Spectroscopic studies and structure of 4-(3-benzoylthioureido)benzoic acid

Article abstract of DOI:10.1007/s10870-010-9799-2

4-(3-Benzoylthioureido)benzoic acid has been synthesized from the reaction of 4-aminobenzoic acid with benzoyl isothiocyanate. The title compound has been characterized by elemental analysis, MS, FT-IR, ¹H-NMR, ¹³C-NMR and UV-Visible

Full text of DOI:10.1007/s10870-010-9799-2

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J Chem Crystallogr (2010) 40:1082–1086
DOI 10.1007/s10870-010-9799-2
ORIGINAL PAPER
Spectroscopic Studies and Structure
of 4-(3-Benzoylthioureido)benzoic Acid
¨
•
•
•
˘
Fatma Aydın Hu¨seyin Unver Dogan Aykac¸
_
Nazan Ocak Iskeleli
Received: 10 June 2008 / Accepted: 20 May 2010 / Published online: 10 June 2010
Ó Springer Science+Business Media, LLC 2010
Abstract 4-(3-Benzoylthioureido)benzoic acid has been
synthesized from the reaction of 4-aminobenzoic acid with
benzoyl isothiocyanate. The title compound has been
characterized by elemental analysis, MS, FT-IR, 1H-NMR,
13C-NMR and UV–Visible techniques. The structure of the
compound has also been examined crystallographically.
The title compound crystallizes in the triclinic space group
reactions [3–5] and for extraction of toxic metals using a
solid supported liquid membrane system [6]. The antiviral
[7], cytotoxic [1, 2] and antifungal [8] activities of these
compounds are well known. Apart from the biological
activities, the corrosion of some metals can be determined
using thiourea and its derivatives [9]. Furthermore these
compounds have been widely used as ligands in the for-
mation of metal complexes [10–21]. In these complexes
thiourea and its derivatives are coordinated to a metal ion
either by the N or S atoms, by both of them or by other
donor atoms available in the molecule [22] (Scheme 1).
In this present study, we have synthesized new thiourea
derivative and investigated by using MS, FT-IR, 1H-NMR,
13C-NMR, UV–Visible spectroscopic and X-ray crystallo-
graphic techniques in order to reveal the hydrogen bonding
and tautomeric equilibrium (Scheme 1). For the title
compound, the tautomeric thioketo-amine form is observed
˚
P-1 with a = 3.969(1), b = 13.039(1), c = 13.504(1) A,
a = 96.50(1)°, b = 92.25(1)°, c = 94.94(1), V = 691.0(1)
3
and Dx = 1.444 g cm-3, respectively. The crystal
˚
A
structure has been solved by direct methods and refined by
full-matrix least squares and found R1 = 0.031 and
wR2 = 0.081 for 2909 observed reflections [I [ 2r(I)].
Keywords Thiourea ꢀ Benzoic acid ꢀ Spectroscopy ꢀ
Crystal structure ꢀ Hydrogen bonds
˚
with C8–S1 distance of 1.6521(14) A. Strong intramolec-
Introduction
ular hydrogen bonds are found between the N2–O1 atoms
with an N2–H2A and N2–O1 distances of 0.858(18) and
˚
2.6147(18) A.
Thiourea and its derivatives have been widely used in
research and technological applications such as in the
pharmaceutical industry [1, 2], as catalysts in chemical
Experimental
Reagents and Techniques
F. Aydın (&) ꢀ D. Aykac¸
Faculty of Science and Arts, Department of Chemistry,
C¸ anakkale Onsekiz Mart University, 17100 C¸ anakkale, Turkey
e-mail: faydin@comu.edu.tr
1
The H and 13C NMR spectra were recorded on a Bruker
AVANCE DPX NMR spectrometer operating at 400 and
101.6 MHz. Infrared absorption spectra were obtained
from a Perkin Elmer BX II spectrometer in KBr discs and
were reported in cm-1 units. The UV–Visible spectra were
measured using a SHIMADZU 1208 series spectrometer.
Carbon, nitrogen and hydrogen analyses were performed
on a LECO CHNS-932 analyzer. Melting points were
¨
H. Unver
Faculty of Science, Department of Physics, Ankara University,
˘
Tandogan, 06100 Ankara, Turkey
_
N. O. Iskeleli
Department of Science Education, Ondokuz Mayıs University,
Atakum, 55200 Samsun, Turkey
123

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J Chem Crystallogr (2010) 40:1082–1086
1083
O
CO–NH–CS); 8.00–7.98 (m, 4H, Ar–HCONH–); 7.67–7.68
(m, 1H, Ar–HCONH–); 7.81 (d, 2H, NH–Ar–HCOOH); 7.53
(d, 2H, NH–Ar–HCOOH).
