Synthesis and crystal structure of tetrabutylammonium 4-(2-bromothiophene- 5-sulfanilamide)-benzoate

Article abstract of DOI:10.1007/s10870-010-9848-x

Tetrabutylammonium 4-(2-bromothiophene-5-sulfanilamide)-benzoate crystallizes in C_2/C lattice with a = 18.3389(17), b = 16.540(16), c = 15.8280(15) A, β = 116.959(2), V = 4279.5(7) A³, Z = 4, and R = 0.0560. In the structure a very short centrosymmetric hydrogen bond and C=O???Br halogen bond interactions, together with N-H???O and C-H???O hydrogen bonds give a three-dimensional network. Graphical Abstract: A extremely short O-H???O hydrogen bond is observed between the two neighboring 4-(2-bromothiophene-5-sulfanilamide)-benzoates. The H atom is fixed at the crystallographic inversion center and bridges the two benzoates to form an anion dimer. Halogen bonds also aid in forming the interest structure in crystal.[Figure not available: see fulltext.]

Full text of DOI:10.1007/s10870-010-9848-x

J Chem Crystallogr (2010) 40:884–887
DOI 10.1007/s10870-010-9848-x
REVIEW PAPER
Synthesis and Crystal Structure of Tetrabutylammonium
4-(2-Bromothiophene-5-Sulfanilamide)-Benzoate
•
•
•
Jing Xiong Yun Guo Zhen-Yu Li
Zhi Min Jin
Received: 15 June 2008 / Accepted: 28 June 2010 / Published online: 14 July 2010
Ó Springer Science+Business Media, LLC 2010
Abstract Tetrabutylammonium 4-(2-bromothiophene-5-
sulfanilamide)-benzoate crystallizes in C2/C lattice with
[3–5]. In the strong O–HÁÁÁO hydrogen bonds, the location
of the proton is uncertain. It may be located precisely at:
(i) the centre of the OÁÁÁO distance; (ii) close to one O atom;
(iii) closer to one O atom but jumps between the two O
atoms [6].
˚
a = 18.3389(17), b = 16.540(16), c = 15.8280(15) A, b =
3
116.959(2), V = 4279.5(7) A , Z = 4, and R = 0.0560. In
˚
the structure a very short centrosymmetric hydrogen bond
and C=OÁÁÁBr halogen bond interactions, together with
N–HÁÁÁO and C–HÁÁÁO hydrogen bonds give a three-dimen-
sional network.
Besides hydrogen bond, another interaction, halogen
bonding, has raided great interest. Because its parallelism
potency with hydrogen bond, such interaction is considered
as an effective and reliable tool in crystal engineering at the
disposal of the supramolecular chemist [7] and even may
constitute some unique supramolecular motif [8].
For possible antimicrobial activity, 4-(2-bromothio-
phene-5-sulfonamido) benzoic acid, which are of interest
since the biological activity of both sulfanilamide [9, 10]
and thiophene [11, 12] was condensed in our library, and
the title complex was obtained. The X-ray analysis dem-
onstrates that the C=OÁÁÁBr halogen bond and extremely
short O–HÁÁÁO hydrogen bond play important roles in
forming complex.
Keywords Sulfanilamide Á C=OÁÁÁBr interaction Á
Short OÁÁÁHÁÁÁO hydrogen bonds
Introduction
Week interactions are used to design and manipulation of
supramolecular system [1]. One of these kinds of the
interactions is hydrogen bond, which plays a crucial role in
many chemical processes. Although conventional hydro-
gen bond such as O–HÁÁÁO, N–HÁÁÁO have been explained
sufficiently, it seems the nature of strong O–HÁÁÁO bond
needs more detailed study [2]. This short hydrogen bond is
frequently observed in salts containing carboxylate group
Experimental
The melting points were taken on a WRS-1A melting point
apparatus. The IR spectra were recorded on a Perkin-Elmer
2000 spectrophotometer as a KBr pellet. The NMR spectra
of the crystalline complexes were recorded on a Bruker
AM-300 spectrometer operating at 25 °C, using DMSO-d
as the solvent and TMS as the internal standard. All
reagents were commercial products and were utilized
without further purification. Differential scanning calo-
rimetry and thermogravimetric analysis (DSC–TGA)
analyses were carried out on a Universal V4.1D TA
Instruments (SDT Q600), at a heating rate of 10 °C/min
under a nitrogen atmosphere.
J. Xiong
College of Chemistry and Materials Engineering, Wenzhou
University, Wenzhou 325027, People’s Republic of China
Y. Guo Á Z. M. Jin (&)
College of Pharmaceutical Sciences, Zhejiang University of
Technology, Hangzhou 310014, People’s Republic of China
e-mail: apharm@sina.com
Z.-Y. Li
Zhejiang Environmental Monitoring Centre, Hangzhou 310012,
People’s Republic of China
123

