Supramolecular structures of four (Z)-5-arylmethylene-2-thioxothia-zolidin- 4-ones: Hydrogen-bonded dimers, chains of rings and sheets

Article abstract of DOI:10.1107/S0108270105021888

In each of the four title compounds, namely (Z)-S-benzyl-idene-2- thioxothiazolidin-4-one, C₁₀H₇NOS₂, (I), which crystallizes with Z′ = 2 in space group P2₁/n, (Z)-5-(4-methylbenzylidene)-2-thioxothiazolidin-4-o

Full text of DOI:10.1107/S0108270105021888

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
ambient temperature; however, no discussion of the supra-
molecular structure was given and there are no atomic coor-
dinates deposited in the Cambridge Structural Database
(Allen, 2002; refcode GOVXIY). Compound (I) crystallizes in
space group P21/n with Z0 = 2, while compounds (II)±(IV) all
crystallize with Z0 = 1; a careful search for possible additional
symmetry in (I) revealed none.
ISSN 0108-2701
Supramolecular structures of four
(Z)-5-arylmethylene-2-thioxothia-
zolidin-4-ones: hydrogen-bonded
dimers, chains of rings and sheets
Paula Delgado,a Jairo Quiroga,a Justo Cobo,b John
N. Lowc and Christopher Glidewelld*
a
Â
Â
Â
Grupo de Investigacion de Compuestos Heterocõclicos, Departamento de Quõmica,
In each of (I)±(IV) (Figs. 1±4), the molecules are nearly
planar, as shown by the values of the torsion angle (Table 1)
de®ning the rotation of the aryl ring relative to the rest of the
rigid skeleton. In addition, the methoxy C atom in (IV) is
virtually coplanar with the adjacent aryl ring. In each
compound, there is a fairly short intramolecular CÐHÁ Á ÁS
contact (Table 2), whose dimensions appear at ®rst sight to
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
Correspondence e-mail: cg@st-andrews.ac.uk
Received 5 July 2005
Accepted 7 July 2005
Online 23 July 2005
In each of the four title compounds, namely (Z)-5-benzyl-
idene-2-thioxothiazolidin-4-one, C10H7NOS2, (I), which crys-
tallizes with Z0 = 2 in space group P21/n, (Z)-5-(4-
methylbenzylidene)-2-thioxothiazolidin-4-one, C11H9NOS2,
(II),
(Z)-2-thioxo-5-[4-(tri¯uoromethyl)benzylidene]thiaz-
olidin-4-one, C11H6F3NOS2, (III), and (Z)-5-(4-methoxy-
benzylidene)-2-thioxothiazolidin-4-one, C11H9NO2S2, (IV),
there is a very wide CÐCÐC angle (ca 130ꢀ) at the methine
C atom linking the two rings. Pairs of NÐHÁ Á ÁO hydrogen
bonds link the two independent molecules in (I) into a cyclic
dimeric unit, and these units are further linked into complex
sheets by three independent CÐHÁ Á Áꢀ(arene) hydrogen
bonds. The molecules of (II) are linked by paired NÐHÁ Á ÁO
hydrogen bonds into centrosymmetric R22(8) dimers; the
molecules of (III) and (IV) are linked into chains of rings,
which are constructed from a combination of NÐHÁ Á ÁS and
CÐHÁ Á ÁO hydrogen bonds in (III), and from a combination of
NÐHÁ Á ÁO and CÐHÁ Á ÁS hydrogen bonds in (IV).
Comment
As part of a programme for the synthesis of new fused
heterocyclic systems of potential biological application, we
have been evaluating the use of (Z)-5-arylmethylene-2-thioxo-
thiazolidin-4-ones as intermediates for cycloconden-
sation reactions, and we report here the structures of
four such compounds, (I)±(IV), which have themselves been
prepared by condensation of rhodanine (2-thioxothiazolidin-
4-one) with arylaldehydes using microwave irradiation in a
solvent-free system.
Figure 1
The two independent molecules of (I), showing the atom-labelling
scheme and the NÐHÁ Á ÁO hydrogen bonds (dashed lines). Displacement
ellipsoids are drawn at the 30% probability level.
