Five symmetrically substituted 2-aryl-3-benzyl-1,3-thia-zolidin-4-ones: Supra-molecular structures in zero, one and two dimensions

Article abstract of DOI:10.1107/S0108270106055272

There are no direction-specific inter-actions between the mol-ecules of 3-(2-methoxy-benz-yl)-2-(2-methoxy-phen-yl)-1,3-thia-zolidin-4-one, C18H19NO3S, (I); the mol-ecules of 3-(4-nitro-benz-yl)-2-(4-nitro-phen-yl)-1,3-thia-zolidin- 4-one, C16H13N3O5S, (I

Full text of DOI:10.1107/S0108270106055272

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
cally pure chiral amines consistently led to products with no
enantioselectivity at C2. A preliminary report has appeared on
compound (V), establishing proof of the constitution of this
unexpected reaction product, but that report gave no stereo-
chemical information nor any discussion of the supra-
molecular aggregation (Cunico et al., 2006).
ISSN 0108-2701
Five symmetrically substituted
2-aryl-3-benzyl-1,3-thiazolidin-
4-ones: supramolecular structures
in zero, one and two dimensions
Wilson Cunico,a Liliane R. Capri,a C. R. B. Gomes,a
Solange M. S. V. Wardell,a John N. Lowb and Christopher
Glidewellc*
a
Â
Instituto de Tecnologia em Farmacos, Far-Manguinhos, FIOCRUZ, 21041-250 Rio
de Janeiro, RJ, Brazil, bDepartment of Chemistry, University of Aberdeen, Meston
Walk, Old Aberdeen AB24 3UE, Scotland, and cSchool of Chemistry, University of
St Andrews, Fife KY16 9ST, Scotland
Correspondence e-mail: cg@st-andrews.ac.uk
Received 6 December 2006
Accepted 19 December 2006
Online 13 January 2007
There are no direction-speci®c interactions between the
molecules of 3-(2-methoxybenzyl)-2-(2-methoxyphenyl)-1,3-
thiazolidin-4-one, C18H19NO3S, (I); the molecules of 3-(4-
nitrobenzyl)-2-(4-nitrophenyl)-1,3-thiazolidin-4-one, C16H13-
N3O5S, (II), are linked by four independent CÐHÁ Á ÁO
hydrogen bonds into complex chains of fused rings. In 3-(4-
methoxybenzyl)-2-(4-methoxyphenyl)-1,3-thiazolidin-4-one,
(III), isomeric with (I), the molecules are linked into sheets by
a combination of CÐHÁ Á ÁO and CÐHÁ Á Áꢀ(arene) hydrogen
bonds, while in 3-(2-nitrobenzyl)-2-(2-nitrophenyl)-1,3-thia-
zolidin-4-one, (IV), isomeric with (II), the sheets are built
from three independent CÐHÁ Á ÁO hydrogen bonds and one
CÐHÁ Á Áꢀ(arene) hydrogen bond, and reinforced by an
aromatic ꢀ±ꢀ stacking interaction. In 3-(2-¯uorobenzyl)-2-
(2-¯uorophenyl)-1,3-thiazolidin-4-one, C16H13F2NOS, (V),
where the 2-aryl ring exhibits orientational disorder, the
molecules are linked into sheets by a combination of CÐ
HÁ Á ÁO and CÐHÁ Á Áꢀ(arene) hydrogen bonds, and the sheets
are linked in pairs, forming bilayers, by an aromatic ꢀ±ꢀ
stacking interaction.
In each of compounds (I)±(V) (Figs. 1±5), atom C2 is a
stereogenic centre; all the compounds, as prepared, are
racemic despite the use of enantiomerically pure l-valine as
the source of the ring N atom. Each compound crystallizes in a
centrosymmetric space group and for each the reference
molecule was selected as one having the S con®guration at C2.
While the amidic portion of the heterocyclic ring is effec-
tively planar in each compound, overall these rings are all non-
planar. In each of compounds (I)±(IV), the heterocyclic ring
adopts an envelope conformation, folded across the line
C2Á Á ÁC5, while in compound (V), the ring adopts the half-
chair conformation, twisted about the S1ÐC5 bond. The bond
distances and angles present no unusual values. The primary
interest in the structures is the dramatic in¯uence exerted
upon the supramolecular aggregation by the nature and
location of the single substituent in the aryl rings; the struc-
tural variation involves both the types of direction-speci®c
intermolecular interaction present in the supramolecular
structures and the effects of these interactions upon the
dimensionality of these structures. We discuss the structures in
order of increasing complexity, from the isolated molecules in
compound (I) up to the bilayers in compound (V).
