Three substituted (Z)-5-benzylidene-2-thioxothiazolidin-4-ones: Hydrogen-bonded dimers that can be effectively isolated or linked into chains either by aromatic π-π stacking interactions or by dipolar carbonyl-carbonyl interactions

Article abstract of DOI:10.1107/S0108270106018038

In each of the isomeric compounds (Z)-5-(2-fluorobenzyl-idene)-2- thioxothiazolidin-4-one, C₁₀H₆FNOS₂, (I), and (Z)-5-(4-fluorobenzylidene)-2-thioxothiazolidin-4-one, C₁₀H ₆FN-OS₂, (II), th

Full text of DOI:10.1107/S0108270106018038

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Acta Crystallographica Section C
Crystal Structure
benzaldehyde using microwave radiation in a solvent-free
system.
Communications
ISSN 0108-2701
Three substituted (Z)-5-benzylidene-
2-thioxothiazolidin-4-ones: hydrogen-
bonded dimers that can be effectively
isolated or linked into chains either by
aromatic p±p stacking interactions or
by dipolar carbonyl±carbonyl inter-
actions
Paula Delgado,a Jairo Quiroga,a Jose M. de la Torre,b Justo
Cobo,b John N. Lowc and Christopher Glidewelld*
a
Â
Â
Â
Grupo de Investigacion de Compuestos Heterocõclicos, Departamento de Quõmica,
b
Â
Universidad de Valle, AA 25360 Cali, Colombia, Departamento de Quõmica
Inorganica y Organica, Universidad de Jaen, 23071 Jaen, Spain, cDepartment of
Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE,
Scotland, and dSchool of Chemistry, University of St Andrews, Fife KY16 9ST,
Scotland
Â
Â
Â
Â
The molecules of compounds (I)±(III) are all effectively
planar, as shown by the values of the Cx5ÐCx57ÐCx51Ð
Cx52 torsion angle, where x is nil for compounds (I) and (II),
and x = 1 or 2, respectively, for the two independent molecules
in compound (III) (Table 1); this angle de®nes the rotation of
the aryl ring relative to the rest of the molecule. In each
isomer, the Cx5ÐCx57ÐCx51 angle is very large, ca 130ꢀ, and
these angles, together with the exocyclic angles at Cx5 and
Cx51, are consistent with the occurrence of a repulsive intra-
molecular interaction between atoms Sx1 and Hx56 (Table 2).
This behaviour closely mimics that in the analogues (IV)±
Correspondence e-mail: cg@st-andrews.ac.uk
Received 15 May 2006
Accepted 16 May 2006
Online 15 June 2006
In each of the isomeric compounds (Z)-5-(2-¯uorobenzyl-
idene)-2-thioxothiazolidin-4-one, C10H6FNOS2, (I), and (Z)-
5-(4-¯uorobenzylidene)-2-thioxothiazolidin-4-one, C10H6FN-
OS2, (II), there is a very wide CÐCÐC angle (ca 130ꢀ) at the
methine C atom linking the two rings. In each isomer, paired
NÐHÁ Á ÁO hydrogen bonds link the molecules into centro-
symmetric R22(8) dimers; the hydrogen-bonded dimers are
linked into chains by an aromatic ꢀ±ꢀ stacking interaction in
isomer (I) and by an antiparallel dipolar carbonyl±carbonyl
interaction in isomer (II). (Z)-5-(3,4,5-Trimethoxybenzyl-
idene)-2-thioxothiazolidin-4-one, C13H13NO4S2, (III), which
crystallizes with Z0 = 2 in the space group P1, shows the same
very wide angle at the bridging methine C atom; the two
independent molecules are linked into an isolated dimer
having no crystallographic symmetry.
Figure 1
A molecule of (I), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 30% probability level.