The structure of (IV) has been reported previously
(Okazaki et al., 1998) using diffraction data collected at
Acta Cryst. (2005). C61, o477±o482
DOI: 10.1107/S0108270105021888
# 2005 International Union of Crystallography o477

organic compounds
suggest an attractive hydrogen-bonding interaction forming an
S(6) ring (Bernstein et al., 1995). However, the bond angles
associated with the central CÐCÐC fragment are all strongly
indicative of a repulsive CÐHÁ Á ÁS interaction; thus, the angles
at the methine C atom linking the two rings are all around
130ꢀ. Moreover, the two exocyclic angles at thiazolidine atom
C5 consistently differ by ca 10ꢀ, and the exocyclic angles at
benzene atom C61 consistently differ by ca 6ꢀ, always in the
sense that the larger angle is that contained within the S(6)
motif. All of these bond angles are thus consistent with a
highly repulsive CÐHÁ Á ÁS contact, and it is noteworthy that
the repulsive contact is accommodated by distortion of the
skeletal bond angles in preference to a rotation about the
C6ÐC61 bond, which might at ®rst sight appear to be the less
energy-costly solution. In this respect, the behaviour of
compounds (I)±(IV) resembles that of a series of 5-(aryl-
methylene)-1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-triones,
whose essentially planar molecular skeletons are character-
ized by very wide CÐCÐC angles (ca 137±139ꢀ) at the brid-
ging methine C atom (Rezende et al., 2005).
involving the C4ÐO4 bonds in the molecules at (x, y, z) and
i
Ê
(1 x, 1 y, 1 z). The O4Á Á ÁC4 distance is 3.042 (2) A and
the C4ÐO4Á Á ÁC4i angle is 81.52 (9)ꢀ [symmetry code: (i) 1 x,
1
y, 1
z], so that this interaction typi®es the nearly
rectangular antiparallel type II motif (Allen et al., 1998). The
effect of this interaction is to link, albeit weakly, the hydrogen-
bonded dimers into a [100] chain. On the other hand, aromatic
ꢀ±ꢀ stacking interactions and intermolecular CÐHÁ Á ÁO and
CÐHÁ Á Áꢀ(arene) hydrogen bonds are all absent.
The notional replacement of the methyl group in (II) by a
tri¯uoromethyl group in (III) causes a marked change in the
supramolecular aggregation. The molecules of (III) are again
linked into centrosymmetric R22(8) dimers, but now by means
of paired NÐHÁ Á ÁS hydrogen bonds, as opposed to the NÐ
HÁ Á ÁO hydrogen bonds in (II). In addition, aryl atom C63 in
the molecule at (x, y, z) acts as a hydrogen-bond donor to
ketone atom O4 in the molecule at ( 1 + x, 1 + y, z), so
generating by translation a C(8) chain running parallel to the
[110] direction. The combination of the two hydrogen bonds
then generates a chain of edge-fused rings along [110], in
which R22(8) rings centred at (n, n 21, 12 ) (n = zero or integer)
In each of (I)±(IV), the ring angle at atom S1 is little greater
than 90ꢀ, while in (IV), the exocyclic bond angles at the ring C
atom ipso to the methoxy substituent show the usual devia-
tions from 120ꢀ.
The supramolecular structure of (I) is considerably more
complex than those of (II)±(IV), and it is the only one of the
series (I)±(IV) in which CÐHÁ Á Áꢀ(arene) hydrogen bonds
occur. For these reasons, we describe ®rst (II), which has the
simplest supramolecular structure, then (III) and (IV), and
®nally (I).
The molecules of (II) are linked by paired NÐHÁ Á ÁO
hydrogen bonds (Table 2) into a centrosymmetric R22(8) dimer
(Fig. 5), but the only direction-speci®c interaction between
these dimers is a dipolar carbonyl±carbonyl interaction
Figure 4
The molecule of (IV), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 30% probability level.
Figure 2
The molecule of (II), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 30% probability level.