Comment
We report here the molecular and supramolecular structures
of ®ve substituted 2-aryl-3-benzyl-1,3-thiazolidin-4-ones, (I)±
(V), all obtained from the reactions of the corresponding aryl
aldehydes with l-valine [(S)-2-amino-3-methylpropionic acid]
and mercaptoacetic acid in the presence of diisopropylethyl-
amine (Cunico et al., 2006). The method of synthesis (Cunico
et al., 2006) represents a one-stage simpli®cation of a
previously published two-stage procedure (Holmes et al.,
1995); in this earlier investigation, it was found that, under the
forcing reaction conditions required, the use of enantiomeri-
o102 # 2007 International Union of Crystallography
DOI: 10.1107/S0108270106055272
Acta Cryst. (2007). C63, o102±o107

organic compounds
There are no direction-speci®c intermolecular interactions
in the crystal structure of compound (I), which thus consists of
effectively isolated molecules.
chain of rings (Fig. 6). Two such chains, related to one another
by the translational symmetry operations, run along the lines
(12, y, 0) and (21, y, 12 ), but there are no direction-speci®c
interactions between adjacent chains.
In the structure of compound (II), there are four indepen-
dent CÐHÁ Á ÁO hydrogen bonds (Table 1), which link the
molecules into complex chains. Atoms C2 and C37 in the
molecule at (x, y, z) act as hydrogen-bond donors, respectively,
to nitro atoms O241 and O342 in the molecules at (x, 1 + y,
z) and (x, 1 + y, z), so generating by translation a chain of
edge-fused R22(20) rings (Bernstein et al., 1995) running
parallel to the [010] direction. This chain is weakly reinforced
by a further, rather long and possibly adventitious, interaction
between C32 at (x, y, z) and O342 at (x, 1 + y, z). Pairs of these
chains are linked by the ®nal hydrogen bond in which atom
C22 in the molecule at (x, y, z) acts as a donor to ring atom O4
in the molecule at (1 x, 1 y, 1 z), so forming a complex
The formation of the hydrogen-bonded sheets in compound
(III) is very simple, utilizing only two hydrogen bonds, one of
CÐHÁ Á ÁO and one of CÐHÁ Á Áꢀ(arene) type (Table 2). Atoms
C5 and C37 in the molecule at (x, y, z) act as hydrogen-bond
donors, respectively, to methoxy atom O34 in the molecule at
( 1 + x, 1 + y, z) and to the C31±C36 ring in the molecule at
( 1 + x, y, z). These interactions thus generate by translation a
sheet lying parallel to (001) (Fig. 7). Four such sheets pass
through each unit cell, in the domains 0.04 < z < 0.31, 0.19 < z <
0.46, 0.54 < z < 0.81 and 0.69 < z < 0.96, but there are no
direction-speci®c intermolecular interactions between the
sheets, nor is there any interweaving of the pairs of sheets
within the domains 0 < z < 0.5 and 0.5 < z < 1.0.
Figure 1
A molecule of (I), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 30% probability level.
Figure 3
A molecule of (III), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 30% probability level.
Figure 2
A molecule of (II), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 30% probability level.
Figure 4
A molecule of (IV), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 30% probability level.
ꢀ
Acta Cryst. (2007). C63, o102±o107
Cunico et al.
