Conformational preferences and supramolecular aggregation in 2-nitrophenylthiolates: Disulfides and thiosulfonates

Article abstract of DOI:10.1107/S0108768100007114

In each of the asymmetrically substituted disulfides 2-nitro-4′-methyldiphenyl disulfide, C₁₃H₁₁NO₂S₂ (1), 2-nitro-4′-chlorodiphenyl disulfide, C₁₂H₈ClNO₂S₂ (2), 2,4-dinitro-4′-methyldiphenyl disulfide, C₁₃H₁₀N₂O₄S₂ (3), and 2,4-dinitrophenyl-2′-methoxycarbonylmethyl disulfide, C₉H₈N₂O₆S₂ (4), and in both of the symmetrically substituted disulfides bis(2-nitrophenyl) disulfide, C₁₂H₈N₂O₄S₂ (5), and bis(2-nitro-4-trifluoromethylphenyl) disulfide, C₁₄H₆F₆N₂O₄S₂ (6), the 2-nitro groups are essentially coplanar with the adjacent aryl ring and the S atom remote from the nitrated aryl ring is also essentially coplanar and transoid to the nitro group. In S-(2-nitrophenyl) 2-nitrobenzene thiosulfonate, C₁₂H₈N₂O₆S₂ (7), which contains three independent molecules in the asymmetric unit, all six of the independent nitro groups are twisted out of the plane of the adjacent aryl rings. The crystal structures of (1)-(3) contain isolated molecules, that of (4) contains centrosymmetric dimers held together by C-H...O hydrogen bonds, while in the structures of (5)-(7), respectively, the C-H...O hydrogen bonds generate one-, two-and three-dimensional arrays. The interplay between molecular conformation and supramolecular aggregation is discussed.

Full text of DOI:10.1107/S0108768100007114

research papers
Acta Crystallographica Section B
Structural
Science
Conformational preferences and supramolecular
aggregation in 2-nitrophenylthiolates: disulfides
and thiosulfonates
ISSN 0108-7681
Christopher Glidewell,a* John N.
Lowb and James L. Wardellc
In each of the asymmetrically substituted disul®des 2-nitro-40-
methyldiphenyl disul®de, C13H11NO2S2 (1), 2-nitro-40-chloro-
Received 17 April 2000
Accepted 27 June 2000
diphenyl disul®de, C12H8ClNO2S2 (2), 2,4-dinitro-40-methyldi-
phenyl disul®de, C13H10N2O4S2 (3), and 2,4-dinitrophenyl-20-
methoxycarbonylmethyl disul®de, C9H8N2O6S2 (4), and in
both of the symmetrically substituted disul®des bis(2-nitro-
phenyl) disul®de, C12H8N2O4S2 (5), and bis(2-nitro-4-
tri¯uoromethylphenyl) disul®de, C14H6F6N2O4S2 (6), the 2-
nitro groups are essentially coplanar with the adjacent aryl
ring and the S atom remote from the nitrated aryl ring is also
essentially coplanar and transoid to the nitro group. In S-(2-
nitrophenyl) 2-nitrobenzene thiosulfonate, C12H8N2O6S2 (7),
which contains three independent molecules in the asym-
metric unit, all six of the independent nitro groups are twisted
out of the plane of the adjacent aryl rings. The crystal
structures of (1)±(3) contain isolated molecules, that of (4)
contains centrosymmetric dimers held together by CÐHÁ Á ÁO
hydrogen bonds, while in the structures of (5)Ð(7), respec-
tively, the CÐHÁ Á ÁO hydrogen bonds generate one-, two- and
three-dimensional arrays. The interplay between molecular
conformation and supramolecular aggregation is discussed.
aSchool of Chemistry, University of St Andrews,
St Andrews, Fife KY16 9ST, Scotland,
bDepartment of Applied Physics and Electronic
and Mechanical Engineering, University of
Dundee, Nethergate, Dundee DD1 4HN,
Scotland, and cDepartment of Chemistry,
University of Aberdeen, University of Aberdeen,
Meston Walk, Old Aberdeen AB24 3UE,
Scotland
Correspondence e-mail: cg@st-andrews.ac.uk
1. Introduction
The structures of 2-nitrophenylthiolates, O2NC6H4SX, fall into
two distinct conformational classes (Low, Storey et al., 2000;
Low, Glidewell & Wardell, 2000). In one, the nitro group is
essentially planar with the adjacent aryl ring and the ꢀ-atom of
the group X also lies in the plane, trans to the nitro group: in
the other, the nitro group is twisted away from the plane of the
adjacent aryl ring, generally by between 30 and 50ꢁ, and at the
same time the group X is also displaced from the C6S plane.
Molecular modelling (Low, Storey et al., 2000) has shown that
the near-planar conformer represents the global energy
minimum and that any rotation of the nitro group out of this
plane incurs an energy cost. Experimental crystal structure
determinations have shown that, for the examples reported so
far, the near-planar conformer is always observed in the
absence of signi®cant intermolecular interactions such as CÐ
HÁ Á ÁO hydrogen bonds (Aupers et al., 1999; Ruostesuo et al.,
1989). On the other hand, the presence of such interactions
appears to be a necessary although not suf®cient condition for
the occurrence of the twisted conformer. Thus, the twisted
conformer is observed when X = SnPh3 (Aupers et al., 1999),
C6H3(NO2)2-2,4 (Aupers et al., 1999), C6H4NO2-2 (Kucsman et
al., 1984) and COPh (Low, Storey et al., 2000), where there are
well de®ned CÐHÁ Á ÁO hydrogen bonds in each case, although
when X = N-succinimido (Low, Storey et al., 2000), N-phtha-
limido (Iwasaki & Masuko, 1986) or CH CHPh (Low, Storey
# 2000 International Union of Crystallography
Printed in Great Britain ± all rights reserved
ꢀ
Acta Cryst. (2000). B56, 893±905
Glidewell et al. 2-Nitrophenylthiolates 893

research papers
et al., 2000) the planar conformer is observed, despite the
presence of CÐHÁ Á ÁO hydrogen bonds.
As part of a systematic structural study of compounds
containing the 2-O2NC6H4ÐSÐSÐ fragment we have now
determined the structures of (1)±(7) from low-temperature
CCD data, including a more precise re-determination for
(O2NC6H4S)2 (5).
