
refined on F2 anisotropically by full-matrix least squares
method. All hydrogen atoms were placed in the geometrically
calculated positions. The contributions of these hydrogen
atoms were included in the structurefactor calculations. The
atomic scattering factors and anomalous dispersion corrections
were taken from International Table for X-ray crystallography10.
The final least-square cycle gave R = 0.0991 and ωR = 0.2400
(w = 1/[σ2(Fo2) + (0.1480P)2 + 0.0000P], where P = (Fo2 +
2Fc2)/3). S = 1.058, (∆ρ)min = -0.434 and (∆ρ)max = 1.118 e/Å3.
CIF file containing complete information on the studied
structure was deposited with CCDC, deposition number
824539 and is freely available upon request from the following
web site: www.ccdc.cam.ac.uk/data_request/cif
INTRODUCTION
Phthalimides and N-substituted phthalimides are an
important class of compounds because of their interesting
biological activities1. Phthalimides have also served as starting
materials and intermediates for the syntheses of alkaloids2 and
pharmacophores3. Several N-substituted tetrachlorophtha-
limides have recently been synthesized and the study revealed
N-(2,4-dinitrophenyl)tetrachloro phthalimide could be a
representative of a new group of α-glucosidase inhibitors and
exhibit significant antihyperglycemic effect4. In our previous
work seveval intermediates, similar to the title compound, have
been synthesized5-7. In this paper, the synthesis and the crystal
structure of the title compound is reported.
EXPERIMENTAL
Synthesis of the title compound: All the reagents were
of AR grade and used without further purification. A mixture
of 4,5,6,7-tetrachloroisobenzofuran-1,3-dione (2.86 g, 0.01
mol) and methanol (15 mL) was refluxed for 0.5 h. And then
4-hydroxyaniline (1.09 g, 0.01 mol) was added to the above
solution, being mixed round for 0.5 h at room temperature.
The above solution was kept at room temperature for 5 d.
Natural evaporation gave colourless single crystals of the title
compound, suitable for X-ray analysis.
RESULTS AND DISCUSSION
In the present work, the reaction of 3,4,5,6-tetrabromo-
2-(methoxycarbonyl)benzoic acid and 4-hydroxyaniline in
methanol is expected to form 4,5,6,7-tetrachloro-2-(4-
Data collection and structure determination:A selected
crystal of the title compound was mounted on a SMART CCD

Vol. 25, No. 2 (2013)
Synthesis of 4-Hydroxyanilinium 3,4,5,6-Tetrachloro-2-(methoxycarbonyl)benzoate Methanol Monosolvate 781
hydroxyphenyl) isoindoline-1,3-dione, but instead formed the
title compound. This may have happened because of the short
time and cool temperature for the reaction.
The atomic coordinates and equivalent isotropic thermal
parameters for the non-H atoms in the title compound are given
in Table-1 and the selected bond distances and bond angles in
Table-2.A displacement ellipsoid plot with atomic numbering
scheme is shown in Fig. 1 and a perspective view of the crystal
packing in the unit cell in Fig. 2.
TABLE-1
ATOMIC COORDINATES (× 104) AND
THERMAL PARAMETERS (Å2 × 103)
Atom
Cl(1)
Cl(2)
Cl(3)
Cl(4)
N(1)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
x
y
Z
U (eq)
55(1)
60(1)
68(1)
73(1)
48(2)
96(3)
116(3)
51(1)
58(2)
66(2)
76(2)
72(3)
43(2)
45(2)
39(2)
38(2)
40(2)
41(2)
47(2)
137(6)
39(2)
44(2)
48(2)
44(2)
45(2)
45(2)
93(4)
2038(3)
1528(3)
1966(4)
2555(4)
7382(10)
3789(13)
987(15)
4361(8)
1222(8)
6628(9)
6846(10)
2423(19)
2702(13)
2443(11)
2428(11)
2165(10)
1961(10)
2110(10)
2318(12)
3430(20)
7195(10)
6920(11)
6723(11)
6831(11)
7083(11)
7253(11)
8271(17)
7559(2)
10334(2)
10789(2)
8499(2)
6069(5)
5094(7)
5865(8)
4962(5)
4918(5)
11027(5)
2980(6)
5913(10)
5438(7)
7028(7)
6793(6)
7825(7)
9051(6)
9269(6)
8249(7)
3931(11)
7386(6)
8378(7)
9618(7)
9841(7)
8838(7)
7611(7)
3559(10)
9787(1)
8629(2)
6291(2)
5135(2)
9171(5)
6468(5)
6001(7)
8786(4)
8756(4)
7112(4)
8010(5)
6404(7)
8558(5)
6945(6)
7984(5)
8497(5)
7982(6)
6946(5)
6424(6)
6033(11)
8643(5)
9179(6)
8687(6)
7647(6)
7107(6)
7618(6)
7397(9)
Fig. 1. Molecular structure with atomic numbering scheme
planes of the methoxycarbonyl and carboxylate groups form
dihedral angles of 65.4(3) and 48.9(3)º, respectively with the
benzene ring. The bond lengths and angles are in agreement
with those in cyclohexanaminium 3,4,5,6-tetrachloro-2-
(methoxycarbonyl)benzoate6 and hexane-1,6-diaminium
3,4,5,6-tetrachloro-2-(methoxycarbonyl) benzoate7. As seen
from Fig. 2 and Table-3, the crystal structure of the title comp-
ound is stabilized by N-H···O and O-H···O hydrogen bonds
interactions. Fig. 2 reveals that in the crystal the components
of the title compound are connected, via the intermolecular
hydrogen bonds interactions, to form network.