C18H19NO3S, C16H13N3O5S and C16H13F2NOS o103

organic compounds
The sheet structure of compound (IV) is much more
complex than that in compound (III) and it is most readily
analysed in terms of two substructures, built, respectively,
from two CÐHÁ Á ÁO hydrogen bonds, and from one CÐHÁ Á ÁO
and one CÐHÁ Á Áꢀ(arene) hydrogen bond (Table 3). In the
®rst of these substructures, atoms C24 and C26 in the molecule
at (x, y, z) act as hydrogen-bond donors, respectively, to atoms
O4 at (x, 1 + y, z) and O31 at (1 x, y, 32 z). Propagation of
these two interactions by translation and rotation then
produces a chain of edge-fused rings running parallel to the
[010] direction and generated by the twofold rotation axis
In the second substructure, atom C35 in the molecule at (x,
y, z) acts as a hydrogen-bond donor to atom O4 in the mol-
1
ecule at (x, y,
+ z), so forming a C(8) chain running
2
parallel to the [001] direction and generated by the c-glide
plane at y = 0 (Fig. 9). At the same time, atom C25 at (x, y, z)
acts as a donor to the C31±C36 ring in the molecule at (x, 1 y,
1
2
+ z), so forming another chain along [001], this time gener-
ated by the c-glide plane at y = 12. The combination of these two
chains along [001] generates a sheet parallel to (100) (Fig. 9).
Hence, the combination of this rather simple two-dimensional
substructure with the chain of fused rings (Fig. 8) generates a
sheet structure of considerable complexity.
3
along (12, y, ), and containing alternating R22(20) and R44(32)
4
rings (Fig. 8).
The molecule of compound (V) exhibits disorder in the
orientation of the C21±C26 ring, where two orientations are
related by a 180ꢁ rotation about the C2ÐC21 bond, so that the
F atom is disordered over two sites, denoted F22 and F26
(Fig. 5), with occupancies 0.647 (4) and 0.353 (4), respectively.
There are only two hydrogen bonds in the structure of
compound (V) (Table 4) and these link the molecules into
sheets, pairs of which are further linked into bilayers by a
single aromatic ꢀ±ꢀ stacking interaction; the formation of the
Figure 5
A molecule of (V), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 30% probability level. Atom sites F22 and F26,
and the associated H-atom sites, have partial occupancies (see Comment).
Figure 7
A stereoview of part of the crystal structure of compound (III), showing
the formation of a sheet parallel to (001) built from CÐHÁ Á ÁO and CÐ
HÁ Á Áꢀ(arene) hydrogen bonds. For the sake of clarity, H atoms not
involved in the motifs shown have been omitted.
Figure 6
Figure 8
A stereoview of part of the crystal structure of compound (II), showing
the formation of a chain of fused rings built from CÐHÁ Á ÁO hydrogen
bonds and running along [010]. For the sake of clarity, H atoms not
involved in the motifs shown have been omitted.
A stereoview of part of the crystal structure of compound (IV), showing
the formation of a chain of edge-fused R22(20) and R44(32) rings built from
CÐHÁ Á ÁO hydrogen bonds and running along [010]. For the sake of
clarity, H atoms not involved in the motifs shown have been omitted.
ꢀ
o104 Cunico et al. C18H19NO3S, C16H13N3O5S and C16H13F2NOS
Acta Cryst. (2007). C63, o102±o107

organic compounds
bilayers is not in¯uenced by the disorder. Atom C24 in the
molecule at (x, y, z) acts as a hydrogen-bond donor to atom
O4 in the molecule at (x, 1 + y, z), so generating by translation
a C(9) chain running parallel to the [010] direction. At the
same time atom C35 in the molecule at (x, y, z) acts as a donor
1
2
1
to the C21±C26 ring in the molecule at (x,
y,
+ z), so
2
forming a chain along [001] generated by the c-glide plane at
y = 0.25; the combination of the chains along [010] and [001]
generates a sheet parallel to (100) (Fig. 10). Two sheets of this
1
4
3
4
type, generated by the c-glide planes at y = and y = , and
related to one another by inversion, pass through each unit
cell and these pairs are linked into bilayers by a centrosym-
metric ꢀ±ꢀ stacking interaction. The C31±C36 rings in the
molecules at (x, y, z) and (1 x, y, 1 z) are strictly parallel
Ê
with an interplanar spacing of 3.695 (2) A; the ring-centroid
Ê
separation is 3.862 (2) A, corresponding to a ring-centroid
Ê
offset of 1.125 (2) A (Fig. 11).