Only a single example of a 2-nitrophenyl disul®de has to
date been structurally characterized. The structure of bis-(2-
nitrophenyl) disul®de, (O2NC6H4S)2, was determined many
years ago from photographic data and re®ned to R = 0.062 for
826 room-temperature data uncorrected for absorption, but
no close intermolecular contacts were noted (Ricci & Bernal,
1970). Closely related to diaryl disul®des ArSSAr0 are the
thiosulfonate esters ArSSO2Ar0. The structures of several such
esters have been reported (Caputo et al., 1984; Ferguson et al.,
2000; Low et al., 2000), but only one example has so far been
reported in which a 2-nitro group is present (Low et al., 2000).
In the ester S-(2-nitrophenyl) 4-toluenethiosulfonate,
O2NC6H4SSO2C6H4CH3, the nitro group is rotated by
44.1 (1)ꢁ out of the plane of the adjacent aryl ring, and there
2. Experimental
2.1. Synthesis
The asymmetrically substituted compounds (1)±(4), ArSSR,
were prepared by the reaction of the appropriate combina-
tions of arenesulfenyl chlorides, ArSCl, and tributyltin
mercaptides, Bu3SnSR (Wardell & Grant, 1969). The products
were crystallized from ethanol, for (1), or methanol, for
(2)±(4), and showed m.p.s of 347±348, 376±377, 376±377 and
372±373 K, respectively. The symmetrically substituted
compounds (5) and (6), ArSSAr, were both obtained by
reaction of the appropriate chloroarene ArCl with Na2S2: after
crystallization from ethanol they showed m.p.s of 466±467 K
for (5) and 433±435 K for (6). Compound (7) was isolated
from the reaction of 2-O2NC6H4SCl with Bu3SnSC6H4SMe-4;
crystals with m.p. 380±381 K were obtained from methanol
solution.
2.2. Data collection, structure solution and refinement
Details of cell data, data collection and re®nement are
summarized in Table 1 (Blessing, 1995, 1997; Ferguson, 1999;
Nonius, 1997; Otwinowski & Minor, 1997; Sheldrick, 1997a,b;
Spek, 2000).1 For (1), (5) and (6), the space group P21/c was
uniquely assigned from the systematic absences; (2), (4) and
Å
(7) are triclinic and for each the space group P1 was assumed,
and subsequently con®rmed by the structure analysis. For (3),
the systematic absences permitted the space groups P21 and
P21/m. The unit-cell dimensions indicated Z = 2, rendering
P21/m implausible, and so P21 was chosen, and subsequently
con®rmed by the successful structure analysis. Compound (7)
diffracted only weakly, with only ca 37% of the re¯ections
labelled observed at the 2ꢁ level, even at 150 (2) K. The
structures were all solved by direct methods using SHELXS97
(Sheldrick, 1997a) and re®ned with all data on F2 using
SHELXL97 (Sheldrick, 1997b). A weighting scheme based
2
2
upon P = [Fo + 2Fc ]/3 was employed in order to reduce
statistical bias (Wilson, 1976). All H atoms were located from
difference maps and all were included in the re®nements as
riding atoms. The methyl group atoms in (1), (3) and (4) were
disordered and in each the H atoms were modelled using two
sets of sites, offset by a 60ꢁ rotation about the exocyclic CÐC
bond and each with 0.50 occupancy. For the symmetrically
substituted compounds (5) and (6), a search for possible
additional symmetry made using the ADDSYM facility in
PLATON (Spek, 2000) indicated that the space group
assignment was correct: similarly for (3), no additional
symmetry was found, but an attempt to determine by Flack
1 Supplementary data for this paper are available from the IUCr electronic
archives (Reference: NA0107). Services for accessing these data are described
at the back of the journal.
are three different types of CÐHÁ Á ÁO hydrogen bond linking
the molecules into a three-dimensional framework.
ꢀ
894 Glidewell et al. 2-Nitrophenylthiolates
Acta Cryst. (2000). B56, 893±905

research papers
re®nement (Flack, 1983) the absolute con®guration for the
crystal selected for data collection was inconclusive: hence, the
Friedel equivalent re¯ections were merged before the ®nal
re®nements. Compound (7) has Z = 6, Z0 = 3, but again an
ADDSYM search for the possible missing symmetry showed
that the space group assignment was correct. However, in (7)
molecules 1 and 2 (containing S1 and S3, respectively) are
related by a pseudo- (non-crystallographic) twofold rotation
axis parallel to [001], as are molecules 2 and 3 (containing S3
and S5, respectively), but no such relationship is obtained
between molecules 1 and 3 (but see also x3.2.4). Supramole-
cular analyses were made, and the diagrams were prepared,
with the aid of PLATON (Spek, 2000).
cules are all chiral: since, however, (1), (2) and (4)±(7) all
crystallize in centrosymmetric space groups, in these
compounds equal numbers of each enantiomer are present in
the solid state.
In the asymmetrically substituted disul®des (1)±(4) (Table
2) and in the symmetrically substituted disul®des (5) and (6)
(Table 3), the CÐSÐSÐC torsional angles are all within 10ꢁ
of Æ90ꢁ. The value of this torsional angle is dominated by the
3p lone pairs on the two S atoms, which seek to become
orthogonal in order to minimize their mutual overlap and
repulsion integrals. The conformation about the central SÐS
bond in each of the independent molecules of the thiosulfo-
nate (7) (Table 4) has one of the SÐO bonds antiperiplanar to
the remote aryl ring Cn1ÐCn6 (n = 2, 4 or 6). This confor-
mation is that usually observed in S-aryl arenethiosulfonates
ArSSO2Ar0 (Caputo et al., 1984; Ferguson et al., 2000; Low,
Glidewell & Wardell, 2000) in preference to the alternative
conformation having the two aryl groups antiperiplanar,
rather than synclinal.
Figs. 1±7 show the molecular units in compounds (1)±(7),
and Figs. 8±17 show aspects of the crystal structures. Tables 2±
4 contain selected geometrical parameters and Table 5 gives
details of the hydrogen bonding.
In each of (1)±(6), the 2-nitro groups are only slightly
rotated out of the plane of the adjacent aryl ring and
accordingly the S1ÐS2ÐC21ÐC22 torsional angles are all
close to 180ꢁ. According to SCF calculations of molecular
energies, described earlier (Low, Storey et al., 2000), at the
global energy minimum for 2-nitrophenylthiolates,
O2NC6H4SX, the substituent X and the nitro group are both
3. Results and discussion
3.1. Molecular structures
3.1.1. Molecular conformations. In crystals of (1)±(7), the
molecules all lie in general positions and hence have no
symmetry imposed upon them. All adopt conformations of C1
symmetry, and hence in the solid state the individual mole-
Figure 1
The asymmetric unit of (1), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 30% probability level.