Figure 5
Part of the crystal structure of (II), showing the formation of a
centrosymmetric hydrogen-bonded dimer. For clarity, H atoms bonded
to C atoms have been omitted. Atoms marked with an asterisk (*) are at
the symmetry position (2 x, 1 y, 1 z).
Figure 3
The molecule of (III), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 30% probability level.
ꢁ
o478 Delgado et al. C10H7NOS2, C11H9NOS2, C11H6F3NOS2 and C11H9NO2S2
Acta Cryst. (2005). C61, o477±o482

organic compounds
alternate with R44(26) rings centred at (n + 21, n, 21 ) (n = zero or
integer) (Fig. 6). The tri¯uoromethyl groups lie on the outer
edges of this chain; there are no direction-speci®c interactions
between adjacent chains.
substructures, one generated by inversion and the other
generated by a 21 screw axis.
In the ®rst substructure, aryl atoms C163 and C266 at (x, y,
z) act as hydrogen-bond donors, respectively, to aryl rings
C261±C266 at (1 x, 1 y, 1 z) and C161±C166 at (1 x,
The supramolecular structure of (IV) also consists of a
chain of rings, but now constructed from a combination of NÐ
HÁ Á ÁO and CÐHÁ Á ÁS hydrogen bonds as opposed to the
combination of NÐHÁ Á ÁS and CÐHÁ Á ÁO hydrogen bonds in
(III). Pairs of molecules are linked by NÐHÁ Á ÁO hydrogen
bonds into a centrosymmetric R22(8) dimer, just as in
compound (II), and these dimers are linked by one component
of a planar three-centre CÐHÁ Á Á(S)2 interaction (Table 2).
The shorter component in this system is probably a repulsive
contact as discussed above, but the longer component appears
to be attractive. Aryl atoms C62 in the molecules at (x, y, z)
and (2 x, 1 y, 1 z), which form the R22(8) dimer centred
at (1, 12, 12 ), act as hydrogen-bond donors, respectively, to thione
atoms S2 in the molecules at (1 x, y, 1 z) and (1 + x, 1 + y,
z), which themselves form parts of the R22(8) dimers centred at
(0, 12, 12 ) and (2, 23, 12 ), respectively, so generating by inversion a
complex chain of rings running parallel to the [110] direction
and containing S(6), R22(8) and R42(8) rings (Fig. 7).
1
y, 1 z), so generating by inversion a chain along (12, y, )
2
In (I), where the two independent molecules are related by
an approximate, but not exact, twofold rotation, the molecules
are again linked by a pair of NÐHÁ Á ÁO hydrogen bonds
(Table 2) into a dimeric aggregate (Fig. 1). These units are
then linked into sheets by three independent CÐ
HÁ Á Áꢀ(arene) hydrogen bonds, and the formation of this sheet
is very readily analysed in terms of two one-dimensional
Figure 7
Part of the crystal structure of (IV), showing the formation of a [110]
chain of rings generated by two-centre NÐHÁ Á ÁO and three-centre CÐ
HÁ Á Á(S)2 interactions. For clarity, H atoms not involved in the motifs
shown have been omitted. Atoms marked with an asterisk (*), a hash (#)
or a dollar sign ($) are at the symmetry positions (2 x, 1 y, 1 z),
(1 x, y, 1 z) and (1 + x, 1 + y, z), respectively.
Figure 6
Part of the crystal structure of (III), showing the formation of a [110]
chain of R22(8) and R44(26) rings. For clarity, H atoms not involved in the
motifs shown have been omitted. Atoms marked with an asterisk (*), a
hash (#), a dollar sign ($), an ampersand (&) or an `at' sign (@) are at the
symmetry positions (2 x, 1 y, 1 z), ( 1 + x, 1 + y, z), (1 x, y,
Figure 8
A stereoview of part of the crystal structure of (I), showing the formation
of a hydrogen-bonded [010] chain generated by inversion. For clarity, H
atoms not involved in the motifs shown have been omitted.
1
z), (3 x, 2 y, 1 z) and (1 + x, 1 + y, z), respectively.