The supramolecular structures described here show some
marked variations consequent upon changes only in the
Figure 11
Part of the crystal structure of compound (V), showing the ꢀ±ꢀ stacking
interaction that links pairs of sheets. For the sake of clarity, all H atoms
have been omitted. Atoms marked with an asterisk (*) are at the
symmetry position (1 x, y, 1 z).
location or identity of a single substituent common to the two
aryl rings. This variation is particularly striking in the pairs of
isomeric compounds (I) and (II), containing methyl substi-
tuents, and (I) and (IV), containing nitro substituents.
Whereas compound (I), containing 2-methoxy substituents,
adopts a structure exhibiting no direction-speci®c inter-
molecular interactions, the isomeric compound (III),
containing 4-methoxy substituents, aggregates into a two-
dimensional structure. On the other hand, compound (IV),
containing 2-nitro substituents, has a two-dimensional struc-
ture, while the isomeric compound (II), containing 4-nitro
substituents, has a supramolecular structure that is only one-
dimensional.
Figure 9
A stereoview of part of the crystal structure of compound (IV), showing
the formation of a sheet parallel to (100) built from CÐHÁ Á ÁO and CÐ
HÁ Á Áꢀ(arene) hydrogen bonds. For the sake of clarity, H atoms not
involved in the motifs shown have been omitted.
Experimental
Samples of compounds (I)±(V) were prepared according to a
published procedure (Cunico et al., 2006); crystals suitable for single-
crystal X-ray diffraction were grown by slow evaporation of solutions
in ethanol.
Compound (I)
Crystal data
C18H19NO3S
Mr = 329.40
Monoclinic, P21=n
Ê
a = 8.3321 (2) A
b = 18.3668 (4) A
Ê
c = 10.8568 (2) A
ꢁ = 94.450 (2)ꢁ
V = 1656.45 (6) A
Z = 4
Dx = 1.321 Mg m
Mo Kꢂ radiation
ꢃ = 0.21 mm
T = 120 (2) K
Block, colourless
0.35 Â 0.35 Â 0.20 mm
3
1
Figure 10
Ê
A stereoview of part of the crystal structure of compound (V), showing
the formation of a sheet parallel to (100) built from CÐHÁ Á ÁO and CÐ
HÁ Á Áꢀ(arene) hydrogen bonds. For the sake of clarity, H atoms not
involved in the motifs shown have been omitted.
3
Ê
ꢀ
Acta Cryst. (2007). C63, o102±o107
Cunico et al.
C18H19NO3S, C16H13N3O5S and C16H13F2NOS o105

organic compounds
Data collection
Data collection
Bruker±Nonius KappaCCD
diffractometer
' and ! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.940, Tmax = 0.959
17857 measured re¯ections
3643 independent re¯ections
3259 re¯ections with I > 2ꢄ(I)
Rint = 0.032
Bruker±Nonius KappaCCD
diffractometer
' and ! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.942, Tmax = 0.985
7975 measured re¯ections
3026 independent re¯ections
2470 re¯ections with I > 2ꢄ(I)
Rint = 0.034
ꢅmax = 27.5ꢁ
ꢅmax = 27.6ꢁ
Re®nement
Re®nement
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.035
wR(F2) = 0.086
S = 1.04
3643 re¯ections
210 parameters
H-atom parameters constrained
w = 1/[ꢄ2(F2o) + (0.0269P)2
+ 1.0914P]
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.061
wR(F2) = 0.239
S = 1.10
3026 re¯ections
w = 1/[ꢄ2(F2o) + (0.1489P)2
+ 1.6071P]
where P = (F2o + 2Fc2)/3
(Á/ꢄ)max = 0.001
where P = (F2o + 2Fc2)/3
(Á/ꢄ)max < 0.001
3
3
Ê
Ê
Áꢆmax = 0.33 e A
Áꢆmax = 0.52 e A
3
3
Ê
0.25 e A
Ê
0.43 e A
Áꢆmin
=
210 parameters
H-atom parameters constrained
Áꢆmin
=
Table 2
Hydrogen-bond geometry (A, ) for (III).
ꢁ
Ê
Compound (II)
Cg1 is the centroid of the C31±C36 ring.