Figure 3
The asymmetric unit of (3), showing the atom-labelling scheme. Atoms
are depicted as in Fig. 1.
Figure 2
The asymmetric unit of (2), showing the atom-labelling scheme. Atoms
are depicted as in Fig. 1.
Figure 4
The asymmetric unit of (4), showing the atom-labelling scheme. Atoms
are depicted as in Fig. 1.
ꢀ
Acta Cryst. (2000). B56, 893±905
Glidewell et al. 2-Nitrophenylthiolates 895

research papers
Table 1
Experimental details.
(1)
(2)
(3)
(4)
(5)
Crystal data
Chemical formula
Chemical formula
weight
C13H11NO2S2
277.35
C12H8ClNO2S2
297.76
C13H10N2O4S2
322.35
C9H8N2O6S2
304.3
C12H8N2O4S2
308.32
Cell setting
Space group
Monoclinic
P21=c
6.6384 (2)
24.4389 (7)
7.9478 (3)
90
93.6346 (10)
90
1286.82 (7)
4
1.432
Triclinic
P1
Monoclinic
P21
10.1301 (2)
6.3474 (1)
11.1133 (2)
90
106.644 (8)
90
684.64 (2)
2
1.564
Triclinic
P1
Monoclinic
P21=c
7.1028 (11)
22.925 (4)
7.7769 (14)
90
95.536 (12)
90
1260.4 (4)
4
1.625
Ê
a (A)
7.0434 (5)
7.8315 (5)
11.3709 (8)
82.576 (4)
80.690 (3)
83.189 (3)
610.71 (7)
2
8.1655 (3)
8.2415 (3)
9.3887 (4)
72.1417 (15)
83.3965 (14)
80.332 (3)
591.48 (4)
2
Ê
b (A)
Ê
c (A)
ꢀ ꢂꢁ†
ꢂ ꢂꢁ†
ꢃ ꢂꢁ†
3
Ê
V (A )
Z
Dx (Mg m
3
)
Radiation type
1.619
1.709
Mo Kꢀ
0.71073
2935
Mo Kꢀ
0.71073
2960
Mo Kꢀ
0.71073
1695
Mo Kꢀ
0.71073
2629
Mo Kꢀ
0.71073
1862
Ê
Wavelength (A)
No. of re¯ections for
cell parameters
ꢄ range (ꢁ)
1.66±27.38
0.406
150 (2)
2.94±30.19
0.645
150 (2)
2.10±27.50
0.406
150 (2)
2.92±29.31
0.476
150 (2)
3.01±28.47
0.437
150 (2)
1
ꢅ (mm
)
Temperature (K)
Crystal form
Crystal size (mm)
Crystal colour
Block
0.25 Â 0.20 Â 0.10
Plate
0.20 Â 0.15 Â 0.02
Needle
0.55 Â 0.10 Â 0.08
Needle
0.35 Â 0.05 Â 0.03
Needle
0.40 Â 0.07 Â 0.07
Yellow
Yellow
Yellow
Yellow
Yellow
Data collection
Diffractometer
Data collection
method
KappaCCD
' and ! scans with ꢆ
offsets
KappaCCD
' and ! scans with ꢆ
offsets
KappaCCD
' and ! scans with ꢆ
offsets
KappaCCD
' and ! scans with ꢆ
offsets
KappaCCD
' and ! scans with ꢆ
offsets
Absorption correc-
tion
Tmin
Tmax
No. of measured
re¯ections
Multi-scan
Multi-scan
Multi-scan
Multi-scan
Multi-scan
0.9054
0.9606
13 605
0.8818
0.9872
6846
0.8077
0.9702
7452
0.8512
0.9882
6105
0.8447
0.9701
3982
No. of independent
re¯ections
2935
2960
1695
2629
1862
No. of observed
re¯ections
1639
2327
1615
1969
1135
Criterion for
observed re¯ec-
tions
I > 2ꢁ(I)
I > 2ꢁ(I)
I > 2ꢁ(I)
I > 2ꢁ(I)
I > 2ꢁ(I)
Rint
ꢄmax (ꢁ)
Range of h, k, l
0.072
27.38
8 ! h ! 8
31 ! k ! 31
10 ! l ! 10
0.036
28.50
9 ! h ! 9
10 ! k ! 10
13 ! l ! 15
0.072
27.50
13 ! h ! 13
7 ! k ! 8
12 ! l ! 14
0.050
27.50
10 ! h ! 10
9 ! k ! 10
11 ! l ! 11
0.059
25.00
8 ! h ! 7
27 ! k ! 28
7 ! l ! 10
Re®nement
Re®nement on
R‰F2>2ꢁꢂF2†Š
wRꢂF2†
F2
F2
F2
F2
F2
0.0459
0.1465
1.028
2935
0.0440
0.1159
1.049
2960
0.0392
0.1069
1.044
1695
0.0435
0.1105
1.044
2629
0.0557
0.1352
1.027
1862
S
No. of re¯ections
used in re®nement
No. of parameters
used
164
163
191
173
181
H-atom treatment
Weighting scheme
H atoms constrained
w = 1/[ꢁ2(Fo2) +
H atoms constrained
w = 1/[ꢁ2(Fo2) +
H atoms constrained
w = 1/[ꢁ2(Fo2) +
(0.0742P)2 +
H atoms constrained
w = 1/[ꢁ2(Fo2) +
H atoms constrained
w = 1/[ꢁ2(Fo2) +
(0.0738P)2], where
(0.0627P)2], where
(0.0536P)2], where
(0.0528P)2], where
2
2
2
2
P = (Fo + 2Fc2)/3
P = (Fo + 2Fc2)/3
0.0709P], where
2
P = (Fo + 2Fc2)/3
P = (Fo + 2Fc2)/3
P = (Fo + 2Fc2)/3
ꢂÁ=ꢁ†
0.001
0.226
0.247
None
0.001
0.398
0.419
None
0.000
0.395
0.514
None
0.008
0.356
0.376
None
0.000
0.326
0.286
None
max
3
Ê
Ê
Áꢇmax (e A
)
3
Áꢇmin (e A
Extinction method
)
ꢀ
896 Glidewell et al. 2-Nitrophenylthiolates
Acta Cryst. (2000). B56, 893±905

research papers
Table 1 (continued)
(1)
(2)
(3)
(4)
(5)
Source of atomic
scattering factors
International Tables
for X-ray Crystal-
lography (1992,
International Tables
for X-ray Crystal-
lography (1992,
International Tables
for X-ray Crystal-
lography (1992,
International Tables
for X-ray Crystal-
lography (1992,
International Tables
for X-ray Crystal-
lography (1992,
Vol. C, Tables
4.2.6.8 and 6.1.1.4)
Vol. C, Tables
4.2.6.8 and 6.1.1.4)
Vol. C, Tables
4.2.6.8 and 6.1.1.4)
Vol. C, Tables
4.2.6.8 and 6.1.1.4)
Vol. C, Tables
4.2.6.8 and 6.1.1.4)
Computer programs
Data collection
KappaCCD server
software (Nonius,
1997)
KappaCCD server
software (Nonius,
1997)
KappaCCD server
software (Nonius,
1997)
KappaCCD server
software (Nonius,
1997)
KappaCCD server
software (Nonius,
1997)
Cell re®nement
Data reduction
DENZO (Otwi-
nowski & Minor,
1997)
DENZO (Otwi-
nowski & Minor,
1997)
DENZO (Otwi-
nowski & Minor,
