1,3-Dibenzoylimidazolidine-2-thione and 1,3-dibenzoyl-3,4,5,6-tetrahydropyrimidine-2(1 H)-thione

Full text of DOI:10.1107/S0108270105009844

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
matoid arthritis (Haynes & Whitehouse, 1989). Metal
complexes are also used as models to understand the elec-
tronic and structural properties of the active sites in metal-
loenzymes (Casella et al., 1988; Gullotti, et al., 1989) and
metal±DNA interactions (Tran Qui & Bagieu, 1990). In the
course of synthesizing new ligands suitable for coordination
chemistry, we prepared two new heterocyclic thiones, namely
1,3-dibenzoylimidazolidine-2-thione, (I), and 1,3-dibenzoyl-
3,4,5,6-tetrahydropyrimidine-2(1H)-thione, (II), from the
reactions of imidazolidine-2-thione and 1,4,5,6-tetrahydro-
pyrimidine-2-thiol, respectively, with benzoyl chloride.
ISSN 0108-2701
1,3-Dibenzoylimidazolidine-2-thione
and 1,3-dibenzoyl-3,4,5,6-tetrahydro-
pyrimidine-2(1H)-thione
Canan Kazak,a Veysel T. Yilmaz,b* Suleyman Servi,c Murat
Kocac and Frank W. Heinemannd
aDepartment of Physics, Faculty of Arts and Sciences, Ondokuz Mayis University,
55139 Kurupelit, Samsun, Turkey, bDepartment of Chemistry, Faculty of Arts and
Sciences, Ondokuz Mayis University, 55139 Kurupelit, Samsun, Turkey, cDepart-
of Arts and Sciences, Firat University, 23169 Elazig, Turkey, and dInstitut fur
È
Anorganische Chemie, Universitat Erlangen-Nurnberg, D-91058 Erlangen, Germany
È
È
Correspondence e-mail: vtyilmaz@omu.edu.tr
Received 12 January 2005
Accepted 29 March 2005
Online 13 May 2005
The title compounds, 1,3-dibenzoylimidazolidine-2-thione,
C17H14N2O2S, (I), and 1,3-dibenzoyl-3,4,5,6-tetrahydro-
pyrimidine-2(1H)-thione, C18H16N2O2S, (II), were obtained
from the reactions of imidazolidine-2-thione and 1,4,5,6-
tetrahydropyrimidine-2-thiol, respectively, with benzoyl
Views of the molecules of (I) and (II), including the atom-
numbering schemes, are shown in Figs. 1 and 2. Selected bond
distances and angles are listed in Tables 1 and 3. Each
compound exhibits a soft thione S-donor and three hard donor
sites (a carbonyl O and two N atoms) and seems to act as a
chelating or a bridging ligand. These compounds are also
interesting building blocks for generating coordination poly-
mers upon metal complexation. Both (I) and (II) consist of
imidazolidinethione and pyrimidinethione moieties bonded to
two benzoyl rings. The sulfur substituents exist in the thione
form. The C S bond lengths in (I) and (II) are consistent with
chloride. Compounds (I) and (II) contain, respectively,
Ê
imidazolidinethione [C
S
=
1.6509 (14) A] and py-
Ê
rimidinethione [C S = 1.6918 (19) A] moieties bonded to
two benzoyl rings. The molecules of (I) exhibit C2 symmetry,
the C S bond lying along the twofold rotation axis, while the
molecules of (II) have mirror symmetry (Cs). The imida-
zolidine ring in (I) is essentially planar, while the pyrimidine
ring in (II) adopts a boat conformation. Molecules of (I) are
linked by weak intermolecular CÐHÁ Á ÁO interactions, while
molecules of (II) are held together by van der Waals
interactions.
