Synthesis, spectral properties and structure of new novel 3,3'-dibenzoyl-1,1'-(propan-1,3-diyl)-bisthiourea

Article abstract of DOI:10.1007/s10870-011-0258-5

A new 3,3'-dibenzoyl-1,1'-propan-1,3-diyl)bisthiourea was synthesized by using benzoylisothiocyanate with 1,3-diaminopropane in aprotic solvent. The structure was determinated by means of FT-IR, ¹H-NMR, ¹³C-NMR and mass spectroscopic

Full text of DOI:10.1007/s10870-011-0258-5

J Chem Crystallogr (2012) 42:381–387
DOI 10.1007/s10870-011-0258-5
ORIGINAL PAPER
Synthesis, Spectral Properties and Structure of New Novel
3,30-Dibenzoyl-1,10-(propan-1,3-diyl)-bisthiourea
¨
•
•
•
˘
Fatma Aydın Dogan Aykac¸ Hu¨seyin Unver
˙
Nazan Ocak Iskeleli
Received: 5 October 2010 / Accepted: 29 December 2011 / Published online: 15 January 2012
Ó Springer Science+Business Media, LLC 2012
Abstract A new 3,30-dibenzoyl-1,10-propan-1,3-diyl)bis-
thiourea was synthesized by using benzoylisothiocyanate
with 1,3-diaminopropane in aprotic solvent. The structure
in 1873 [1]. The synthesis of monoalkylfuroylthioureas,
ArCONHCSNHR, was already described by Douglass
and Daws in 1934 [2]. Recently, many thioureas such
as N-alkyl-N0-acyl(aroyl)thioureas, R/ArCONHCSNHR0,
and N,N-dialkyl-N0-acyl(aroyl) thioureas, R/ArCONHCS
NR0R0, have been synthesised. They are largely important
in synthesis of heterocyclic compounds and many of these
substrates have interesting biological activities [3–5].
Aroyl thioureas which have at least three potential donor
atoms (N, O, S), have been found to display a remarkably
rich coordination chemistry, showing a more varied
coordination behaviour than the structurally related
ß-diketones, which have been thoroughly investigated
[6–8]. Early reports revealed that these compounds con-
taining carbonyl and thiocarbonyl groups have confirmed
the utility among organic reagents as potential donor
ligands for transition metal ions by the research groups
[9]. Thiourea derivatives can be regarded as model com
pounds for different intra- and intermolecular interactions
involving S atoms [10–13]. Metal complexes of these type
ligands containing oxygen and sulfur as donor atoms
are known to possess antifungal and antibacterial activi-
ties. Furthermore, some thiourea derivatives have been
used in commercial fungicides. Both thiourea derivatives
and their metal complexes display a wide range of bio-
logical activity including antibacterial, antifungal, insec-
ticidal, herbicidal, and plant-growth regulator properties
[5, 14–16].
1
was determinated by means of FT-IR, H-NMR, 13C-NMR
and mass spectroscopic techniques. The crystal structure of
3,30-dibenzoyl-1,10-(propan-1,3-diyl)bisthiourea has also
been examined by using X-ray crystallographic techniques
and found to be crystallized in the monoclinic space group
˚
P21/c with the unit cell parameters: a = 5.968(1) A, b =
˚
˚
19.471(2) A, c = 16.585(2) A, b = 98.32(1)°, V = 1907.0
(4) A , Dx = 1.395 g cm-3, and Z = 4 respectively.
3
˚
Keywords Bisthiourea ꢀ Crystal structure determination ꢀ
Spectroscopic studies ꢀ FT-IR
Introduction
The N,N-dialkyl-N0-aroyl-thioureas, ArCONHCSNR0R0,
have long been known since their first synthesis by Neucki
F. Aydın (&) ꢀ D. Aykac¸
Department of Chemistry, Canakkale Onsekiz Mart University,
17100 Canakkale, Turkey
e-mail: faydin@comu.edu.tr
In the present study, a new 3,30-dibenzoyl-1,10-(pro-
pane-1,3-diyl)bisthiourea was synthesized (Scheme 1)
and its structure was determinated by using differ-
ent spectroscopic methods (Scheme 2). In addition,
the crystal structure of title compound was also exam-
ined by means of X-ray crystallographic techniques
(Fig. 1).