1997)
DENZO (Otwi-
nowski & Minor,
1997)
DENZO (Otwi-
nowski & Minor,
1997)
DENZO (Otwi-
nowski & Minor,
1997)
DENZO (Otwi-
nowski & Minor,
1997)
DENZO (Otwi-
nowski & Minor,
1997)
DENZO (Otwi-
nowski & Minor,
1997)
DENZO (Otwi-
nowski & Minor,
1997)
Structure solution
SHELXS97 (Shel-
drick, 1997a)
SHELXL97 (Shel-
drick, 1997b)
SHELXL97 and
WordPerfect
SHELXS97 (Shel-
drick, 1997a)
SHELXL97 (Shel-
drick, 1997b)
SHELXL97 and
WordPerfect
SHELXS97 (Shel-
drick, 1997a)
SHELXL97 (Shel-
drick, 1997b)
SHELXL97 and
WordPerfect
SHELXS97 (Shel-
drick, 1997a)
SHELXL97 (Shel-
drick, 1997b)
SHELXL97 and
WordPerfect
SHELXS97 (Shel-
drick, 1997a)
SHELXL97 (Shel-
drick, 1997b)
SHELXL97 and
WordPerfect
Structure re®nement
Preparation of mate-
rial for publication
macro
PRPKAPPA
(Ferguson, 1999)
macro
PRPKAPPA
(Ferguson, 1999)
macro
PRPKAPPA
(Ferguson, 1999)
macro
PRPKAPPA
(Ferguson, 1999)
macro
PRPKAPPA
(Ferguson, 1999)
(6)
(7)
Crystal data
Chemical formula
Chemical formula weight
Cell setting
C14H6F6N2O4S2
444.33
Monoclinic
P21=c
14.1617 (5)
5.3367 (2)
22.6233 (10)
90
91.7376 (13)
90
1709.01 (12)
4
1.727
Mo Kꢀ
0.71073
3812
2.33±27.45
0.400
150 (2)
C12H8N2O6S2
340.32
Triclinic
P1
8.8211 (18)
11.042 (2)
21.258 (4)
101.06 (3)
91.97 (3)
91.07 (3)
2030.3 (7)
6
1.670
Mo Kꢀ
0.71073
8996
2.93±29.68
0.426
150 (2)
Space group
Ê
a (A)
Ê
b (A)
Ê
c (A)
ꢀ ꢂꢁ†
ꢂ ꢂꢁ†
ꢃ ꢂꢁ†
3
Ê
V (A )
Z
Dx (Mg m
3
)
Radiation type
Ê
Wavelength (A)
No. of re¯ections for cell parameters
ꢄ range (ꢁ)
1
ꢅ (mm
)
Temperature (K)
Crystal form
Crystal size (mm)
Crystal colour
Needle
0.35 Â 0.10 Â 0.05
Plate
0.05 Â 0.05 Â 0.01
Yellow
Yellow
Data collection
Diffractometer
Data collection method
Absorption correction
Tmin
KappaCCD
' and ! scans with ꢆ offsets
Multi-scan
0.8728
KappaCCD
' and ! scans with ꢆ offsets
Multi-scan
0.9790
Tmax
0.9803
14 106
3812
1646
I > 2ꢁ(I)
0.081
27.45
0.9958
19 285
8996
3364
I > 2ꢁ(I)
0.075
27.50
No. of measured re¯ections
No. of independent re¯ections
No. of observed re¯ections
Criterion for observed re¯ections
Rint
ꢄmax (ꢁ)
Range of h, k, l
18 ! h ! 18
6 ! k ! 6
28 ! l ! 29
11 ! h ! 10
11 ! k ! 14
29 ! l ! 27
Re®nement
Re®nement on
R‰F2>2ꢁꢂF2†Š
F2
0.0534
F2
0.0788
ꢀ
Acta Cryst. (2000). B56, 893±905
Glidewell et al. 2-Nitrophenylthiolates 897

research papers
Table 1 (continued)
(6)
(7)
wRꢂF2†
0.1492
0.941
0.1892
0.917
S
No. of re¯ections used in re®nement
No. of parameters used
H-atom treatment
Weighting scheme
3812
253
8996
595
H atoms constrained
w = 1/[ꢁ2(Fo2) + (0.0668P)2], where
P = (Fo + 2Fc2)/3
H atoms constrained
w = 1/[ꢁ2(Fo2) + (0.0515P)2], where
P = (Fo + 2Fc2)/3
2
2
ꢂÁ=ꢁ†
0.000
0.373
0.247
0.001
0.733
0.429
max
3
Ê
Ê
Áꢇmax (e A
)
3
Áꢇmin (e A
Extinction method
Source of atomic scattering factors
)
None
International Tables for Crystallography (1992,
Vol. C, Tables 4.2.6.8 and 6.1.1.4)
None
International Tables for Crystallography (1992,
Vol. C, Tables 4.2.6.8 and 6.1.1.4)
Computer programs
Data collection
Cell re®nement
Data reduction
Structure solution
KappaCCD server software (Nonius, 1997)
DENZO (Otwinowski & Minor, 1997)
DENZO (Otwinowski & Minor, 1997)
SHELXS97 (Sheldrick, 1997a)
KappaCCD server software (Nonius, 1997)
DENZO (Otwinowski & Minor, 1997)
DENZO (Otwinowski & Minor, 1997)
SHELXS97 (Sheldrick, 1997a)
Structure re®nement
Preparation of material for publication
SHELXL97 (Sheldrick, 1997b)
SHELXL97 and WordPerfect macro
PRPKAPPA (Ferguson, 1999)
SHELXL97 (Sheldrick, 1997b)
SHELXL97 and WordPerfect macro
PRPKAPPA (Ferguson, 1999)
Ê
essentially coplanar with the aryl ring with X transoid to the
NO2 group. The symmetrically substituted compounds (5) and
(6), having a 2-nitro group in each ring, thus adopt confor-
mations in which both SÐSÐCÐC fragments are nearly
planar. By contrast, in (1)±(4) the S2ÐS1ÐC11ÐC12 [in (1)±
(3)] or S2ÐS1ÐC1ÐC2 [in (4)] torsional angles vary between
4.7 (2)ꢁ in (2) and 99.6 (2)ꢁ in (3), although the rings C11±C16
differ in (2) and (3) only in the nature of the 4-substituent,
chloro versus methyl. All of the six independent 2-nitro groups
in (7) are rotated out of the plane of the adjacent aryl ring by
between 37 and 52ꢁ, in every case associated with SÐSÐCÐC
torsional angles close to 90ꢁ (Table 4). It is interesting to note
(x3.2) that in (7) there is a much more extensive network of
CÐHÁ Á ÁO hydrogen bonds than in any of (1)±(6). A similar
SÐSÐCÐC torsional angle, close to 90ꢁ, is also observed in 2-
O2NC6H4SSO2C6H4CH3, associated with a nitro-group twist
angle of 44.1 (1)ꢁ.