Crystal data
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
C16H13N3O5S
Mr = 359.35
Z = 4
Dx = 1.492 Mg m
Mo Kꢂ radiation
ꢃ = 0.24 mm
T = 120 (2) K
Plate, colourless
0.18 Â 0.16 Â 0.02 mm
3
C5ÐH52Á Á ÁO34i
0.99
0.99
2.43
2.81
3.360 (5)
3.525 (4)
156
129
C37ÐH37AÁ Á ÁCg1ii
Monoclinic, P21=c
1
Ê
a = 14.2230 (7) A
Ê
b = 7.9862 (4) A
Symmetry codes: (i) x 1; y 1; z; (ii) x 1; y; z.
Ê
c = 14.1156 (7) A
ꢁ = 93.908 (3)ꢁ
V = 1599.63 (14) A
3
Ê
Compound (IV)
Data collection
Bruker±Nonius KappaCCD
diffractometer
' and ! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.966, Tmax = 0.995
3641 measured re¯ections
3641 independent re¯ections
2630 re¯ections with I > 2ꢄ(I)
Rint = 0.0
Crystal data
C16H13N3O5S
Mr = 359.35
Z = 8
Dx = 1.476 Mg m
Mo Kꢂ radiation
ꢃ = 0.23 mm
T = 120 (2) K
Block, colourless
0.40 Â 0.30 Â 0.20 mm
3
Monoclinic, C2=c
ꢅmax = 27.5ꢁ
1
Ê
a = 22.3000 (4) A
Ê
b = 9.9352 (3) A
Ê
c = 14.6945 (4) A
Re®nement
ꢁ = 96.435 (2)ꢁ
V = 3235.13 (14) A
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.122
wR(F2) = 0.438
S = 1.10
3641 re¯ections
227 parameters
H-atom parameters constrained
w = 1/[ꢄ2(F2o) + (0.35P)2]
where P = (F2o + 2Fc2)/3
(Á/ꢄ)max < 0.001
3
Ê
Data collection
3
Bruker±Nonius KappaCCD
diffractometer
' and ! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.929, Tmax = 0.955
34307 measured re¯ections
3713 independent re¯ections
2956 re¯ections with I > 2ꢄ(I)
Rint = 0.044
Ê
Áꢆmax = 1.01 e A
3
Ê
0.68 e A
Áꢆmin
=
ꢅmax = 27.5ꢁ
Table 1
Hydrogen-bond geometry (A, ) for (II).
ꢁ
Ê
Re®nement
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.036
wR(F2) = 0.096
S = 1.06
3713 re¯ections
w = 1/[ꢄ2(F2o) + (0.0484P)2
+ 2.1203P]
C2ÐH2Á Á ÁO241i
1.00
0.95
0.95
0.99
2.37
2.45
2.52
2.39
3.263 (8)
3.210 (7)
3.355 (7)
3.327 (7)
148
137
147
158
C22ÐH22Á Á ÁO4ii
C32ÐH32Á Á ÁO342iii
C37ÐH37BÁ Á ÁO342iii
where P = (F2o + 2Fc2)/3
(Á/ꢄ)max = 0.001
3
Ê
Áꢆmax = 0.26 e A
3
Ê
0.35 e A
226 parameters
H-atom parameters constrained
Áꢆmin
=
Symmetry codes: (i) x; y 1; z; (ii) x ‡ 1; y ‡ 1; z ‡ 1; (iii) x; y ‡ 1; z.
Table 3
Hydrogen-bond geometry (A, ) for (IV).
ꢁ
Ê
Compound (III)
Cg1 is the centroid of the C31±C36 ring.
Crystal data
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
C18H19NO3S
Mr = 329.42
Monoclinic, P21=c
Z = 4
Dx = 1.379 Mg m
Mo Kꢂ radiation
ꢃ = 0.22 mm
T = 120 (2) K
Plate, colourless
0.32 Â 0.15 Â 0.07 mm
3
C24ÐH24Á Á ÁO4i
C26ÐH26Á Á ÁO31ii
C35ÐH35Á Á ÁO4iii
C25ÐH25Á Á ÁCg1iv
0.95
0.95
0.95
0.95
2.38
2.45
2.46
2.96
3.2724 (18)
3.1985 (19)
3.1163 (18)
3.7624 (17)
156
135
126
143
1
Ê
Ê
a = 4.6687 (4) A
b = 9.6210 (8) A
Ê
c = 35.478 (3) A
ꢁ = 95.335 (3)ꢁ
V = 1586.7 (2) A
Symmetry codes: (i) x; y ‡ 1; z; (ii) x ‡ 1; y; z ‡ 32; (iii) x, y; z 21; (iv) x, y ‡ 1,
z ‡ 12.