Comment
Heterocyclic thioamides usually occurring in their thioketo
form are referred to as `thiones'. Heterocyclic thiones have a
wide range of applications as analytical reagents, as metal
corrosion inhibitors and in the pharmaceutical ®eld (Hussain
et al., 1990). These compounds are of particular interest in
coordination chemistry because they display both hard and
soft donor sites. In many instances, heterocyclic thiones
behave as polyfunctional ligands, with monodentate, chelating
and bridging coordination modes, and form a wide range of
transition metal complexes, many of which have important
chemical and biological properties (Raper, 1985, 1994, 1996,
1997; Akrivos, 2001). Furthermore, metal complexes of
heterocyclic thiones exhibit interesting anticarcinogenic
properties (Reedijk, 1992; van Boom & Reedijk, 1993;
Barnham et al., 1994) and are used in the treatment of rheu-
Figure 1
The molecule of (I), showing the atom-labelling scheme and 40%
probability displacement ellipsoids.
o348 # 2005 International Union of Crystallography
DOI: 10.1107/S0108270105009844
Acta Cryst. (2005). C61, o348±o350

organic compounds
chloride (2.81 g, 20 mmol) was added to the reaction mixture drop-
wise and the resulting mixture was re¯uxed for 4 h. The solution was
evaporated under vacuum to half the volume and then poured into
ice water to precipitate. The residue was ®ltered off and single
crystals of (I) suitable for X-ray measurements were obtained by
crystallization from acetone. The procedure and molar quantities
of the reactants for the preparation of (II) were the same as for (I),
with 1,4,5,6-tetrahydropyrimidine-2-thiol replacing imidiazolidine-2-
thione.
Compound (I)
Crystal data
C17H14N2O2S
Mr = 310.36
Orthorhombic, P21212
Mo Kꢁ radiation
Cell parameters from 128
re¯ections
Figure 2
The molecule of (II), showing the atom-labelling scheme and 40%
ꢂ = 6.0±20.0ꢀ
Ê
a = 11.8543 (8) A
probability displacement ellipsoids. [Symmetry code: (i) x; 32 y; z.]
1
Ê
b = 5.7221 (2) A
ꢃ = 0.23 mm
T = 100 (2) K
Ê
c = 10.6312 (6) A
3
Ê
V = 721.13 (7) A
Prism, yellow
0.37 Â 0.16 Â 0.12 mm
Z = 2
Dx = 1.429 Mg m
3
a double bond and are similar to those in other reported
heterocyclic thione derivatives containing imidazolethione
È
and pyrimidinethione rings (Ozbey et al., 1991, 2004; Akkurt et
al., 1992, 2000; Cox et al., 1996; Liu et al., 2003; Brito et al.,
2004). The C8ÐN1 bond distances in both compounds are
Ê
intermediate between standard single CÐN (1.47 A) and
Data collection
Nonius KappaCCD diffractometer
' and ! scans
1772 re¯ections with I > 2ꢄ(I)
Rint = 0.029
ꢂmax = 28.7ꢀ
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
Tmin = 0.925, Tmax = 0.967
21 502 measured re¯ections
1864 independent re¯ections
h = 16 ! 16
k = 7 ! 7
Ê
double C N (1.28 A) bonds, being signi®cantly shorter than
l = 14 ! 14
the C9ÐN1 bonds, because atom C8 is in an sp2-hybridized
state, while atom C9 is sp3. The remaining bond lengths in both
compounds show no unusual values.
Re®nement
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.024
wR(F2) = 0.059
S = 1.09
1864 re¯ections
101 parameters
(Á/ꢄ)max = 0.001
The molecules of (I) show C2 symmetry and the C8ÐS1
bond lies on the twofold rotation axis, while the molecules of
(II) have mirror symmetry (Cs), with atoms S1, C8, C10, H10A
and H10B situated on the mirror plane. The ®ve-membered
imidazolidine ring in (I) is essentially planar, with maximum
3
Ê
Áꢅmax = 0.26 e A
3
Ê
0.19 e A
Áꢅmin
=
Absolute structure: Flack (1983),
757 Friedel pairs
Flack parameter: 0.03 (6)
H-atom parameters constrained
w = 1/[ꢄ2(Fo2) + (0.0278P)2
+ 0.1874P]
deviations from the mean plane of
0.1418 (8) and
i
Ê
0.1397 (8) A for atoms N1 and C9 [symmetry code: (i) x + 1,
y + 2, z], respectively. The six-membered pyrimidine ring in
(II) adopts a half-boat conformation, in which atoms C8 and
C10 are displaced from the mean plane by 0.0387 (10) and
where P = (Fo2 + 2Fc )/3
2
Table 1
Selected geometric parameters (A, ) for (I).