quartile values of 1.476 and 1.460 A, respectively. Similarly,
the CÐC distances within the aryl rings are reasonably
uniform. None of (1)±(7) exhibits the quinonoid-type bond
®xation observed in 2-O2NC6H4SCH CHPh, where the CÐ
Ê
N distance is only 1.383 (4) A, well below the typical range for
such bonds, and the CÐC distances in the nitrated ring vary
Ê
between 1.310 (4) and 1.374 (5) A. The C(aryl)ÐS distances
show no signi®cant variation between the differently substi-
tuted aryl groups, nor between those involving two- or four-
coordinate S, as in (7). The SÐSO2 distances in (7) are
somewhat larger than the simple SÐS distances in (1)±(6), as
typically observed in esters of this type. Other bond lengths
are typical of their types (Allen et al., 1987).
Within the nitrated aryl rings, the CÐCÐC angles show
signi®cant deviations from 120ꢁ in all compounds, but in all
cases these are in reasonable accord with the values predicted
by the use of additive substituent constants (Domenicano &
Murray-Rust, 1979). The OÐNÐO and OÐSÐO angles are
3.1.2. Molecular dimensions. The CÐN bond distances
Ê
Ê
vary between 1.448 (5) A in (5) and 1.486 (8) A in (7): these
values are typical of C(aryl)ÐNO2 distances, where the mean
Ê
value is 1.468 A (Allen et al., 1987), with upper and lower
Figure 5
The asymmetric unit of (5), showing the atom-labelling scheme. Atoms
are depicted as in Fig. 1.
Figure 6
The asymmetric unit of (6), showing the atom-labelling scheme. Atoms
are depicted as in Fig. 1.
ꢀ
898 Glidewell et al. 2-Nitrophenylthiolates
Acta Cryst. (2000). B56, 893±905

research papers
Table 2
Selected geometric parameters (A, ) for (1)±(4).
ꢁ
Ê
(1)
(2)
(3)
(4)
S1ÐS2
S1ÐC11
S2ÐC21
C22ÐN22
N22ÐO221
N22ÐO222
C24ÐN24
N24ÐO241
N24ÐO242
S1ÐC1
2.054 (1)
1.776 (3)
1.781 (2)
1.453 (4)
1.224 (4)
1.222 (4)
±
±
±
±
±
2.040 (1)
1.784 (2)
1.789 (2)
1.460 (2)
1.230 (2)
1.223 (2)
±
2.059 (1)
1.784 (3)
1.774 (3)
1.461 (4)
1.217 (4)
1.238 (3)
1.464 (4)
1.233 (4)
1.220 (4)
±
2.046 (1)
±
1.777 (2)
1.467 (3)
1.229 (3)
1.222 (2)
1.468 (3)
1.224 (3)
1.228 (2)
1.819 (2)
±
±
±
±
1.743 (2)
C14ÐCl14
±
C11ÐS1ÐS2
C1ÐS1ÐS2
C21ÐS2ÐS1
102.07 (8) 105.25 (7) 102.51 (9)
±
±
105.22 (8) 103.78 (7) 104.7 (1)
±
±
102.72 (8)
104.16 (7)
123.7 (2)
117.2 (2)
119.2 (2)
124.0 (2)
118.2 (2)
117.7 (2)
±
O221ÐN22ÐO222
O221ÐN22ÐC22
O222ÐN22ÐC22
O241ÐN24ÐO242
O241ÐN24ÐC24
O242ÐN24ÐC24
C12ÐC11ÐC16
C22ÐC21ÐC26
C21ÐC22ÐC23
123.1 (3)
117.7 (3)
119.1 (3)
±
±
±
118.5 (2)
116.0 (2)
122.5 (3)
123.3 (2)
117.4 (2)
119.2 (2)
±
±
±
120.0 (2)
116.0 (2)
122.7 (2)
123.5 (3)
118.4 (3)
118.1 (3)
123.9 (3)
117.7 (3)
118.3 (3)
119.7 (3)
116.0 (3)
122.5 (3)
115.6 (2)
123.6 (2)
C11ÐS1ÐS2ÐC21
S1ÐS2ÐC21ÐC22
S2ÐS1ÐC11ÐC12
C21ÐC22ÐN22ÐO221
C23ÐC24ÐN24ÐO241
C1ÐS1ÐS2ÐC21
S2ÐS1ÐC1ÐC2
85.4 (2)
169.8 (2)
83.8 (2)
3.6 (4)
±
±
±
±
±
81.50 (9) 94.6 (2)
172.0 (2)
4.7 (2)
4.5 (3)
±
178.5 (2) 171.1 (2)
99.4 (2)
1.7 (4)
±
11.0 (3)
0.4 (3)
84.0 (2)
67.0 (2)
115.4 (2)
66.0 (2)
±
±
±
±
±
7.5 (4)
±
±
±
±
S1ÐC1ÐC2ÐO3
S1ÐC1ÐC2ÐO4
Figure 8
Part of the crystal structure of (4) showing the formation of a
2
centrosymmetric R2 (18) motif. H atoms not involved in the hydrogen-
bonding motif shown are omitted for the sake of clarity. Atoms marked
with a star (*) are at the symmetry position ( x, 2 y, 1 z).
