Supramolecular architecture of two 4-(methylsulfonyl) benzaldehyde Schiff bases

Article abstract of DOI:10.1007/s10870-012-0290-0

Two crystalline forms of 1,4-dimethyl-2-(4- (methyl-sulfonyl) styryl)benzene (1) and 1,3-diisopropyl-2- (4-(methyl-sulfonyl)styryl) benzene (2) were obtained and their structures were determined by X-ray diffraction technique. Both compound 1 and 2 crystallized in a triclinic space group P-1 with cell parameters a = 5.375(2) A, b = 18.402 (7) A, c = 23.109(9) A, α = 95.838(4), β = 94.579(4)8, γ = 91.407(4)8, V = 2265.3(15) A 3, Dc = 1.264 g/cm³, Z = 6, and a = 9.332(7) A, b = 11.028(8) A, c = 11.574 (9) A, α = 111.795(6)8, β = 94.162(8)8, γ = 92.177(7)8, V = 1100.3(14) A³, Dc = 1.161 g/cm³, Z = 2, respectively. Both of them display a trans-configuration with respect to the C=N double bond. Their crystal packings are stabilized by weak C-H· · ·O hydrogen bonds and van der Waals interactions. Springer Science+Business Media, LLC 2012.

Full text of DOI:10.1007/s10870-012-0290-0

J Chem Crystallogr (2012) 42:611–614
DOI 10.1007/s10870-012-0290-0
ORIGINAL PAPER
Supramolecular Architecture of Two 4-(Methylsulfonyl)
Benzaldehyde Schiff Bases
•
•
•
Shao-Song Qian Yue-Hu Chen Hong-You Cui
Hai-Liang Zhu
Received: 22 July 2011 / Accepted: 14 February 2012 / Published online: 3 March 2012
Ó Springer Science+Business Media, LLC 2012
Abstract Two crystalline forms of 1,4-dimethyl-2-(4-
(methyl-sulfonyl) styryl)benzene (1) and 1,3-diisopropyl-2-
(4-(methyl-sulfonyl)styryl) benzene (2) were obtained and
their structures were determined by X-ray diffraction tech-
nique. Both compound 1 and 2 crystallized in a triclinic space
of Schiff bases. Not only have Schiff base compounds
attracted attention for the development of coordination
chemistry related to catalysis and enzymatic reactions, mag-
netism and molecular architectures [1], but also they have
beenofgreatofinterestowingtotheirwiderangeofbiological
activities. They have been found to possess pharmacological
activities such as antimalarial [2], anticancer [3], antibacterial
[4], antifungal, antitubercular, antiinflammatory, antimicro-
bial and antiviral [5]. In view of above biological importance
of Schiff bases, we have synthesized and studied a few crys-
tal structures of 4-(methylsulfonyl)benzaldehyde’s Schiff
bases [6–8], and attempt to investigate their biological activ-
ities and synthesize more these Schiff bases. Herein, the
crystal structures of 1,4-dimethyl-2-(4-(methylsulfonyl)sty-
ryl)benzene and 1,3-diisopropyl-2-(4-(methylsulfonyl)sty-
ryl)benzene were reported.
˚
group P-1 with cell parameters a = 5.375(2) A, b = 18.402
˚
˚
(7) A, c = 23.109(9) A, a = 95.838(4), b = 94.579(4)8,
3
3
˚
c = 91.407(4)8, V = 2265.3(15) A , Dc = 1.264 g/cm ,
˚
Z = 6, and a = 9.332(7) A, b = 11.028(8) A, c = 11.574
˚
˚
(9) A, a = 111.795(6)8, b = 94.162(8)8, c = 92.177(7)8,
3
3
˚
V = 1100.3(14) A , Dc = 1.161 g/cm , Z = 2, respec-
tively. Both of them display a trans-configuration with
respect to the C=N double bond. Their crystal packings are
stabilized by weak C–HÁÁÁO hydrogen bonds and van der
Waals interactions.
Keywords 4-(Methylsulfonyl)benzaldehyde Á
Schiff base Á Crystal structure
Experimental
Introduction
All reagents, unless otherwise stated, were purchased as
AR grade and used without further purification. The
melting point was determined by an XT-4 microscopic
melting apparatus and uncorrected. IR spectra were
recorded on a Bruker Tensor 27 spectrophotometer using
4-(Methylsulfonyl)benzaldehyde is an important precursor
for the synthesis of amino alcohol with applications to the
synthesis of antibiotics thiamphenicol, which is well
acknowledged to possess a wide spectrum of antibacterial
bioactivities. In addition, the 4-(methylsulfonyl)benzalde-
hyde may be condensed with organic amines to prepare kinds
1
KBr disks with wave numbers in cm-1. HNMR spectra
were recorded on a Bruker AV-300 instrument at 300 MHz
in CDCl3. Crystal data were obtained on a Bruker APEX-II
CCD diffractometer. The synthesis route of the title com-
pounds is shown in Scheme 1.
S.-S. Qian Á Y.-H. Chen Á H.-L. Zhu (&)
School of Life Sciences, Shandong University of Technology,
Zibo 255049, China
e-mail: zhuhl@nju.edu.cn
1,4-Dimethyl-2-(4-(methylsulfonyl)styryl)benzene (1)
H.-Y. Cui
School of Chemical Engineering, Shandong University of
Technology, Zibo 255049, China
4-(Methylsulfonyl)benzaldehyde (0.184 g) and 2,5-
dimethylaniline (0.121 g) were dissolved in acetonitrile
123