H2N
COOH
C
N
C
S
CH3COCH3
3h
N
X-ray Structure Determination
The crystal of title molecule was mounted on goniometer
of a STOE IPDS 2 diffractometer with a graphite mono-
O
H
OH
C
˚
chromatized Mo Ka radiation (k = 0.71073 A). Data col-
NH
lection, reduction and corrections for absorption and
decomposition were achieved using X-AREA, X-RED
software [23]. The structure was solved by SHELXS-97
and refined with SHELXL-97 [24, 25]. The positions of the
H atoms bonded to C atoms were calculated (C–H distance
O
S
Thioketo-amine
˚
0.96 A), and refined using a riding model. The H atom
O
displacement parameters were restricted to be 1.2 Ueq of
the parent atom. The details of the X-ray data collection,
structure solution and structure refinements are given in
Table 1. Selected bond distances and angles are listed in
Table 2. The molecular structure with the atom-numbering
scheme is shown in Fig. 1 [26]. Crystallographic data
(excluding structure factors) for the structures reported in
OH
C
N
NH
O
SH
Thiol-imine
Scheme 1 Synthesis route and chemical structures of the title
compound
Table 1 Crystal and experimental data
Compound
C15H12N2O3S
measured on an Electro Thermal IA 9100 apparatus using
a capillary tube. LC mass spectra were obtained on an
AGILENT 1100 MSD spectrometer with an ion source
temperature of 240 °C. 4-Aminobenzoic acid, benzoyl
chloride, KSCN, CH3COCH3, ethyl acetate, dichloro-
methane were purchased from Merck.
Compound weight
300.3
CCDC deposit no.
690508
Crystal system
Triclinic
Space group
P-1
0.25 9 0.33 9 0.42 mm3
Crystal dimension
Unit cell parameters
˚
Synthesis of 4(3-Benzoylthioureido)benzoic Acid
a
b
c
3.969(1) A a = 96.50(1)°
˚
13.039(1) A b = 92.25(1)°
A solution of benzoyl chloride (1.40 g; 1 9 10-2 mol) in
acetone (50 mL) was added slowly to a solution of KSCN
(0.97 g; 1 9 10-2 mol) in acetone (50 mL) in a dried flask
and the reaction mixture was stirred at room temperature,
the progress of the reaction was monitored by TLC anal-
ysis. After completion of the reaction, for 1 h or so, a
solution of 4-amino-benzoic acid (1.37 g; 1 9 10-2 mol)
in 15 mL acetone was added dropwise to the benzoyl
isothiocyanate and stirred at ambient temperature. When
the solution was added completely, the mixture was
refluxed for 3 h. The mixture was added cool water and
stirred for more than 10 min. It was filtered and crystallized
from ethyl acetate/dichloromethane as pale-yellow crystals,
m.p. 243–244 °C, 2.76 g (92%) yield. Found: C, 59.96; H,
4.01; N, 9.33. Calc. For C14H10N2OS; C, 59.99; H, 4.03; N,
˚
13.504(1) A c = 94.94(1)°
3
˚
V
691.0(1) A
Z
2
Dc (g cm-3
l (Mo Ka)
F(000)
)
1.444 g cm-3
0.246 mm-1
239
2hmax
53.6°
h, k, l range
-5 B h B 5
-16 B k B 16
-17 B l B 17
0.986
Goodness of fit on F2
No. of reflections used
Final R indices [I [ 2r(I)]
R indices (all data)
Measurement
2909
R1 = 0.031 and wR2 = 0.081
R1 = 0.042 and R2 = 0.084
STOE IPDS 2
STOE X-AREA
SHELXS-97
9.33%. IR (KBr, cm-1); mN–H; 3378, 3255 m, mAr–H
;
;
Program system
3039 m, mCOO; 1690 s, mC=O; 1672 s, mC=C; 1593 s, mC–N
Structure determination
(Dq)max, (Dq)min
1
1430 s, mC=S; 1154 s. H-NMR(DMSO); d ppm, 12.97 (s,
1H, Ar–COOH); 12,78 (s, 1H, CS–NH–Ar); 11.66 (s, 1H,
-3
˚
0.160, -0.141 e A
123

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J Chem Crystallogr (2010) 40:1082–1086
1
˚
the H NMR spectrum of compound indicates that the NH
and NH resonances appear at 12.78 and 11.66 ppm, but
these resonances vary with different parameters, such as
the substituted groups on the rings, which release and
withdraw electron density in each ring, their positions and
intra- and inter-hydrogen bondings [28–31]. The aromatic
protons of benzamide are observed 8.00–7.98 ppm multi-
plet (4H) and 7.67–7.68 ppm multiplet (1H) for compound.