Figure 7
The three individual molecules in the asymmetric unit of (7), showing the
atom-labelling scheme. Atoms are depicted as in Fig. 1.
ꢀ
Acta Cryst. (2000). B56, 893±905
Glidewell et al. 2-Nitrophenylthiolates 899

research papers
Table 3
Selected geometric parameters (A, ) for (5) and (6).
Table 4
Selected geometric parameters (A, ) for (7).
ꢁ
ꢁ
Ê
Ê
(5)
(6)
Molecule (1)
(m,n = 1, 2)
Molecule (2)
(m,n = 3, 4)
Molecule (3)
(m,n = 5, 6)
S1ÐS2
S1ÐC11
S2ÐC21
C12ÐN12
N12ÐO121
N12ÐO122
C22ÐN22
N22ÐO221
N22ÐO222
2.057 (2)
1.784 (4)
1.795 (5)
1.460 (5)
1.236 (4)
1.217 (4)
1.448 (5)
1.232 (5)
1.228 (4)
2.048 (2)
1.777 (3)
1.787 (3)
1.455 (4)
1.225 (4)
1.217 (4)
1.467 (5)
1.217 (4)
1.211 (4)
SmÐSn
SmÐOm
SmÐOn
SmÐCm1
SnÐCn1
Cm2ÐNm2
Nm2ÐOm21
Nm2ÐOm22
Cn2ÐNn2
Nn2ÐOn21
Nn2ÐOn22
2.073 (2)
1.430 (4)
1.433 (4)
1.764 (6)
1.768 (6)
1.477 (7)
1.214 (6)
1.242 (7)
1.486 (8)
1.219 (6)
1.226 (6)
2.070 (2)
1.428 (4)
1.440 (4)
1.773 (6)
1.782 (6)
1.471 (7)
1.219 (6)
1.237 (6)
1.483 (7)
1.226 (6)
1.237 (6)
2.076 (2)
1.427 (4)
1.437 (4)
1.771 (6)
1.781 (6)
1.464 (7)
1.223 (6)
1.233 (7)
1.466 (8)
1.226 (6)
1.221 (6)
C11ÐS1ÐS2
C21ÐS2ÐS1
105.1 (2)
104.4 (2)
122.6 (4)
117.6 (4)
119.7 (3)
122.4 (4)
117.9 (4)
119.6 (4)
116.2 (4)
122.7 (4)
117.2 (4)
121.6 (4)
104.7 (2)
104.5 (2)
123.2 (3)
118.1 (3)
118.7 (4)
123.8 (4)
117.5 (4)
118.7 (4)
116.2 (3)
122.7 (3)
116.6 (3)
122.5 (3)
O121ÐN12ÐO122
O121ÐN12ÐC12
O122ÐN12ÐC12
O221ÐN22ÐO222
O221ÐN22ÐC22
O222ÐN22ÐC22
C12ÐC11ÐC16
C11ÐC12ÐC13
C22ÐC21ÐC26
C21ÐC22ÐC23
OmÐSmÐOn
SnÐSmÐCm1
SmÐSnÐCn1
119.3 (3)
107.4 (2)
97.6 (2)
119.1 (3)
107.6 (2)
97.3 (2)
118.7 (3)
106.2 (2)
97.4 (2)
Om21ÐNm2ÐOm22
Om21ÐNm2ÐCm2
Om22ÐNm2ÐCm2
On21ÐNn2ÐOn22
On21ÐNn2ÐCn2
On22ÐNn2ÐCn2
Cm2ÐCm1ÐCm6
Cm1ÐCm2ÐCm3
Cn2ÐCn1ÐCn6
Cn1ÐCn2ÐCn3
125.9 (6)
118.4 (6)
115.7 (5)
125.4 (6)
118.9 (5)
115.6 (5)
117.5 (6)
121.6 (6)
116.3 (6)
122.3 (6)
125.5 (6)
118.2 (5)
116.2 (5)
124.7 (6)
118.8 (5)
116.4 (5)
118.3 (6)
120.9 (6)
118.2 (6)
122.1 (6)
123.7 (5)
119.1 (6)
117.2 (5)
124.0 (5)
118.1 (5)
117.8 (5)
118.3 (5)
120.9 (6)
118.2 (6)
121.4 (6)
C11ÐS1ÐS2ÐC21
S1ÐS2ÐC21ÐC22
S2ÐS1ÐC11ÐC12
C11ÐC12ÐN12ÐO121
C21ÐC22ÐN22ÐO221
84.4 (3)
159.6 (3)
167.5 (4)
7.6 (7)
89.9 (2)
170.2 (2)
173.6 (2)
1.1 (5)
16.7 (5)
0.3 (5)
Cm1ÐSmÐSnÐCn1
OmÐSmÐSnÐCn1
OnÐSmÐSnÐCn1
SmÐSnÐCn1ÐCn2
SnÐSmÐCm1ÐCm2
Cm1ÐCm2ÐNm2ÐOm21
Cn1ÐCn2ÐNn2ÐOn21
71.3 (3)
42.5 (3)
171.3 (3)
84.3 (5)
85.2 (5)
50.5 (8)
43.4 (8)
69.7 (3)
44.5 (3)
173.4 (3)
80.5 (5)
88.1 (5)
52.3 (7)
37.3 (8)
68.4 (3)
45.9 (3)
174.3 (3)
79.2 (5)
87.8 (5)
49.8 (8)
37.9 (8)
all greater than the ideal trigonal or tetrahedral values,
respectively: this can be traced to the substantial negative
charges on the paired O atoms in these units.
It is notable that in (7) the SÐSÐC angles at the four-
coordinate sulfur atoms, Sm (m = 1, 3, 5), are all close to 107ꢁ
(Table 4) and are thus similar to the SÐSÐC angles in the
disul®des (1)±(6) (Tables 2 and 3). On the other hand, the SÐ
SÐC angles at the two-coordinate sulfur atoms in (7), Sn
(n = 2, 4, 6) are all signi®cantly smaller, close to 97ꢁ.
from room-temperature photographic data, uncorrected for
absorption, to R = 0.062. The structure reported here from
absorption-corrected CCD data at 150 K shows that no change
of phase has occurred and that the structure is essentially the
same at the two temperatures. The s.u.s on the bond distances
and angles reported here are typically less than half those
reported earlier. However, subject to this, corresponding pairs
of derived geometric parameters
3.1.3. Molecular dimensions in (5). The structure of (5) has
been reported earlier (Ricci & Bernal, 1970): it was re®ned
for the two determinations are all
within 3ꢁ, with the sole exception
of the SÐS distance found here as
Ê
2.057 (2) A and reported earlier
Ê
as 2.045 (3) A.