¨
H. Unver
˘
Department of Physics, Ankara University, Tandogan,
06100 Ankara, Turkey
˙
N. O. Iskeleli
Department of Physics, Faculty of Science and Arts, Ondokuz
Mayıs University, Kurupelit, 55139 Samsun, Turkey
123

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J Chem Crystallogr (2012) 42:381–387
O
H2N
NH2
O
S
H
N
S
C
O
N
Cl
KSCN
N
NH
HN
S
acetone
reflux, 3 h
acetone
O
H
Scheme 1 Synthesis route of title compound
180.4
26.5
spectra were recorded on a Bruker AVANCE DPX NMR
spectrometer operating at 400 and 101.6 MHz. Elemental
analyses were performed on a Carlo-Erba 1106 Elemental
Analysis instrument. LC mass spectrum was recorded on
an AGILENT 1100 MSD spectrometer with an ion source
temperature of 240 °C using the impact mode (70 eV). All
chemicals used for the preparation of the compounds were
of reagent grade quality.
S
H
132.5
2.17
O
N
N
10.45
7.55
131.7
HN
NH
3.85
O
42.6
7.89
7.44
128.0
167.3
H
S
127.8
11.08
Scheme 2 The H-NMR and 13C-NMR data for the title compound
1
Preparation of Title Compound
Experimental Section
A solution of benzoyl chloride (2.34 mL, 2.81 g, 20 mmol)
in acetone (20 mL) was added dropwise to a suspension of
potassium thiocyanate (1.94 g, 20 mmol) in acetone
(20 mL). The reaction mixture was refluxed with stirring
for 0.5 h to obtain white colour benzoyl isothiocyanate and
then cooled to room temperature. A solution of 0.084 mL
(0.074 g, 10 mmol) of 1,3-diaminopropane in 20 mL ace-
tone was added dropwise to the benzoyl isothiocyanate and
Reagents and Techniques
Melting points were measured on an Electro Thermal IA
9100 apparatus using a capillary tube. Infrared absorption
spectra, which were obtained through the use of with KBr
pellets, were recorded in the range 4000–400 cm-1 on a
Perkin-Elmer BX II spectrometer. The H and 13C NMR
1
Fig. 1 The molecular structure
of the title compound
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J Chem Crystallogr (2012) 42:381–387
383
refluxed with stirring ca. 3 h. The progress of reaction was
controlled by TLC. As the reaction was completed, the
solution was poured into water containing ice (100 mL).
Then, the resulting yellow precipitate was filtered and
washed with 10 mL water at four times, dried in under
vacuum. Finally, the crude product was recrystallized from
tetrahydrofurane: ethanol (V:V, 3:1) to give the product.
The physical and spectral data of title compound are given
follow: Colourless crystal, yield 85%, m.p. 159–160 °C. IR
(KBr, m, cm-1): 3404 (N–H), 3218 (N–H), 3060 (C–
5.03; N, 13.99, S: 16.01, %. Found: C, 56.86; H, 5.09; N,
13.95, S: 16.06%.
X-Ray Structure Determination
The crystal of title molecule was mounted on goniometer
of a STOE IPDS 2 diffractometer with a graphite mono-
˚
chromatized Mo-Ka radiation (k = 0.71073 A). Data
˚
Table 2 Some selected bond lengths (A), bond angles (°) and torsion
H
arom.), 2929 (C–Haliphatic), 1670 (C=O), 1250 (C=S), 1514
angles (°)
(N–CO), 1317 (SC–N), 1180 (C=Ostretching), 724
(C=Sstretching); 1H NMR (400 MHz, dppm, DMSO-d6):
11.08 (s, 1H, NH), 10.45 (s, 1H, NH), 7.89 (d, 4H, ph-H),
7.55 (t, 2H, ph-H), 7.44 (t, 4H, ph-H), 3.85 (q, 4H, –NH–
CH2), 2.17 (m, 2H, –CH2–); 13C NMR (100 MHz, dppm):
180.41 (C=S), 167.33 (C=O), 132.57, 131.77, 128.08,
127.81 (Carom.), 42.62 and 26.51 (Caliphatic), MS (m/z):
400.10 (M?). Anal. calcd. for C19H20N4O2S2: C, 56.98; H,
˚
Bond lengths (A)
S1–C8
1.672(4)
1.317(5)
1.324(5)
1.374(5)
1.228(5)