Comment
We report here the structures of three substituted (Z)-5-
benzylidene-2-thioxothiazolidin-4-ones, namely two isomers
of (Z)-5-(¯uorobenzylidene)-2-thioxothiazolidin-4-one, (I)
and (II) (Figs. 1 and 2), and (Z)-5-(3,4,5-trimethoxybenzyl-
idene)-2-thioxothiazolidin-4-one, (III) (Fig. 3), and we brie¯y
compare these with the structures of the four analogues (IV)±
(VII) (see scheme), which have been reported recently
(Delgado et al., 2005). As for compounds (IV)±(VII),
compounds (I)±(III) have been prepared by condensation of
2-thioxothiazolidin-4-one (rhodanine) with a substituted
Figure 2
A molecule of (II), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 30% probability level.
o382 # 2006 International Union of Crystallography
DOI: 10.1107/S0108270106018038
Acta Cryst. (2006). C62, o382±o385

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(VII). In each of the molecules in (III), the methoxy groups at
Cx53 and Cx55 have their C atoms almost coplanar with the
adjacent aryl rings (Table 1), but those at Cx54 have the C
atoms well removed from this plane for steric reasons.
The supramolecular structures of compounds (I)±(III) are
very simple. In the isomers (I) and (II), the molecules are
linked by paired NÐHÁ Á ÁO hydrogen bonds (Table 2) into
centrosymmetric R22(8) (Bernstein et al., 1995) dimers; in each
isomer, the asymmetric unit was selected such that the dimer
containing the reference molecule is centred at (12, 21, 21 ) (Figs. 4
and 5). The structures of (I) and (II) differ, however, in the
manner in which the hydrogen-bonded dimers are linked into
chains. In (III), the two independent molecules are again
linked into a dimer but this does not exhibit even approximate
centrosymmetry. There are no direction-speci®c interactions
between the dimeric units in (III).
symmetric. The molecules at (x, y, z) and ( x, 1 y, 1 z) are
1
1
1 1
2 2
components of the dimers centred at (12, , ) and ( 21, , ),
respectively; their carbonyl groups are antiparallel, with a
2
2
ii
ii
Ê
CÁ Á ÁO distance of 3.181 (4) A and an OÐCÁ Á ÁO angle of
The hydrogen-bonded dimers in (I) are linked by an
aromatic ꢀ±ꢀ stacking interaction. The aryl rings in the mol-
ecules at (x, y, z) and (2 x, y, 1 z), which lie, respectively,
in the R22(8) dimers centred at (21, 21, 21 ) and (23, 21, 12 ), are strictly
Ê
parallel, with an interplanar spacing of 3.366 (2) A; the ring-
Ê
centroid separation is 3.692 (2) A, corresponding to an almost
Ê
ideal ring offset of 1.515 (2) A. Propagation by inversion of
this interaction links the dimers into chains running parallel to
the [110] direction (Fig. 6).
In (II), the hydrogen-bonded dimers are linked by an
antiparallel carbonyl±carbonyl interaction, which is centro-
Figure 4
Part of the crystal structure of (I), showing the formation of a
centrosymmetric hydrogen-bonded dimer. For the sake of clarity, H
atoms bonded to C atoms have been omitted. Atoms marked with an
asterisk (*) are at the symmetry position (1 x, 1 y, 1 z).
Figure 5
Figure 3
Part of the crystal structure of (II), showing the formation of a
centrosymmetric hydrogen-bonded dimer. For the sake of clarity, H
atoms bonded to C atoms have been omitted. Atoms marked with an
asterisk (*) are at the symmetry position (1 x, 1 y, 1 z).
The two independent molecules of (III), showing the atom-labelling
scheme and the NÐHÁ Á ÁO hydrogen bonds (dashed lines). Displacement
ellipsoids are drawn at the 30% probability level.
ꢁ
Acta Cryst. (2006). C62, o382±o385
Delgado et al.
C10H6FNOS2, C10H6FNOS2 and C13H13NO4S2 o383

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organic compounds
100.5 (2)ꢀ [symmetry code: (ii) x, y + 1, z + 1], producing
a slightly sheared interaction of type II (Allen et al., 1998),
which links the dimers into chains running parallel to the [100]
direction (Fig. 7).