The aromatic protons of benzoic acid are observed
7.81 ppm doublet (2H) and 7.53 doublets (2H). The three
Table 2 Some selected bond lengths (A), bond angles (°) and torsion
angles (°)
S1–C8
1.652(1)
1.375(2)
1.393(2)
129.2(1)
127.6(1)
118.4(1)
129.7(1)
3.8(3)
N2–C8
1.345(2)
1.411(2)
1.224(2)
121.6(1)
122.0(1)
116.4(1)
114.0(1)
-180.0(1)
-177.4(1)
1.7(2)
N1–C7
N2–C9
N1–C8
O1–C7
C7–N1–C8
N2–C8–S1
O1–C7–N1
O1–C7–C6
N1–C7–C6
N2–C8–N1
N2–C9–C10–C11
C9–N2–C8–N1
C9–N2–C8–S1
C7–N1–C8–N2
C7–N1–C8–S1
N1–C8–S1
C8–N2–C9
C8–N1–C7–O1
C8–N1–C7–C6
C5–C6–C7–O1
C1–C6–C7–N1
N2–C9–C14–C13
3
bond proton couplings JHCCH = 8.67 Hz. According to
-176.6(1)
-156.4(2)
-158.9(1)
-179.5(1)
the proton de-coupled 13C NMR spectra, the title com-
pound has 11 signals. The aliphatic ArCONH–C=S–NH–
ArCOOH, –ArCOOH and ArCONH carbons are observed
at d = 179.50 ppm, d = 168.70 and d = 167.17 ppm for
compound. The chemical shifts d ppm; 142.41 (s, 1C, C1,
Cipso-, –NH–), 133.71 (s, 1C, C5, Cipso-, –CONH–),
132.51 (s, 1C, C8), 130.41 (s, 1C, C3-30), 129.21 (s, 1C,
C7-70), 128.93 (s, 1C, C6-60), 128.55 (s, 1C, C2-20), 123.96
(s, 1C, C4, Cipso-, –COOH). The compound seems to have
symmetric carbon atoms (2–20, 3–30, 6–60 and 7–70) in
solution. The chemical shifts of carbon of the C=S bond in
compound was about 179.50 ppm. This similar chemical
shift could be due to the isolated position of the thione
group in these compounds [22, 32].
6.0(2)
-173.2(1)
this paper has been deposited with the Cambridge Crys-
tallographic Data Centre as supplementary publication no.
CCDC 690508 [27].
Result and Discussion
FT-IR, H-NMR, 13C-NMR and UV–Visible
1
Spectroscopic Studies
The UV–Visible spectra of the compound were studied
in DMSO and basic DMSO (Et3N, tetrabutylammonium
hydroxide and NaOH) solution. The compound shows
absorption at the 275 and 324 nm in DMSO and basic Et3N
and tetrabutylammonium hydroxide. The band is smaller of
275, while it is larger of the 324 nm in basic Et3N and
tetrabutylammonium hydroxide media. Although the
absorption band is observed at the 324 nm, it is not
observed at the 275 nm in the NaOH media. The absorp-
tion band at the 275 nm is disappeared in the NaOH media.
The N–C=S bond character turn in to the N=C–S bond in
basic media. The ionic form (–N–C–S-) is occured in the
strong basic media. The band (275 nm) is smaller than the
other band (324 nm) due to the –N–C–S- ionic form.
The IR spectra of the compounds are given in synthetic
procedures. Vibration bands with the wave numbers of
3378, 3255 cm-1 (mN–H), 3039 cm-1 (mC–H, Ar–H), 1690 cm-1
(mCOO, ArCOOH), 1672 cm-1 (mC=O), 1593 cm-1 (mC=C),
1430 cm-1 (mC–N) were observed for compound, respec-
tively. The C=S stretching band is observed at 1154 cm-1
.
The IR spectra of the compound do not display the S–H mode
at about 2600 cm-1 indicating that in the solid state this
compound remains in the thioketo-amine form.
1
According to the H NMR spectra, the COOH carbox-
ylic proton is observed as singlet d = 12.97 ppm for
compound. The N–H protons appear as singlets 12.78 and
11.66 ppm, respectively. Corresponding to the literature,
Fig. 1 The molecular structure
of the title compound
O2
C2
C1
O1
C13
C12
C14
C6
C3
C15
N2
C9
C4
C7
O3
C10
C5
C11
C8
N1
S1
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1085
In conclusion; UV–Visible, 1H NMR and 13C NMR
results show that the compound exists in the thioketo-
amine form in solutions.