J Chem Crystallogr (2010) 40:884–887
885
A solution of ethyl acetate (30 mL) with 5-bromothio-
phene-2-sulfonyl chloride (10 mmol) was dropped into a
sodium carbonate (30 mmol, 3.1 g) solution (30 mL) with
4-amino-benzoic acid (10 mmol) and tetrabutylammonium
bromide (10 mmol) at room temperature. Then the pH of
the solution was adjusted to 2 after 6 h, then followed with
filtration and extraction, and a colorless single crystal was
obtained after 3 days. Melting point: 210 °C, IR (KBr):
3448(s), 3095, 2955, 2869, 1679(s), 1605(s), 1510, 1403(s),
1332(s), 1222, 1153(s), 936, 782, 590(s). Analysis for
the title complex: C:47.21%, H:5.35%, N:4.37%; calcd
for [C38H51Br2N3O8S4]: C:47.25%, H:5.32%, N:4.35%.
1HNMR (300MHZ, DMSO-d): 8.66(s,1H, NH), 7.56(d, 2H,
Ar–H, J = 8.7 Hz), 6.97(d,1H, BrC=CH, J = 3.7 Hz),
6.75(d,1H, C=CH, J = 3.7 Hz), 6.67(d, 2H, Ar–H, J =
8.7 Hz), 3.24–1.33(m, 24H, CH2 of tetrabutylammonium),
0.93(t, 12H, CH3 of tetrabutylammonium, J = 7.2 Hz);
13CNMR: 190, 152.5, 130.5, 127.6, 115.4, 133.5, 128.3,
126.2, 112.4, 61.3, 26.5, 21.3, 13.7.
The structure of the title complex was determined by
single crystal X-ray diffraction method. The intensity data
were collected on a Bruker Smart-Apex CCD diffraction
diffractometer using MoKa radiation at room temperature.
The structure was solved by direct methods, and refined by
SHELXS program package. Detailed of data collection and
those of refinement procedure are given in Table 1. The
selected conformational parameters and hydrogen bond
interactions are summarized in Tables 2 and 3, respectively.
Results and Discussion
The DSC-TGA measurement demonstrates the title com-
plex is remarkable stability. As shown in Fig. 1, it
decomposes at 300 °C, and lost 93.3% of its weight.
The title complex crystallizes in the space group C2/C
with two anions and one cation in the asymmetric unit of
the cell. The conformation of sulfonamide group is con-
sistent with the result of a previous research [13].
˚
The length of S–N bond is 1.613(3) A and the torsion angle
Table 1 Crystal data and details of the structure determination of the
title complex
of C4–S2–N1–C5 is 76.1°. As shown in Fig. 2, the plane of
the thiophene ring and the phenyl ring are almost perpen-
dicular, which is indicated by the dihedral angle between
them at 96.7°. This structure is the same as that in the case
CCDC number
Formula
675799
C38H51Br2N3O8S4
965.90
Formula weight
Crystal system
Space group
Monoclinic
C
2/C
˚
Table 2 Selected bond lengths (A) or angles (°) for the title complex
˚
a, b, c [A]
18.3389(17)
16.5409(16)
15.8280(15)
90.00, 116.959(2), 90.00
4279.5(7)
Atoms involved
Data
Atoms involved
Data
C5–C6
1.378(6)
1.376(6)
1.382(5)
1.383(6)
1.428(3)
1.426(3)
128.2(3)
105.35(19)
124.2(4)
C9–C10
O3–C11
O4–C11
Br1–C1
1.377(6)
1.287(5)
1.230(5)
1.875(5)
1.418(5)
1.501(5)
125.9(4)
121.3(2)
a, b, m [°]
C6–C7
3
˚
V [A ]
C7–C8
Z
4
C8–C9
D(calc) [g/cm3]
Mu(MoKa) [/mm]
F(000)
1.498
S2–O1
N1–C5
2.142
S2–O2
C8–C11
C3–C4–S2
S1–C4–S2
1988
C5–N1–S2
N1–S2–C4
O4–C11–O3
Crystal size [mm]
Data collection
Temperature (K)
0.39 9 0.16 9 0.12
293
˚
Radiation [A]
Theta min–max [°]
Data set
1.75, 25.02
˚
-21:21; -16:19; -17:18
3778, 2909, 0.0266
2909
Table 3 Distance (A) and angles (°) of hydrogen bond interactions
Total, unique data, R(int)
Observed data [I [ 2.0 r(I)]
Refinement
Atoms involved
Symmetry
Distance
Angle
D–HÁÁÁA
DÁÁÁA
HÁÁÁA
Nref, Npar
3778,251
O(3)–H(3O)ÁÁÁO(3) x ? 3/2, y ? 3/2,
z ? 1
2.481(4) 1.24 180
R, wR2, S
0.0560, 0.1499, 1.030
w = 1/[r2c (Fo2) ? (0.0650P)2 ? 1.9900P] where P = (Fo2 ? 2Fc2)/
3
N(1)–H(1)ÁÁÁO(4)
x, -y ? 1, ?z - 1/2 2.793(6) 1.96 164
3.021(5) 2.42 122
C(10)–H(10)ÁÁÁO(10) x, y, z
Max. and av. shift/error
Min. and max. resd. dens. [eA
0.00, 0.00
C(9)–H(9)ÁÁÁO(2)
C(6)–H(6)ÁÁÁO(4)
x, -y ? 1, ?z ? 1/2 3.270(7) 2.52 138
x, -y ? 1, ?z - 1/2 3.268(6) 2.55 135
-3
]
˚
-1.186, 1.992
123