We note very brie¯y the different patterns of supra-
molecular aggregation in the analogues (IV)±(VII) (Delgado
et al., 2005). In (IV), which crystallizes with Z0 = 2 in the space
group P21/n, the two independent molecules are linked by NÐ
HÁ Á ÁO bonds into a dimer, as in (III), but these dimers are not
isolated; instead they are linked by CÐHÁ Á Áꢀ(arene)
hydrogen bonds into sheets. Compound (V) is effectively
isomorphous with (III) and the molecules form centrosym-
metric dimers, which are linked into chains by a dipolar
carbonyl±carbonyl interaction. No dimers formed by paired
NÐHÁ Á ÁO hydrogen bonds are discernible in the structure of
(VI); instead the molecules are linked into chains of rings by a
combination of NÐHÁ Á ÁS and CÐHÁ Á ÁO hydrogen bonds. In
(VII), the usual R22(8) dimers are formed and these are linked
into chains of rings by CÐHÁ Á ÁS hydrogen bonds. Thus, within
the extended series (I)±(VII), it is apparent that rather modest
changes to the peripheral substituents can have a signi®cant
in¯uence on the overall supramolecular aggregation.
Experimental
Equimolar quantities (1 mmol of each component) of 2-thioxothia-
zolidin-4-one and the appropriate substituted benzaldehyde were
placed in open Pyrex glass vessels in the absence of any solvent and
irradiated in a domestic microwave oven for 3 min (at 600 W); the
reactions were monitored by thin-layer chromatography. The reac-
tion mixtures were extracted with ethanol; after removal of this
solvent, the products were recrystallized from dimethylformamide to
give crystals suitable for single-crystal X-ray diffraction. (I): orange
crystals, m.p. 438 K, yield 53%; MS (70 eV) m/z (%): 239 (4, M+), 152
(100), 108 (2). (II): orange crystals, m.p. 495 K, yield 88%; MS
(70 eV) m/z (%): 239 (24, M+), 152 (100), 107 (20). (III): orange
crystals, m.p. 474 K, yield 85%; MS (70 eV) m/z (%): 313 (18, M+2),
312 (11, M+1), 311(88, M+), 224 [100, (M ± C2HNOS)+], 209 (94),
181 (16), 166 (9).
Compound (I)
Crystal data
C10H6FNOS2
Mr = 239.28
Z = 4
Dx = 1.552 Mg m
Mo Kꢂ radiation
ꢃ = 0.50 mm
T = 298 (2) K
Plate, orange
0.36 Â 0.32 Â 0.04 mm
3
Monoclinic, P21=c
1
Ê
a = 11.1848 (4) A
Ê
b = 7.7651 (4) A
Ê
c = 12.3611 (5) A
ꢁ = 107.417 (3)ꢀ
V = 1024.35 (8) A
3
Ê
Figure 6
Data collection
A stereoview of part of the crystal structure of (I), showing the formation
of a ꢀ-stacked [110] chain of hydrogen-bonded dimers. For the sake of
clarity, H atoms bonded to C atoms have been omitted.
Bruker±Nonius KappaCCD
diffractometer
' and ! scans
9920 measured re¯ections
2337 independent re¯ections
1768 re¯ections with I > 2ꢄ(I)
Rint = 0.042
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.869, Tmax = 0.980
ꢅmax = 27.5ꢀ
Re®nement
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.037
wR(F2) = 0.105
S = 1.04
2337 re¯ections
w = 1/[ꢄ2(F2o) + (0.0479P)2
+ 0.3103P]
where P = (F2o + 2Fc2)/3
(Á/ꢄ)max < 0.001
3
Ê
Áꢆmax = 0.22 e A
3
Ê
0.32 e A
141 parameters
H-atom parameters constrained
Áꢆmin
=
Compound (II)
Crystal data
C10H6FNOS2
Mr = 239.28
Z = 4
Dx = 1.550 Mg m
Mo Kꢂ radiation
ꢃ = 0.50 mm
T = 298 (2) K
Lath, orange
0.60 Â 0.35 Â 0.12 mm
3
Monoclinic, P21=c
1
Figure 7
Ê
a = 4.9173 (2) A
Ê
b = 19.8906 (10) A
A stereoview of part of the crystal structure of (II), showing the
formation of a [100] chain of hydrogen-bonded dimers linked by dipolar
carbonyl±carbonyl interactions. For the sake of clarity, H atoms bonded
to C atoms have been omitted.