ꢁ
Acta Cryst. (2005). C61, o477±o482
Delgado et al.
C10H7NOS2, C11H9NOS2, C11H6F3NOS2 and C11H9NO2S2 o479

organic compounds
Data collection
Nonius KappaCCD diffractometer
' and ! scans
3154 re¯ections with I > 2ꢅ(I)
Rint = 0.048
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.888, Tmax = 0.950
20659 measured re¯ections
4399 independent re¯ections
ꢃmax = 27.5ꢀ
h = 15 ! 15
k = 8 ! 9
l = 30 ! 30
Re®nement
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.038
wR(F2) = 0.095
S = 1.03
4399 re¯ections
w = 1/[ꢅ2(F2o) + (0.0403P)2
+ 0.8482P]
where P = (F2o + 2Fc2)/3
(Á/ꢅ)max = 0.001
3
Ê
Áꢆmax = 0.53 e A
Figure 9
3
Ê
0.33 e A
253 parameters
H-atom parameters constrained
Áꢆmin
=
Part of the crystal structure of (I), showing the formation of a hydrogen-
bonded [010] chain generated by a screw axis. For clarity, H atoms not
involved in the motifs shown have been omitted. Atoms marked with an
asterisk (*), a hash (#) or a dollar sign ($) are at the symmetry positions
3
2
Compound (II)
(
x, 12 + y, 32 z), (x, 1 + y, z) and (23 x, 21 + y, 32 z), respectively.
Crystal data
3
C11H9NOS2
Mr = 235.31
Dx = 1.463 Mg m
Mo Kꢂ radiation
containing three types of ring, two of which are centrosym-
metric (Fig. 8). In the second substructure, which involves only
one of the two independent molecules, aryl atom C166 at
(x, y, z) acts as a hydrogen-bond donor to the C161±C166 aryl
ring at (32 x, 21 + y, 32 z), so forming another [010] chain,
this time generated by the 21 screw axis along (34, y, 43 ) (Fig. 9).
Monoclinic, P21=c
Cell parameters from 2450
re¯ections
Ê
a = 4.9428 (1) A
b = 20.0473 (8) A
ꢃ = 3.6±27.5ꢀ
Ê
1
Ê
c = 10.7834 (4) A
ꢄ = 0.47 mm
T = 120 (2) K
ꢁ = 90.753 (2)ꢀ
V = 1068.43 (6) A
Z = 4
3
Ê
Lath, orange
0.56 Â 0.10 Â 0.08 mm
1
3
The molecule at (32
x,
+ y,
z) forms part of the
2
2
Data collection
inversion-generated chain lying along (1, y, 1), and hence the
combination of these two types of [010] chain generates a
sheet parallel to (101).
Nonius KappaCCD diffractometer
' and ! scans
2092 re¯ections with I > 2ꢅ(I)
Rint = 0.041
ꢃmax = 27.5ꢀ
h = 6 ! 6
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.780, Tmax = 0.964
11502 measured re¯ections
2450 independent re¯ections
k = 26 ! 26
l = 13 ! 14
Experimental
Equimolar quantities (1 mmol of each component) of 2-thioxothia-
zolidin-4-one and the appropriate benzaldehyde 4-XC6H4CHO
[where X = H for (I), CH3 for (II), CF3 for (III) and CH3O for (IV)]
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
reaction 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 analysis. For
(I) (orange crystals, m.p. 478 K, yield 58%), MS (70 eV) m/z (%): 221
(23, M+), 134 (100), 108 (40), 89 (8), 51 (4), 77 (2). For (II) (orange
crystals, m.p. 504 K, yield 56%), MS (70 eV) m/z (%): 235 (39, M+),
148 (100), 115 (10), 91 (9), 77 (4), 59 (9). For (III) (orange crystals,
m.p. 488 K, yield 62%), MS (70 eV) m/z (%): 291 (10, M+2), 290 (10,
M+1), 289 (100, M+), 152 (35), 138 (11). For (IV) (orange crystals,
m.p. 516 K, yield 87%), MS (70 eV) m/z (%): 164 (9), 149 (61),
121 (100), 89 (17), 77 (34), 63 (12).