3.2. Supramolecular structures
It has recently been noted that
the criteria for acceptance of non-
covalent
contacts
involving
hydrogen as genuine hydrogen
bonds seem to be undergoing
continual relaxation (Cotton et
al., 1997). It therefore seems
desirable to specify the accep-
tance criteria adopted here for
the hydrogen bonds listed in
Figure 9
Part of the crystal structure of (5) showing C(9) chains running parallel to [001] and linked by ꢈÁ Á Áꢈ
stacking interactions. Atoms are depicted as in Fig. 8. The atom marked with a star (*) is at the symmetry
position (x,
1
2
1
y,
+ z).
2
ꢀ
900 Glidewell et al. 2-Nitrophenylthiolates
Acta Cryst. (2000). B56, 893±905

research papers
Table 5
Hydrogen bond dimensions (A, ) for (4)±(7).
Table 5. The CÐHÁ Á ÁO hydrogen bonds in Table 5 all involve
aromatic CÐH bonds and all have CÁ Á ÁO distances below
ꢁ
Ê
ꢁ
Ê
3.50 A and CÐHÁ Á ÁO angles not less than 130 : these values
are within the ranges now accepted for such bonds (Desiraju,
1991, 1996; Braga et al., 1995).
D
H
A
DÁ Á ÁA
HÁ Á ÁA
2.35
DÐHÁ Á ÁA
176
Compound (4)
C23 H23
O3i
O222ii
3.299 (3)
3.197 (5)
In (1)±(3) there are neither CÐHÁ Á ÁO hydrogen bonds nor
aromatic ꢈÁ Á Áꢈ stacking interactions so that the structures
consist of isolated molecules. By contrast in (4)±(7), the CÐ
HÁ Á ÁO hydrogen bonds generate supramolecular structures of
dimensionality zero, one, two and three, respectively. Thus, in
(4) the molecules are linked by CÐHÁ Á ÁO hydrogen bonds
Compound (5)
C16 H16
2.49
131
Compound (6)
C15
C26
H15
H26
O222iii
O122iv
3.421 (5)
3.239 (5)
2.57
2.46
152
141
Compound (7)
C14
C34
C35
C44
C54
C64
C13
C46
C56
C63
H14
H34
H35
H44
H54
H64
H13
H46
H56
H63
O4
O6
3.209 (8)
3.183 (9)
3.298 (9)
3.502 (8)
3.459 (8)
3.403 (8)
3.214 (7)
3.466 (8)
3.320 (8)
3.277 (7)
2.37
2.41
2.56
2.56
2.55
2.49
2.52
2.53
2.53
2.57
147
139
134
172
161
161
130
168
141
131
O621v
O6v
O1vi
O2vii
O3viii
O222ix
O622x
O5x
1
2
1
2
Symmetry codes: (i) x; 2 y; 1 z; (ii) x; 12 y;
‡ z; (iii) 1 x;
‡ y; 12 z; (iv)
1
x;
‡ y; 12 z; (v) x; 1 ‡ y; z; (vi) x; y; 1 ‡ z; (vii) x; 1 ‡ y; 1 ‡ z; (viii)
2
1
x; y; 1 z; (ix) 2 x; 1 y; 1 z; (x) 2 x; 2 y; 2 z.
into ®nite, i.e. zero-dimensional, dimers, while in (5) they are
linked into chains. In (6) and (7) the CÐHÁ Á ÁO hydrogen
bonds link the molecules into sheets and into a continuous
three-dimensional framework, respectively. The chains in (5)
are further linked by aromatic ꢈÁ Á Áꢈ stacking interactions.
3.2.1. Zero-dimensional hydrogen bonding. In (4) the
aromatic CÐH bond between the two nitro groups (C23Ð
H23; Fig. 4) is expected to be the most acidic bond in the
molecule, and thus to show the highest propensity for CÐ
HÁ Á ÁO hydrogen-bond formation. Accordingly, C23 at (x, y, z)
acts as a donor to carbonyl O3 at ( x, 2 y, 1 z), so forming
Figure 10
Part of the crystal structure of (6) showing a C(10) spiral running parallel
to [010]. H atoms not involved in the hydrogen-bonding motif shown, and
the CF3 groups, are omitted for the sake of clarity. The atom marked with
2
1
1
2
a star (*) is at the symmetry position (1 x,
+ y, 12 z).
a centrosymmetric R2 (18) motif, centred at (0, 1, ) (Fig. 8).
2
There are no aromatic ꢈÁ Á Áꢈ
stacking interactions, so the
supramolecular aggregation in
this structure is limited to the
formation of these dimeric units.
2
Entirely analogous R2 (18)
dimers formed by paired
CÐHÁ Á ÁO hydrogen bonds
have been observed in the
structure of 4-ferrocenylcarb-
onyl-40-chlorocarbonylbiphenyl
(Ahmed et al., 1999).
3.2.2.
hydrogen bonding. The crystal
structure of (5) exhibits
One-dimensional
a
combination of CÐHÁ Á ÁO
hydrogen bonds and aromatic
ꢈÁ Á Áꢈ stacking interactions. The
hydrogen bonds link the mole-
cules into zigzag chains: C16 at
(x, y, z) acts as a donor to O222
Figure 11
Part of the crystal structure of (6) showing a C(9) spiral running parallel to [010]. Atoms are depicted as in
1
Fig. 10. The atom marked with a star (*) is at the symmetry position ( x,
+ y, 12 z).
2
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Glidewell et al. 2-Nitrophenylthiolates 901

research papers
molecules at (x, y, z) and ( x,
y, z) are parallel, with an
1
interplane spacing of 3.62 A and
Ê
Ê
a centroid offset of 1.34 A, so
forming a ꢈÁ Á Áꢈ stacking contact
across the inversion centre at (0,
12, 0). Propagation of this inter-
action serves to generate
multiple links between pairs of
adjacent chains. Each molecule
in (5) is thus linked to three
others, two via the hydrogen
bonds and one via the ꢈÁ Á Áꢈ
stacking.
In the earlier account of this
structure, no signi®cant inter-
molecular interactions were
reported. Indeed the packing
Figure 12
Part of the crystal structure of (6) showing an (001) sheet built from R4 (38) rings. Atoms are depicted as in
4
Fig. 10. The atoms marked with a star (*) or a hash (#) are at the symmetry positions (1 x, 12 + y, 21 z)
1
1
and ( x,
+ y,
z), respectively.