Ê
c = 10.4976 (6) A
ꢁ = 92.929 (3)ꢀ
V = 1025.41 (9) A
3
Ê
ꢁ
o384 Delgado et al. C10H6FNOS2, C10H6FNOS2 and C13H13NO4S2
Acta Cryst. (2006). C62, o382±o385

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organic compounds
Data collection
Table 2
Hydrogen bonds and short intramolecular contacts (A, ) for compounds
(I)±(III).
ꢀ
Ê
Bruker±Nonius KappaCCD
diffractometer
' and ! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.753, Tmax = 0.942
7246 measured re¯ections
2287 independent re¯ections
1430 re¯ections with I > 2ꢄ(I)
Rint = 0.053
Compound
(I)
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
ꢅmax = 27.5ꢀ
C56ÐH56Á Á ÁS1
N3ÐH3Á Á ÁO4i
0.93
0.86
2.51
2.00
3.226 (2)
2.843 (2)
134
168
Re®nement
(II)
C56ÐH56Á Á ÁS1
N3ÐH3Á Á ÁO4i
0.93
0.87
2.51
2.00
3.230 (3)
2.831 (3)
135
159
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.082
wR(F2) = 0.110
S = 1.09
2287 re¯ections
w = 1/[ꢄ2(F2o) + (0.0211P)2
+ 1.095P]
where P = (F2o + 2Fc2)/3
(Á/ꢄ)max < 0.001
(III)
C156ÐH156Á Á ÁS11
N13ÐH13Á Á ÁO24
C256ÐH256Á Á ÁS21
N23ÐH23Á Á ÁO14
0.95
0.88
0.95
0.88
2.50
1.95
2.49
1.96
3.237 (2)
2.814 (3)
3.227 (2)
2.807 (3)
134
168
134
162
3
Ê
Áꢆmax = 0.31 e A
3
Ê
0.27 e A
137 parameters
H-atom parameters constrained
Áꢆmin
Extinction correction: SHELXL97
=
Symmetry code: (i) x ‡ 1; y ‡ 1; z ‡ 1.
Extinction coef®cient: 0.0071 (17)
Compound (III)
1.5Ueq(methyl C);H atoms bonded to N atoms were allowed to ride at
Ê
the distances found from the difference maps [NÐH = 0.86±0.88 A
with Uiso(H) = 1.2Ueq(N)].
Crystal data
3
Ê
V = 1394.72 (9) A
Z = 4
Dx = 1.483 Mg m
C13H13NO4S2
Mr = 311.36
Triclinic, P1
a = 10.3432 (4) A
b = 10.9105 (4) A
For all compounds, data collection: COLLECT (Hooft, 1999); cell
re®nement: DENZO (Otwinowski & Minor, 1997) and COLLECT;
data reduction: DENZO and COLLECT; program(s) used to solve
structure: SIR2004 (Burla et al., 2005); program(s) used to re®ne
structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick,
1997); molecular graphics: PLATON (Spek, 2003); software used to
prepare material for publication: SHELXL97 and PRPKAPPA
(Ferguson, 1999).