Re®nement
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.033
wR(F2) = 0.086
S = 1.05
2450 re¯ections
w = 1/[ꢅ2(F2o) + (0.0356P)2
+ 0.7076P]
where P = (F2o + 2Fc2)/3
(Á/ꢅ)max = 0.001
3
Ê
Áꢆmax = 0.33 e A
3
Ê
0.28 e A
137 parameters
H-atom parameters constrained
Áꢆmin
=
Compound (III)
Crystal data
C11H6F3NOS2
Mr = 289.29
Triclinic, P1
a = 5.2859 (2) A
Ê
b = 6.2263 (3) A
Z = 2
Dx = 1.707 Mg m
Mo Kꢂ radiation
3
Ê
Cell parameters from 2566
re¯ections
ꢃ = 3.5±27.7ꢀ
ꢄ = 0.50 mm
T = 120 (2) K
Ê
c = 17.1885 (8) A
1
ꢂ = 91.753 (2)ꢀ
ꢁ = 95.326 (3)ꢀ
ꢇ = 90.129 (3)ꢀ
Compound (I)
Lath, orange
0.34 Â 0.18 Â 0.09 mm
3
Crystal data
Ê
V = 562.99 (4) A
3
C10H7NOS2
Mr = 221.29
Monoclinic, P21=n
Ê
a = 11.7286 (3) A
Dx = 1.527 Mg m
Mo Kꢂ radiation
Cell parameters from 4399
re¯ections
Data collection
Nonius KappaCCD diffractometer
' and ! scans
2144 re¯ections with I > 2ꢅ(I)
Rint = 0.035
ꢃmax = 27.7ꢀ
Ê
b = 7.0215 (2) A
ꢃ = 3.0±27.5ꢀ
ꢄ = 0.51 mm
T = 120 (2) K
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.849, Tmax = 0.957
10662 measured re¯ections
2566 independent re¯ections
1
Ê
c = 23.7552 (6) A
h = 6 ! 6
ꢁ = 100.2630 (12)ꢀ
k = 8 ! 8
3
Ê
V = 1925.00 (9) A
Z = 8
Block, orange
0.38 Â 0.20 Â 0.10 mm
l = 22 ! 22
ꢁ
o480 Delgado et al. C10H7NOS2, C11H9NOS2, C11H6F3NOS2 and C11H9NO2S2
Acta Cryst. (2005). C61, o477±o482

organic compounds
Table 1
Selected geometric parameters (A, ) for compounds (I)±(IV).
ꢀ
Ê
Parameter
(I), mol 1
1
(I), mol 2
2
(II)
nil
(III)
nil
(IV)
nil
x =
Sx1ÐCx2
Cx2ÐNx3
Nx3ÐCx4
Cx4ÐCx5
Cx5ÐSx1
Cx2ÐSx2
Cx4ÐOx4
Cx5ÐCx6
Cx6ÐCx61
1.753 (2)
1.363 (3)
1.383 (3)
1.477 (3)
1.757 (2)
1.635 (2)
1.225 (2)
1.351 (3)
1.454 (3)
1.7502 (19)
1.366 (3)
1.379 (3)
1.478 (3)
1.756 (2)
1.626 (2)
1.224 (2)
1.348 (3)
1.452 (3)
1.7494 (17)
1.370 (2)
1.378 (2)
1.750 (2)
1.358 (3)
1.390 (3)
1.487 (3)
1.753 (2)
1.643 (2)
1.212 (2)
1.347 (3)
1.457 (3)
1.748 (2)
1.367 (3)
1.372 (2)
1.474 (3)
1.758 (2)
1.624 (2)
1.227 (2)
1.342 (3)
1.455 (3)
1.483 (2)
1.7553 (16)
1.6337 (17)
1.2238 (19)
1.344 (2)
1.455 (2)
Cx5ÐSx1ÐCx2
Sx1ÐCx5ÐCx6
Cx4ÐCx5ÐCx6
Cx5ÐCx6ÐCx61
Cx6ÐCx61ÐCx62