ꢀ
Ê
Ê
0.2561 (13) A. The benzoyl rings in (I) make dihedral angles
of 76.55 (3) and 79.85 (3)ꢀ with the mean plane of the imida-
zole ring. The dihedral angle between the two planar benzoyl
fragments is 75.92 (3)ꢀ in (I) and 61.08 (4)ꢀ in (II). A non-
planar disposition of the three rings has been observed in
other reported heterocyclic thione derivatives with similar
N1ÐC7
N1ÐC8
N1ÐC9
1.4073 (15)
1.3766 (13)
1.4777 (15)
O1ÐC7
S1ÐC8
C9ÐC9i
1.2135 (16)
1.6504 (14)
1.530 (2)
C7ÐN1ÐC9
C8ÐN1ÐC7
C8ÐN1ÐC9
119.83 (9)
126.84 (10)
111.59 (9)
N1iÐC8ÐN1
N1ÐC8ÐS1
106.48 (13)
126.76 (6)
È
compositions (Ozbey et al., 1991; Cox et al., 1996; Akkurt et al.,
È
2000; OzcËelik et al., 2004).
C9ÐN1ÐC8ÐN1i
C9ÐN1ÐC8ÐS1
9.82 (6)
170.18 (6)
C8ÐN1ÐC9ÐC9i
C7ÐN1ÐC9ÐC9i
23.99 (13)
170.02 (11)
The molecules of (I) are linked by weak intermolecular CÐ
HÁ Á ÁO interactions (Table 2). There are no ꢀ±ꢀ stacking
interactions in (II). Examination of the structures with
PLATON (Spek, 2003) indicates that there are no solvent-
accessible voids in either (I) or (II).
Symmetry code: (i) x ‡ 1; y ‡ 2; z.
Table 2
Hydrogen-bond geometry (A, ) for (I).
ꢀ
Ê
Experimental
DÐHÁ Á ÁA
C9ÐH9AÁ Á ÁO1ii
Symmetry code: (ii) x ‡ 1; y ‡ 1; z.
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
Triethylamine (TEA; 2.02 g, 20 mmol) was added to a solution of
imidiazolidine-2-thione (1.02 g, 10 mmol) dissolved in tetrahydro-
furan (100 ml) with stirring in an ice bath for 30 min. Benzoyl
0.99
2.47
3.2231 (16)
132
ꢁ
Acta Cryst. (2005). C61, o348±o350
Kazak et al. C17H14N2O2S and C18H16N2O2S o349

organic compounds
Compound (II)
For both compounds, data collection: COLLECT (Bruker, 2002);
cell re®nement: EVALCCD (Bruker, 2002); data reduction:
EVALCCD; structure solution: SHELXTL (Bruker, 2002); structure
re®nement: SHELXTL; molecular graphics: SHELXTL; software
used to prepare material for publication: SHELXTL.
Crystal data
C18H16N2O2S
Mr = 324.39
Mo Kꢁ radiation
Cell parameters from 150
re¯ections
Orthorhombic, Pnma
Ê
a = 8.6803 (6) A
ꢂ = 6.0±20.0ꢀ
ꢃ = 0.22 mm
T = 100 (2) K
1
Ê
The authors thank Ondokuz Mayis and Firat Universities
for the ®nancial support given to the study.
b = 21.946 (1) A
Ê
c = 8.1845 (9) A
Ê
V = 1559.1 (2) A
3
Irregular, colourless
0.23 Â 0.23 Â 0.16 mm
Z = 4
Dx = 1.382 Mg m
3
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: TR1118). Services for accessing these data are
described at the back of the journal.
Data collection
Nonius KappaCCD diffractometer
' and ! scans
1707 re¯ections with I > 2ꢄ(I)
Rint = 0.040
ꢂmax = 28.7ꢀ
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Absorption correction: multi-scan
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Tmin = 0.941, Tmax = 0.972
22 525 measured re¯ections
2051 independent re¯ections
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2051 re¯ections
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ꢀ
Ê
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N1ÐC8
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1.4537 (18)
1.3478 (15)
1.4760 (17)
O1ÐC7
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115.08 (11)
119.80 (12)
123.87 (12)
N1iiiÐC8ÐN1
N1ÐC8ÐS1
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È
È
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6.7 (2)
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ꢁ
o350 Kazak et al. C17H14N2O2S and C18H16N2O2S
Acta Cryst. (2005). C61, o348±o350