3
Ê
Ê
Ê
Mo Kꢂ radiation
1
ꢃ = 0.39 mm
T = 120 (2) K
c = 13.4621 (4) A
ꢂ = 100.399 (2)ꢀ
ꢁ = 91.572 (2)ꢀ
ꢇ = 110.301 (2)ꢀ
Plate, orange
0.10 Â 0.08 Â 0.03 mm
Data collection
X-ray data were collected at the EPSRC X-ray Crystal-
lographic Service, University of Southampton, England. JC
Bruker±Nonius KappaCCD
diffractometer
' and ! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.952, Tmax = 0.988
29714 measured re¯ections
6377 independent re¯ections
3786 re¯ections with I > 2ꢄ(I)
Rint = 0.106
Â
and JT thank the Consejerõa de Innovacion, Ciencia y
Empresa (Junta de Andalucõa, Spain) and the Universidad de
Â
ꢅmax = 27.5ꢀ
Â
Â
Jaen for ®nancial support. JT also thanks the Universidad de
Â
Jaen for a research scholarship supporting a short stay at
Re®nement
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.063
wR(F2) = 0.119
S = 1.00
6377 re¯ections
367 parameters
H-atom parameters constrained
w = 1/[ꢄ2(F2o) + (0.0539P)2]
where P = (F2o + 2Fc2)/3
(Á/ꢄ)max = 0.001
the EPSRC X-ray Crystallographic Service, University of
Southampton, England. JP thanks COLCIENCIAS and
UNIVALLE (Universidad del Valle, Colombia) for ®nancial
support.
3
Ê
Áꢆmax = 0.33 e A
3
Ê
0.42 e A
Áꢆmin
=
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK3027). Services for accessing these data are
described at the back of the journal.
Table 1
Selected bond angles and torsion angles (ꢀ) for compounds (I)±(III).
Parameter
(I)
nil
(II)
nil
(III)
(III)
References
x
1
2
Allen, F. H., Baalham, C. A., Lommerse, J. P. M. & Raithby, P. R. (1998). Acta
Cryst. B54, 320±329.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555±1573.
Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De
Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38,
381±388.
Delgado, P., Quiroga, J., Cobo, J., Low, J. N. & Glidewell, C. (2005). Acta Cryst.
C61, o477±o482.
Cx5ÐCx57ÐCx51
Sx1ÐCx5ÐCx57
Cx4ÐCx5ÐCx57
Cx52ÐCx51ÐCx56
Cx57ÐCx51ÐCx56
Cx5ÐCx57ÐCx51ÐCx52
Cx52ÐCx53ÐOx53ÐCx58
Cx53ÐCx54ÐOx54ÐCx59
Cx54ÐCx55ÐOx55ÐCx50
129.25 (17) 130.6 (3)
130.48 (14) 130.1 (2)
120.50 (17) 121.1 (3)
115.44 (16) 118.6 (3)
124.47 (17) 123.6 (3)
174.60 (19) 179.9 (3)
131.3 (3)
130.0 (2)
120.8 (2)
119.4 (2)
123.0 (2)
179.9 (3)
5.1 (4)
130.6 (3)
130.2 (2)
120.9 (2)
117.8 (2)
123.0 (2)
179.5 (3)
15.8 (4)
48.1 (3)
174.3 (2)
±
±
±
±
±
±
77.3 (3)
179.3 (2)
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.
Hooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands.
McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography
Centre, Chemistry Department, NUI Galway, Ireland.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276,
Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M.
Sweet, pp. 307±326. New York: Academic Press.
For each of (I) and (II), the space group P21/c was uniquely
assigned from the systematic absences. Crystals of (III) are triclinic;
the space group P1 was selected and con®rmed by the subsequent
structure analysis. All H atoms were located in difference maps. H
atoms bonded to C atoms were treated as riding atoms, with CÐH
È
Sheldrick, G. M. (1997). SHELXL97. University of Gottingen, Germany.
Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Gottingen,
È
Ê
distances of 0.93 A for (I) and (II), and 0.95 (aromatic) and 0.98 A
Ê
Germany.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7±13.
(methyl) for (III), and with Uiso(H) values of 1.2Ueq(C) or
ꢁ
Acta Cryst. (2006). C62, o382±o385
Delgado et al.
C10H6FNOS2, C10H6FNOS2 and C13H13NO4S2 o385