Cx6ÐCx61ÐCx66
Cx63ÐCx64ÐOx41
Cx65ÐCx64ÐOx41
Cx64ÐOx41ÐCx41
92.51 (9)
130.27 (16)
120.19 (18)
130.97 (19)
124.02 (18)
117.51 (18)
92.47 (15)
129.82 (16)
120.79 (18)
130.13 (19)
124.71 (15)
118.04 (18)
92.60 (8)
130.43 (13)
120.26 (14)
130.98 (15)
123.97 (19)
117.50 (14)
92.42 (10)
129.84 (17)
120.43 (18)
130.25 (19)
124.19 (18)
118.14 (19)
92.42 (10)
130.64 (16)
120.14 (18)
131.07 (19)
118.22 (18)
115.42 (18)
124.70 (19)
117.45 (16)
Cx5ÐCx6ÐCx61ÐCx62
Cx63ÐCx64ÐOx41ÐCx41
2.9 (3)
4.5 (3)
3.1 (3)
3.6 (4)
4.7 (3)
178.99 (17)
Table 2
Hydrogen bonds and short intramolecular contacts (A, ) for compounds
(I)±(IV).
Re®nement
ꢀ
Ê
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.038
wR(F2) = 0.103
S = 1.07
2566 re¯ections
w = 1/[ꢅ2(F2o) + (0.0459P)2
+ 0.5642P]
where P = (F2o + 2Fc2)/3
(Á/ꢅ)max < 0.001
Cg1 and Cg2 are the centroids of the C161±C166 and C261±C266 rings,
respectively
3
Ê
Áꢆmax = 0.50 e A
3
Ê
0.54 e A
163 parameters
H-atom parameters constrained
Áꢆmin
=
Compound DÐHÁ Á ÁA
DÐH HÁ Á ÁA DÁ Á ÁA
DÐHÁ Á ÁA
(I)
N13ÐH13Á Á ÁO24
0.95
0.95
0.95
0.95
0.95
0.95
0.95
1.94
1.99
2.56
2.50
2.68
2.82
2.76
2.829 (2)
2.868 (2)
3.281 (2)
3.231 (2)
3.352 (2)
3.519 (2)
3.435 (2)
168
165
133
134
128
131
129
N23ÐH23Á Á ÁO14
C162ÐH162Á Á ÁS11
C262ÐH262Á Á ÁS21
C163ÐH163Á Á ÁCg2i
C166ÐH166Á Á ÁCg1ii
C266ÐH266Á Á ÁCg1iii
Compound (IV)
Crystal data
C11H9NO2S2
Mr = 251.31
Monoclinic, P21=c
Ê
a = 5.1314 (2) A
Mo Kꢂ radiation
Cell parameters from 2515
re¯ections
(II)
N3ÐH3Á Á ÁO4iv
0.93
0.95
1.93
2.58
2.8507 (18) 168
3.2911 (16) 132
C62ÐH62Á Á ÁS1
ꢃ = 3.6±27.5ꢀ
1
Ê
b = 10.4543 (5) A
ꢄ = 0.47 mm
T = 120 (2) K
(III)
N3ÐH3Á Á ÁS2iv
C62ÐH62Á Á ÁS1
C63ÐH63Á Á ÁO4v
N3ÐH3Á Á ÁO4iv
C62ÐH62Á Á ÁS1
C62ÐH62Á Á ÁS2iii
0.90
0.95
0.95
2.41
2.51
2.34
3.3048 (18) 172
Ê
c = 20.5324 (9) A
3.230 (2)
3.114 (2)
133
138
ꢁ = 91.702 (2)ꢀ
V = 1100.98 (8) A
Plate, orange
0.44 Â 0.18 Â 0.08 mm
3
Ê
Z = 4
Dx = 1.516 Mg m
(IV)
0.90
0.95
0.95
1.90
2.57
2.86
2.789 (2)
3.288 (2)
3.588 (2)
169
133
135
3
Data collection
3
2
1
2
Symmetry codes: (i) 1 x; 1 y; 1 z; (ii)
(iv) 2 x; 1 y; 1 z; (v) 1 ‡ x; 1 ‡ y; z.