3
Ê
ꢀ
o106 Cunico et al. C18H19NO3S, C16H13N3O5S and C16H13F2NOS
Acta Cryst. (2007). C63, o102±o107

organic compounds
Compound (V)
all other H atoms. The structure of compound (II) indicated twinning.
The TwinRotMAt procedure in PLATON (Spek, 2003) was used to
generate a HKLF5 ®le containing 3641 re¯ections, with an estimated
BASF value of 0.41; the ®nal BASF value was 0.299 (7). Accordingly,
the ®nal R factors are high because of the lack of any averaging of
equivalent re¯ections. It was apparent from an early stage that one of
the F atoms in compound (V) was disordered over two sites, denoted
F22 and F26; the ®nal re®ned occupancies were 0.647 (4) and
0.353 (4).
Crystal data
C16H13F2NOS
Mr = 305.33
Z = 4
Dx = 1.469 Mg m
Mo Kꢂ radiation
ꢃ = 0.26 mm
T = 120 (2) K
Plate, colourless
0.36 Â 0.30 Â 0.04 mm
3
Monoclinic, P21=c
1
Ê
Ê
a = 13.9981 (6) A
b = 10.1236 (3) A
Ê
c = 10.1491 (4) A
ꢁ = 106.333 (2)ꢁ
V = 1380.20 (9) A
3
Ê
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).
Data collection
Bruker±Nonius KappaCCD
diffractometer
' and ! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.944, Tmax = 0.990
15108 measured re¯ections
3123 independent re¯ections
2575 re¯ections with I > 2ꢄ(I)
Rint = 0.034
ꢅmax = 27.5ꢁ
Re®nement
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.059
wR(F2) = 0.145
S = 1.05
3123 re¯ections
w = 1/[ꢄ2(F2o) + (0.0597P)2
+ 1.6351P]
X-ray data were collected at the EPSRC National Crystal-
lography Service, University of Southampton, England; the
authors thank the staff of the Service for all their help and
advice. JLW thanks CNPq for ®nancial support.
where P = (F2o + 2Fc2)/3
(Á/ꢄ)max < 0.001
3
Ê
Áꢆmax = 0.84 e A
3
Ê
0.93 e A
200 parameters
H-atom parameters constrained
Áꢆmin
=
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: GG3061). Services for accessing these data are
described at the back of the journal.
Table 4
Hydrogen-bond geometry (A, ) for (V).
ꢁ
Ê
Cg2 is the centroid of the C21±C26 ring.
References
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555±1573.
Cunico, W., Capri, L. R., Gomes, C. R. B., Sizilio, R. H. & Wardell, S. M. S. V.
(2006). Synthesis, pp. 3405±3408.
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.
Holmes, C. P., Chinn, J. P., Look, G. C., Gordon, E. M. & Gallop, M. A. (1995).
J. Org. Chem. 60, 7328±7333.
C24ÐH24Á Á ÁO4i
0.95
0.95
2.40
2.86
3.274 (3)
3.569 (3)
153
133
C35ÐH35Á Á ÁCg2ii
3
Symmetry codes: (i) x; y ‡ 1; z; (ii) x;
y
12; z
.
2
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 compound (I), the space group P21/n was uniquely assigned
from the systematic absences; the space group P21/c was similarly
assigned for each of compounds (II), (III) and (V). For compound
(IV), the systematic absences permitted Cc and C2/c as possible space
groups; C2/c was selected and then con®rmed by the structure
analysis. All H atoms were located in difference maps and then
treated as riding atoms, with CÐH distances of 0.95 (aromatic), 0.98
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
È
Gottingen, Germany.
Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Gottingen,
È
Ê
(CH3), 0.99 (CH2) or 1.00 A (aliphatic CH), and with Uiso(H) =
kUeq(C), where k = 1.5 for the methyl groups in (III) and k = 1.2 for
Germany.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7±13.
ꢀ
Acta Cryst. (2007). C63, o102±o107
Cunico et al.
C18H19NO3S, C16H13N3O5S and C16H13F2NOS o107