1.658(4)
1.449(5)
1.454(5)
1.384(5)
1.224(5)
N3–C12
N2–C8
N1–C7
O2–C13
S2–C12
N3–C11
N2–C9
N1–C8
O1–C7
Table 1 Crystallographic data and refinement parameter for the title
compound
CCDC number
780265
19H20N4O2S2
Empirical formula
C
Bond angles (°)
Compound weight
400.51
C12–N3–C11
C7–N1–C8
C13–N4–C12
N1–C8–S1
123.5(4)
129.6(4)
130.3(4)
118.3(3)
121.1(4)
114.9(4)
124.2(4)
115.6(4
123.9(4)
125.2(4)
112.4(4)
117.3(4)
Crystal system
Monoclinic
Space group
P21/c
0.12 9 0.18 9 0.34 mm3
Crystal dimension
Unit cell parameters
O2–C13–N4
N2–C9–C10
C8–N2–C9
N1–C7–C6
N2–C8–S1
˚
5.968(1) A
a
˚
b, b
c
19.471(2) A, 98.32(1)°
˚
16.585(2) A
3
˚
V
1907.0(4) A
Z
4
Dc (g cm-3
l(MoKa)
F(000)
)
1.395
0.302 mm-1
N3–C12–S2
N3–C11–C10
N4–C13–C14
840
2 hmax
51.98°
Torsion angles (°)
h, k, l range
-7 B h B 7
-24 B k B 24
-20 B l B 20
STOE IPDS 2
STOE X-AREA
SHELXS-97
Full-matrix least-squares on F2
31,180
C8–N1–C7–C6
179.9(4)
-178.2(4)
85.4(5)
C13–N4–C12–S2
C8–N2–C9–C10
O2–C13–C14–C19
O2–C13–C14–C15
C12–N4–C13–O2
C7–N1–C8–S1
Measurement
-165.0(5)
17.4(6)
Program system
Structure determination
Refinement method
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness of fit on F2
Final R indices[I [ 2r (I)]
(Dq)max, (Dq)min
-6.3(7)
-178.0(4)
-3.5(6)
175.5(4)
2.2(6)
C9–N2–C8–S1
3,755
C9–N2–C8–N1
3,755/0/244
1.174
C11–N3–C12–S2
N3–C11–C10–C9
C12–N3–C11–C10
179.4(3)
106.5(5)
R1 = 0.0991, wR2 = 0.1064
-3
˚
0.186, -0.211 e A
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J Chem Crystallogr (2012) 42:381–387
collection, reduction and corrections for absorption and
decomposition were achieved using X-AREA, X-RED
software [17]. The structure was solved by SHELXS-97
and refined with SHELXL-97 [18, 19]. The positions of the
H atoms bonded to C atoms were calculated (C–H distance
known thioureido. The t (C=S) stretching vibration can be
observed at 609–724 cm-1 range that are in close agree-
ment with previously studied of other thiourea derivatives
[22–25] (Fig. 2).
˚
0.86, 0.93 and 0.97 A), and refined using a riding model.
NMR Studies
The H atom displacement parameters were restricted to be
1.2Ueq 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. Crystallographic
data (excluding structure factors) for the structures reported
in this paper has been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication
number CCDC 7802651.
The experimental 1H-NMR data of the title compound
1
corresponds to those of similar compounds. The H NMR
signal for N1–H1 and N3–H3 shifted downfield to about
11.08 (s, 1H, NH) ppm and 10.45 (s, 1H, NH) ppm, while
that N–H appeared at about *8.00 and *4.00 ppm,
respectively. The resonance values of the phenyl protons
were confirmed 7.89 (d, 4H, ph-H), 7.55 (t, 2H, ph-H), 7.44
1
(t, 4H, ph-H). The H-NMR spectra of compound (C–H)
peaks is observed at 3.85 ppm (q, 4H, CH2), 2.17 ppm (m,
2H, CH2) due to the difference in the interaction of the
CSNH group with the aliphatic groups. The most
de-shielded 13C-NMR signals correspond to C=O and C=S
groups. The carbon atoms of thiocarbonyl show the highest
value such as 180.41 ppm, due to the lower excitation
energy n–p*. It is possible that very strong electron-with-
drawing neighbors reduce the nucleophilic character of the
C=S group. The 13C-NMR signal of the carbonyl groups in
compound appeared at 167.3 ppm due to the existence of
the intra-molecular hydrogen bond related to the carbonyl
oxygen atom (Figs. 3, 4).