x;
‡ y; 32 z; (iii) 1 x; y; 1 z;
Nonius KappaCCD diffractometer
' and ! scans
1958 re¯ections with I > 2ꢅ(I)
Rint = 0.041
ꢃmax = 27.5ꢀ
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.820, Tmax = 0.963
11472 measured re¯ections
2515 independent re¯ections
h = 6 ! 6
k = 13 ! 13
l = 26 ! 26
For compound (I), the space group P21/n was uniquely assigned
from the systematic absences. Likewise, the space group P21/c was
uniquely assigned for both (II) and (IV). Although the unit cells for
(II) and (IV) appear to have very different dimensions and shapes,
with the b parameter for (II) nearly double that for (IV), both cells
have values of ꢁ close to 90ꢀ, so that not only are their reduced cells
similar in dimensions but both are close to orthorhombic metrics.
Crystals of (III) are triclinic; the space group P1 was selected and
con®rmed by the successful structure analysis. All H atoms were
located from difference maps and then treated as riding atoms. H
Re®nement
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.038
wR(F2) = 0.103
S = 1.04
2515 re¯ections
w = 1/[ꢅ2(F2o) + (0.0494P)2
+ 0.5614P]
where P = (F2o + 2Fc2)/3
(Á/ꢅ)max = 0.001
3
Ê
Áꢆmax = 0.33 e A
3
Ê
0.40 e A
146 parameters
H-atom parameters constrained
Áꢆmin
=
ꢁ
Acta Cryst. (2005). C61, o477±o482
Delgado et al.
C10H7NOS2, C11H9NOS2, C11H6F3NOS2 and C11H9NO2S2 o481

organic compounds
atoms bonded to C atoms were assigned CÐH distances of 0.95
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK1860). Services for accessing these data are
described at the back of the journal.
Ê
(aromatic and methine) or 0.98 A (methyl) [with Uiso(H) = 1.2Ueq(C),
or 1.5Ueq(C) for the methyl groups]. H atoms bonded to N atoms
Ê
were allowed to ride at the NÐH distances (0.90±0.93 A) deduced
from the difference maps [with Uiso(H) = 1.2Ueq(N)]. In (III), the
displacement parameters for the F atoms indicated some libration of
the CF3 group, but it was not found necessary to model this group
with more than three F-atom sites.
References
Allen, F. H. (2002). Acta Cryst. B58, 380±388.
Allen, F. H., Baalham, C. A., Lommerse, J. P. M. & Raithby, P. R. (1998). Acta
Cryst. B54, 320±329.
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: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick,
1997); program(s) used to re®ne structure: OSCAIL and SHELXL97
(Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); soft-
ware used to prepare material for publication: SHELXL97 and
PRPKAPPA (Ferguson, 1999).
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555±1573.
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.
Okazaki, M., Uchino, N., Ishihara, M. & Fukunaga, H. (1998). Bull. Chem. Soc.
Jpn, 71, 1713±1718.
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.
X-ray data were collected at the EPSRC X-ray Crystal-
lographic Service, University of Southampton. JC thanks the
Rezende, M. C., Dominguez, M., Wardell, J. L., Skakle, J. M. S., Low, J. N. &
Glidewell, C. (2005). Acta Cryst. C61, o306±o311.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
Â
Â
Consejerõa de Innovacion, Ciencia y Empresa (Junta de
È
Gottingen, Germany.
Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Gottingen,
Â
Â
Andalucõa, Spain) and the Universidad de Jaen for ®nancial
support. PD and JQ thank COLCIENCIAS and UNIVALLE
(Universidad del Valle, Colombia) for ®nancial support.
È
Germany.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7±13.
ꢁ
o482 Delgado et al. C10H7NOS2, C11H9NOS2, C11H6F3NOS2 and C11H9NO2S2
Acta Cryst. (2005). C61, o477±o482