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J Chem Crystallogr (2012) 42:611–614
Scheme 1 The synthesis route
of two Schiff bases
(20 mL). The mixture was stirred at room temperature for
10 min to give a clear yellow solution. After keeping the
solution in air for 7 days, yellow block-shaped crystals
were obtained at the bottom of the vessel. Yield 78%; m.p.
147.6–148.7 °C. IR (KBr): 3435.8, 1653.0, 3000.2,
1628.4,1569.4, 1499.9, 1309.0, 1291.8, 1148.6, 1120.0,
x - 2 h scan technique. The structure was solved by direct
methods and refined on F2 by full-matrix least-squares with the
Bruker’s SHELXL-97 program [9]. All nonhydrogen atoms
were refined anisotropically. All hydrogen atoms were treated
using a riding model. Experimental details for X-ray data col-
lection of 1 and 2 are presented in Table 1, and the molecular
structure and the atomic numbering Scheme of 1 and 2 are
shown in Fig. 1, respectively.
1088.3 cm-1
;
1H NMR (CDCl3, 300 MHz)d ppm:
8.64(1H, s, H-C7), 8.11 (2H, d, H-C1, H-C5), 8.01 (2H, d,
H-C2, H-C4), 7.05–7.25 (3H, m, H-C10, H-C11, H-C13),
3.32(3H, s, H-C16), 2.35(6H, s, H-C14, H-C15).
Table 1 Crystal data for 1 and 2
Compound
1
2
2,6-Diisopropyl-N-(4-(methylsulfonyl)
Empirical formula
C16H17NO2S
C20H25NO2S,
C2H3N
benzylidene)aniline (2)
Formula weight
T (K)
287.38
296
384.52
296
4-(Methylsulfonyl)benzaldehyde (0.184 g) and 2,6-diiso-
propylaniline (0.177 g) were dissolved in acetonitrile
(20 mL). The mixture was stirred at room temperature for
10 min to give a clear yellow solution. After keeping the
solution in air for 7 days, yellow block-shaped single
crystals of 2 suitable for X-ray diffraction (XRD) analysis
were obtained at the bottom of the vessel, Yield 81%; m.p.
153.4–154.6 °C.
Crystal system
Space group
Triclinic
P-1
Triclinic
P-1
˚
a (A)
5.375(2)
18.402(7)
23.109(9)
95.838(4)
94.579(4)
91.407(4)
2265.3(15)
6
9.332(7)
11.028(8)
11.574(9)
111.795(6)
94.162(8)
92.177(7)
1100.3(14)
2
˚
b (A)
˚
c (A)
a (8)
b (8)
c (8)
IR (KBr): 3436.7, 2960.9, 1640.0, 1572.1, 1458.5, 1310.8,
1292.6, 1144.0, 1086.1, 968.1 cm-1 1H NMR(CDCl3,
;
3
˚
V (A )
300 MHz) d ppm: 8.66(1H, s, H-C7), 8.11 (2H, d, H-C4,
H-C5), 8.02 (2H, d, H-C2, H-C6), 7.12–7.51 (3H, m, H-C10,
H-C11, H-C12), 3.32(3H, s, H-C20), 2.87(2H, m, H-C14,
H-C17), 1.2 (12H, d, H-C15, H-C15, H-C16, H-C18, H-C19).
Z
h range (8)
l (/mm)
F (000)
Dc (g/cm3)
2.19–25.3
0.215
2.77–25.3
0.165
912
412
1.264
1.161
X-Ray Crystal Structure Determination
2
3
˚
Goodness-of-fit on F (e/A )
No. data collected
No. unique data
Rint
0.966
1.08
15,101
8,103
6,402
The two title compounds gave yellow block crystals. The single
crystals with approximate dimensions of 0.23 9 0.20 9
0.16 mm3 (1) and 0.23 9 0.22 9 0.20 mm3 (2) were used to
respectively perform for XRD studies. The data were collected
on a Bruker APEX-II CCD diffractometer with graphite-
monochromated Mo Ka radiation (k = 0.071073 nm) using
3,901
0.0597
0.04
R1, wR2 [I [ 2r(I)]
R1, wR2 (all data)
3
Largest diff. peak and hole (e/A ) 0.28, -0.25
0.0663, 0.0861 0.0714, 0.1478
0.1560, 0.1053 0.1016, 0.1634
˚
0.96, -0.48.
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J Chem Crystallogr (2012) 42:611–614
613
composed of 2 and an acetonitrile molecule, which is
linked to the oxygen atom in methylsulfonyl of 2 via C21–
H21BÁÁÁO2 hydrogen bond. Both of compound 1 and 2
display a trans-configuration with respect to the C=N
double bond. Their crystal packings are stabilized by weak
C–HÁÁÁO hydrogen bonds, C–HÁÁÁp interactions and van der
Waals interactions.
All the bond lengths of 1 are very close to those of 2,
and comparable to the values observed in similar com-
pounds [6–8]. However, there are significant differences in
the dihedral angle between the aromatic ring A plane and