Results and Discussion
FT-IR Studies
Infrared spectra of title compound reveal all the expected
frequency region of the t (N–H), t (C=O), t (C=S), t (CO–
N), t (CS–N). The band at N–H 3405 and 3218 cm-1
,
correspond to the stretching t (NH) vibrations of the
hydrogen bond NH groups in the bis-thiourea group. These
assignments were supported by the literature that N(2)–
H(2)ꢀꢀꢀ(O1) can be seen at above 3200 cm-1 and the N(3)–
H(3)ꢀꢀꢀ(O3, S1) can be found at above 3000 cm-1 have
been examined due to the existence of inter- and intra-
molecular hydrogen bonding [20]. The strong absorb t
C=O band in the IR spectra of the compound appears at
about 1670 cm-1, apparently decreasing in frequencies
comparing with the ordinary carbonyl absorption
(1700 cm-1). This is interpreted as being a result of its
conjugated resonance with the phenyl ring due to a delo-
calized pi-bond in it and the possible formation of intra-
molecular hydrogen bonding with N–H [21]. In addition,
the abnormal intensity ratio between t (C=O) and 1550 and
1514 cm-1 bands revealed that intromolecular hydrogen
bonding might exist in this compound as observed in the
X-ray analysis. The t (C–N) stretching frequencies have
been found at around 1334–1317 cm-1. In fact, these
vibrational frequencies have been assigned by comparison
with the assignments of acylthiourea derivatives at
1400–1000 cm-1. The bands at ca. 1300 cm-1, such as
1317 cm-1, are assigned to the vibration of –N–C=S as
Crystallographic Study
3,30-Dibenzoyl-1,10-(propan-1,3-diyl)-bisthiourea consists
of three 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 [C19,
C18, C17, C16, C15, C14, C13, C12, N4, O2 and S2;
˚
planar with a maximum deviation of 0.1289(12) A for the
N2 atom] are inclined at an angle of 10.07(3)°. However, it
is accepted that it is essentially planar with the only sig-
nificant deviation for the N1–C8–S1 and N4–C12–S2
moiety.
The conformation of the compound with respect to the
thiocarbonyl and carbonyl moieties is twisted, as reflected
by the torsion angles O2–C13–C14–C19 and C11–N3–
C12–S2, -165.0°, 2.2° and benzoyl moivety is almost
planar, as reflected by the torsion angles O2–C13–C14–
C15, C7–N1–C8–N2, C12–N4–C13–O2 17.4°, -178.0°,
-6.3° respectively. Symmetrical thiourea moiety is flexible
due to C8–N2–C9–C10 and C12–N3–C11–C10, 84.5°,
106.5°, respectively.
1
Further information may be obtained from: Cambridge Crystallo-
X-ray structure determinations revealed that thio-keto
graphic Data Center (CCDC), 12 Union Road, Cambridge CB21EZ,
UK, by quoting the depository number CCDC-780265. E-mail:
deposit@ccdc.cam. ac.uk
form is favoured over the thiol-imine form. This is evident
˚
from the observed C8=S1 bond distance of 1.672(4) A,
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J Chem Crystallogr (2012) 42:381–387
385
Fig. 2 FT-IR spectrum of title compound
Fig. 3 1H-NMR spectrum of
title compound
˚
˚
which is consistent with the C = S double bond; similarly
˚
the N1–C8 and N2–C8 distance of 1.384(5) and 1.324(5) A
N1–C8 = 1.384(5) A and N2–C8 = 1.324(5) A bond
length differ significantly from each other, and the N2–C8
bond length is shorter than the N1–C8 bond length. This
may be due to the strong intramolecular hydrogen [OꢀꢀꢀH–
N] bonding (see Fig. 5) between the keto(C=O) group and
and they are also consistent with the N–C single bonding.
The C=S double bond length of 1.672(5) is in agreement
with similar related compounds (see footnote 1). The
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J Chem Crystallogr (2012) 42:381–387
Fig. 4 13C-NMR spectrum of
title compound
character. The bond lengths and angles are in good
agreement with those of other thiourea derivatives.
According to the obtained results, the different packing
arrangements of benzoylthiourea derivatives are all based
on the formation of characteristic dimers and can be
described in terms of the packing of the dimmers.
Acknowledgments The synthesis section of this study is a part of
Dogan AYKAC¸ ’s Ms Thesis and was supported by C¸ anakkale
Onsekiz Mart University Research Fund (Project No: BAP-2008-35).
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˚
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˚
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˚
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