886
J Chem Crystallogr (2010) 40:884–887
perpendicular conformation formed by thiophene ring and
phenyl ring.
A very short O(3)–H(3O)ÁÁÁO(3)(x ? 3/2, y ? 3/2, z ? 1)
˚
distance[2.481(4) A] is observed between the two neigh-
boring
4-(2-bromothiophene-5-sulfanilamide)-benzoate
(BZT). The H(3O) is fixed with 0.5 occupancy at the
crystallographic inversion center and bridge two groups of
BZT to form an anion dimer. Such a location of the acidic
proton means that the short OÁÁÁO hydrogen bond between
the carboxylate groups is characterized by a symmetrical
double-minimum potential curve [15]. The dimer is cent-
rosymetric and planar, and has the two BZT groups in trans
orientation [C(11)–O(3)ÁÁÁO(3A)–C(11A) 180°, Fig. 2]
regarding the O(3)ÁÁÁHÁÁÁO(3) line as axis, such hydrogen
bonding could be described by graph set of D12(3) [16]. For
comparison, in solid state, carboxylic acids tend to be tied
via O–HÁÁÁO hydrogen bond to form dimmer, where the
hydrogen binding graph set could be indicated by R22(8)
[17]. The very short hydrogen bond cause a shift of the
carbonyl absorption in the IR spectrum to lower frequency
Fig. 1 DSC–TGA curvers of the title complex
of about 20 cm-1 at 1679 cm-1
.
As shown in Fig. 3, the BZT anion dimers are linked
together with its inversion equivalent BZT at (-x ? 1/2,
-y ? 3/2, -z ? 1) by N–HÁÁÁO hydrogen bond. As a
result rows of BZT anion dimer are formed. Further rows
are connected to form the ‘‘wall’’. The walls are associated
by C(11)–O(3)ÁÁÁBr(1) with the O(3)ÁÁÁBr(1) halogen bond
˚
length of 3.120(3) A and an angle of 116.2°, the bond
length is shorter than the sum of their Van der Waals radii
˚
(3.35 A) [18]. In general, this non-covalent contact is
Fig. 2 An illustration of the inclusion compound, showing 30%
probability displacement ellipsoids
considered as a result of the specific attractive force which
is in analogy to the transfer of charge from Lewis base to
a Lewis acid [19]. While Price et al. [20] argued that
the highly directional short intermolecular contacts are
of its analogous compound [14]. The intramolecular
C(10)–H(10)ÁÁÁO(10) hydrogen bonds interactions serve as
a barrier of S(2)–N(1) single bond rotation and stabilize the
Fig. 3 A view of the hydrogen
bonding that links to
neighboring carboxylate
dimmer. Hydrogen bonds are
shown as dashed lines. Atom
lableled with an asterisk (*) or
hash (#) are at the symmetry
positions of (-x ? 1/2,
-y ? 3/2, -z ? 1) and
(x ? 3/2, y ? 3/2, z ? 1)
123

J Chem Crystallogr (2010) 40:884–887
887
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tetrabutylammonium remains in its fully extension form,
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˚
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˚
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halogen bond interactions, together with N–HÁÁÁO and
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