the aromatic ring B plane in 1 and 2. The dihedral angle is
67.95(19) in 1, but it is 87.64(19) in 2. Although the
chemical compositions of aromatic ring A in 1 is the same
as that in 2, but the torsion angles are very different for two
compounds. The torsion angles in 1 are C2–C3–S1–
C16 = -26.0(3) and C4–C3–S1–C16 = -175.7(3), in
contrast, the corresponding torsion angles in 2 are 109.3(3)
for C2–C1–S1–C20 and -71.2(3) for C6–C1–S1–C20.
There are both intramolecular and intermolecular
hydrogen bonds in the crystal structure of 1. Methylsulfo-
nyl carbon atom C16 in the molecule acts as hydrogen-
bond donor to sulfonyl atom O1and O2 in the molecule at
(-x, 2 - y, 2 - z) and (1 ? x, y, z) respectively, forming
the intramolecular hydrogen bonds. And the intermolecular
hydrogen bonds include: (1) methylsulfonyl oxygen atom
O5 in a molecule as a hydrogen-bond acceptor to carbon
atom C18 in aromatic ring A in another molecule at
(-1 ? x, y, z) to form hydrogen bond C18–H18ÁÁÁO5 with
˚
CÁÁÁO distance of 3.311(5) A, and (2) methylsulfonyl car-
Fig. 1 The molecular configuration and atom numbering scheme for
1 and 2, atoms are shown as 30% probability ellipsoids
bon atom C48 as a donor to methylsulfonyl oxygen atom
O4 in another molecule at (1 - x, 1 - y, -z) to form
hydrogen bond C48–H48ÁÁÁO4 with CÁÁÁO distance of
˚
3.351(4) A (as shown in Table 2).
Results and Discussion
Dissimilar to 1, the carbon atom C2 in the aromatic ring
A of compound 2, rather than methylsulfonyl carbon atom
in compound 1, acts as hydrogen-bond donor to sulfonyl
Compound 1 contains three molecules in the asymmetric
unit, meanwhile the crystal unit of compound 2 is
Table 2 Hydrogen-bonding
˚
Bond
1
Symmetry code
D–H
HÁÁÁA
D(D_A)
Angle
geometry (A and 8) for 1 and 2
C(16)–H(16A)ÁÁÁO(1)
-x, 2 - y, 2 – z
1 ? x, y, z
0.96
0.96
0.93
0.96
0.96
0.96
2.57
2.42
2.53
2.48
2.46
2.40
3.525(4)
3.287(4)
3.311(5)
3.357(4)
3.317(4)
3.351(4)
174
150
141
152
148
171
C(16)–H(16B)ÁÁÁO(2)
C(18)–H(18)ÁÁÁO(5)
C(32)–H(32B)ÁÁÁO(3)
C(48)–H(48B)ÁÁÁO(6)
C(48)–H(48C)ÁÁÁO(4)
-1 ? x, y, z
1 ? x, y, z
-1 ? x, y, z
1 - x, 1 - y, -z
2
C(2)–H(2)ÁÁÁO(2)
0.93
0.98
0.98
0.96
2.54
2.41
2.39
2.53
2.915(5)
2.878(6)
2.878(7)
3.453(8)
105
109
110
161
C(14)–H(14)ÁÁÁN(1)
C(17)–H(17)ÁÁÁN(1)
C(21)–H(21B)ÁÁÁO(2)
- x, -y, 1 - z
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J Chem Crystallogr (2012) 42:611–614
plays an important role in stabilizing crystal packing
structure of 2. Besides, the nitrogen atoms of the Schiff
bases also participate in the formation of the weak intra-
molecular hydrogen C–HÁÁÁN in the crystal structure of 1
and 2.
In addition, there are C–HÁÁÁp interactions in the both
compounds. The C15–H15C ? Cg interactions with
˚
2.92 A of distance of C15ÁÁÁCg (2) exists in compound 1
˚
and the C6-H6 ? Cg (2) interactions with 2.83 A of dis-
tance of C6ÁÁÁCg (2) for compound 2.
These hydrogen bonds and C–HÁÁÁp interactions men-
tioned above not only play crucial roles in the formation,
the stability and the crystallization of compound 1 and
compound 2, but also these hydrogen bonding, C–HÁÁÁp
interactions and van der Waals interactions lead to the
moieties into
(Fig. 2).
a three-dimensional network structure
Acknowledgment The authors are grateful to Natural Science
Foundation of Shandong Province (ZR2009BL023) for the financial
support on this work.
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Fig. 2 The packing diagram for 1 and 2, hydrogen-bonding interac-
tions are represented by dashed lines
atom O2 in the molecule, forming intramolecular hydrogen
bond.
Carbon atom C21 of acetonitrile solvent molecule takes
part in the formation of intermolecular hydrogen bond
C21–H21BÁÁÁO2 (symmetry code: -x, -y, 1 - z), which
123