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
TABLE-2
SELECTED BOND LENGTHS (Å) AND BOND ANGLES (º)
Bond
Length (Å)
1.711(7)
1.722(7)
1.715(7)
1.709(8)
1.465(8)
1.174(11)
1.546(13)
1.209(13)
1.228(9)
1.244(9)
1.348(8)
1.384(12)
1.514(12)
1.522(10)
–
Bond
Angle (º)
110.7(10)
123.8(11)
116.3(11)
119.7(10)
126.1(7)
117.0(7)
116.9(7)
121.1(7)
120.8(7)
117.9(7)
120.3(6)
119.4(6)
120.1(6)
122.6(7)
116.8(7)
Cl(1)-C(5)
Cl(2)-C(6)
Cl(3)-C(7)
Cl(4)-C(8)
N(1)-C(10)
O(1)-C(1)
O(1)-C(9)
O(2)-C(1)
O(3)-C(2)
O(4)-C(2)
O(5)-C(13)
O(6)-C(16)
C(1)-C(3)
C(2)-C(4)
–
C(1)-O(1)-C(9)
O(1)-C(1)-O(2)
O(1)-C(1)-C(3)
O(2)-C(1)-C(3)
O(3)-C(2)-O(4)
O(3)-C(2)-C(4)
O(4)-C(2)-C(4)
C(8)-C(3)-C(4)
C(8)-C(3)-C(1)
C(4)-C(3)-C(1)
C(5)-C(4)-C(2)
C(15)-C(10)-N(1)
C(11)-C(10)-N(1)
O(5)-C(13)-C(12)
O(5)-C(13)-C(14)
Fig. 2. View of crystal packing down the a-axis
TABLE-3
HYDROGEN BOND SCHEMES (Å, º)
D-H···A
D-H
H···A
D-A
D-H···A
N1-H1A···O3
N1-H1B···O3a
N1-H1B···O4a
N1-H1C···O4b
O5-H5···O6c
O6-H6···O3
0.89
0.89
0.89
0.89
0.82
0.82
1.86
2.36
2.24
1.93
1.87
1.95
2.75
2.99
3.03
2.77
2.64
2.77
172
128
148
156
156
173
As seen from Fig. 1, the asymmetric unit of the title com-
pound contains one 4-hydroxyanilinium cation, one 3,4,5,6-
tetrachloro-2-(methoxycarbonyl)benzoate anions and one
methanol molecules. The two benzene rings are approximately
parallel with a dihedral angle of 0.8(2)º. In the anion, the mean
Symmetry codes: (a) 1-x, 1-y, 2-z (b) 1+x, y, z (c) x, 1+y, z.

782 Li
Asian J. Chem.
4. S. Mahapatra, J. Singh, R. Raju, B.C. Maiti and T.K. Maity, Asian J.
Chem., 23, 1581 (2011).
ACKNOWLEDGEMENTS
5. Z.P. Liang and J. Li, Asian J. Chem., 25, 657 (2013).
6. J. Li, Acta Cryst., E67, o842 (2011).
7. J. Li, Acta Cryst., E67, o901 (2011).
This work was supported by Shandong Provincial Natural
Science Foundation, China (No. ZR2009BL027).
8. G.M. Sheldrick, SADABS, Program for Empirical Absorption Correc-
tion of Area Detector Data, University of Gottingen, Germany (1996).
9. G.M. Sheldrick, SHELXTL V 5.1 Software Reference Manual, Bruker
AXS, Inc., Madison, Wisconsin, USA (1997).
10. Siemens, SMART and SAINT, Area Detector Control and Integration
Software. Siemens Analytical X-Ray Systems, Inc., Madison, Wiscon-
sin, USA (1996).
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