Crystallographic Study
The title compound consists of two parts. The part A [C1,
C2, C3, C4, C5, C6, C7, C8, O1, N1 and S1; planar with a
˚
maximum deviation of 0.3422(8) A for the S1 atom] and
another part B [C9, C10, C11, C12, C13, C14, C15, N2, O3
˚
and O2; planar with a maximum deviation of 0.1289(12) A
for the N2 atom] are inclined at an angle of 10.07(3)°. But,
the title molecule is accepted that it is essentially planar
with the only significant deviation for the N1–C8–S1
moiety.
Fig. 2 A perspective view of the title molecule in the unit cell. The
intramolecular and intermolecular hydrogen bonds have been indi-
cated by dashed lines
The crystal structure is stabilized by intramolecular and
intermolecular hydrogen bonding and its geometrical details
˚
are listed Table 3. The O1ꢀꢀꢀN2 (2.615(2) A) bond distance is
which is consistent with the C–S double bond; similarly the
˚
N1–C8 and N2–C8 distance of 1.393(2) and 1.345(2) A
clearly indicative of an intramolecular hydrogen bonding; a
criterion for hydrogen bonding between oxygen and nitrogen
atoms is considered to be that the distance OꢀꢀꢀN should be
and they are also consistent with the N–C single bonding.
The C=S double bond length of 1.652(1) is agree with
similar related compounds [34–37]. The N1–C8 =
˚
shorter than the sum, 3.07 A, of the van der Waals radii [33].
˚
˚
This intramolecular hydrogen bond length is shorter than
expected because this distance is rather forced on the atoms
by the need for the thione and carbonyl to be coplanar and in a
‘‘trans’’ arrangement. The only significant hydrogen bond-
ing interaction is the expected acid–acid head-to-head
dimeric arrangement. In the crystal structure, the molecules
are linked through intermolecular hydrogen bonds. Inter-
molecular hydrogen bonds also occurs between N1–
1.393(2) A and N2–C8 = 1.345(2) A bond length differ
significantly from each other. The N2–C8 bond length is
shorter than N1–C8 bond length. This may be due to
the strong intramolecular hydrogen [OꢀꢀꢀH–N] bonding
between the keto (C=O) group and the amine (–NH–)
˚
nitrogen. The bond C8–S1 = 1.652(1) A is significantly
longer than a C–S double bond. This (C–S) distance is
˚
smaller than single C–S bond distance of 1.82 A but bigger
˚
˚
˚
than double C–S bond of 1.56 A [22, 38–40]. Conse-
H1AꢀꢀꢀS1 [N1–S1 = 3.563(1) A, H1AꢀꢀꢀS1 = 2.78(2) A
and N1–H1AꢀꢀꢀS1 = 161(2)°], O2–H2BꢀꢀꢀO3 [O2–O3 =
quently, the C–S bond like in these compounds possesses
only partial double-bond character.
˚
˚
2.619(2) A, H2BꢀꢀꢀO3 = 1.65(3) A and O2–H2BꢀꢀꢀO3 =
˚
177(2)°] and C2–H2ꢀꢀꢀO3 [C2–O3 = 3.414(2) A,
˚
Acknowledgments The authors thank C¸ anakkale Onsekiz Mart
University Grants Commission for a research grant (Project Number:
2008/35).
H2ꢀꢀꢀO3 = 2.52(2) A and C2–H2ꢀꢀꢀO3 = 161(2)°] as seen
Fig. 2.
X-ray structure determinations reveal that thio-keto
form is favoured over the thiol-imine form. This is evident
˚
from the observed C8–S1 bond distance of 1.652(1) A,
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Table 3 Geometric details of intra- and intermolecular hydrogen
bonding for the title compound
˚
˚
˚
D–HꢀꢀꢀA (A)
D–H
HꢀꢀꢀA (A) DꢀꢀꢀA (A) \D–HꢀꢀꢀA (°)
N2–H2AꢀꢀꢀO1
C1–H1ꢀꢀꢀO1
0.86(2) 1.87(2)
0.92(2) 2.46(2)
0.96(2) 2.64(2)
0.81(2) 2.78(2)
2.615(2)
2.814(2)
3.183(2)
3.563(1)
2.619(2)
3.414(2)
145(2)
103(1)
116(1)
161(2)
177(2)
161(2)
C10–H10ꢀꢀꢀS1
´
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´ ´
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N1–H1AꢀꢀꢀS1i
O2–H2BꢀꢀꢀO3ii 0.97(3) 1.65(3)
0.93(2) 2.52(2)
`
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C2–H2ꢀꢀꢀO3iii
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Note: D donor, A acceptor. Symmetry transformation used to generate
equivalent atoms: (i) 1 - x, -y, -z; (ii) -1 - x, -1 - y, 1 - z;
(iii) 2 ? x, 1 ? y, z
123