2
2
diagram given by Ricci & Bernal
(1970), viewed down the [001]
direction, necessarily obscures the effect of the CÐHÁ Á ÁO
hydrogen bonds.
3.2.3. Two-dimensional hydrogen bonding. There are two
different types of CÐHÁ Á ÁO hydrogen bond in the structure of
the symmetrically substituted compound (6): these involve
aromatic CÐH bonds at different sites in the two rings, and
give rise to different hydrogen-bonding motifs so precluding
any possibility that the molecules of (6) could exhibit internal
symmetry. The two types of hydrogen bond generate spiral
motifs around different 21 screw axes and together they
generate a two-dimensional sheet.
Atom C15 in the molecule at (x, y, z) (Fig. 6) acts as a
1
1
2
hydrogen-bond donor to O222 at (1
x,
+ y,
z):
2
propagation of this interaction generates a C(10) spiral chain,
running parallel to [010] and lying around the 21 axis along (12,
y, 14) (Fig. 10). At the same time, C26 in the other aryl ring of
the molecule at (x, y, z) (Fig. 6) acts as a donor to O122 at ( x,
1
2
1
2
+ y,
z): this generates a second spiral motif running
parallel to [010], this time a C(9) chain lying around the 21 axis
1
along (0, y, ) (Fig. 11).
The combination of these two spiral motifs leads to the
production of a continuous sheet parallel to (001) built from a
4
single type of R4 (38) ring (Fig. 12). The formation of one such
4
sheet utilizes only half of the contents of the unit cell, lying in
the domain 0 < z < 12. There is a second sheet running through
each unit cell, related to the ®rst by the action of the centres of
inversion and lying in the domain 12 < z < 1.0. Adjacent parallel
sheets are thus not interwoven.
3.2.4. Three-dimensional hydrogen bonding. The three
independent molecules in compound (7) (Fig. 7) all show
different behaviour as donors and acceptors of hydrogen
bonds (Table 5). In all three molecules, both of the sulfone O
atoms act as hydrogen-bond acceptors, but O6 in molecule 3 is
the only double acceptor. Of the 12 independent O atoms in
the nitro groups, only O222 in molecule 1 and O621 and O622,
both in molecule 3 act as hydrogen-bond acceptors. Thus, the
hydrogen-bond acceptor properties alone serve to discrimi-
Figure 13
3
Part of the crystal structure of (7) showing a C3 (21) chain parallel to
[001] built from molecules of types 1, 2 and 3. Atoms are depicted as in
Fig. 8.
at (x, 12 y, 12 + z), while C16 at (x, 21 y, 12 + z) in turn acts
as a donor to O222 at (x, y, 1 + z). In this way, a C(9) chain
running parallel to [001] is generated by the action of the glide
plane at y = 0.25 (Fig. 9). A similar, but antiparallel, chain is
generated by the glide plane at y = 0.75, and neighbouring
pairs of chains are linked by means of aromatic ꢈÁ Á Áꢈ stacking
interactions into a sheet. The rings containing C11ÐC16 in the
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902 Glidewell et al. 2-Nitrophenylthiolates
Acta Cryst. (2000). B56, 893±905

research papers
nate between the three independent
molecules, hence con®rming the
correctness of Z0 = 3. In terms of
hydrogen-bond
donor
properties,
molecule 1 is a double donor, while
molecules 2 and 3 are both quadruple
donors, but these two molecules utilize
a different selection of CÐH bonds in
hydrogen-bond formation. The donor
properties thus also discriminate
between the three molecules in the
asymmetric unit.
Of the ten signi®cant hydrogen bonds
in the structure of (7) (Table 5) two,
C14ÐH14Á Á ÁO4 and C34ÐH34Á Á ÁO6,
are within the asymmetric unit. Four
others generate chain motifs by trans-
lation along the [010] and [001] direc-
tions and, together, these one-
dimensional motifs generate sheets. The
®nal four hydrogen-bond types all
generate distinct centrosymmetric ring
motifs, whose effect is to link the
neighbouring sheets, so generating a
continuous three-dimensional frame-
work.
Figure 14
2
Part of the crystal structure of (7), showing a C2 (15) chain parallel to [010] built from molecules of
types 1 and 3 only. Atoms are depicted as in Fig. 8. Atoms are depicted as in Fig. 8. The atoms
marked with a star (*) or a hash (#) are at the symmetry positions (x, y, 1 + z) and (x, 1 + y, 1 + z),
respectively.
The chain running parallel to the
[001] direction includes all three inde-
pendent molecules and in each of the
hydrogen bonds the CÐH bond para to the SO2 unit acts as a
donor to a sulfone O in the neighbouring molecule. Thus, C14
and C34 act as donors to O4 and O6, respectively, within the
asymmetric unit, while C54 at (x, y, z) acts as a donor to O1 at
3
(x, y, 1 + z), thus forming by translation a C3 (21) chain (Fig.
13).
There are two distinct chain motifs running parallel to [010].
The simpler of the two involves only molecules 1 and 3: atoms
C54 and C64 in molecule 3 at (x, y, z) act as hydrogen-bond
donors to O1 at (x, y, 1 + z) and O2 at (x, 1 + y, 1 + z),
respectively. This pair of hydrogen bonds thus generates, again
2
by translation, a C2 (15) chain (Fig. 14). The other [010] motif
is a chain of rings (Bernstein et al., 1995), which utilizes only
molecules 2 and 3. Atoms C34 and C35 in molecule 2 at (x, y,
z) act as donors to sulfone O6 atoms in type 3 molecules at (x,
1
y, z) and (x 1 + y, z), respectively, so producing a C2 (13)
chain (Fig. 15). At the same time, C35 at (x, y, z) acts as a
2
donor to nitro O621 at (x, 1 + y, z) producing a C2 (11) chain
2
(Fig. 15), and the two parallel chains enclose R2 (18) rings
(Fig. 15). Overall this [010] motif has graph-set descriptor
1
C2 (13)C2 (11)[R2 (18)] (Bernstein et al., 1995).
2
2
The combination of the various [010] and [001] chains (Figs.
13±15), all generated by translation, serves to produce a
continuous two-dimensional sheet parallel to (100). There are
two of these sheets passing through each unit cell: they are
related by the centres of inversion and one, containing the
reference molecules at (x, y, z), lies in the domain 0.5 < x < 1.0,
while the other lies in the domain 0 < x < 0.5. As with the
Figure 15
Part of the crystal structure of (7) showing a C2 (13) chain embodying
1
2
R2 (18) rings parallel to [010] and built from molecules of types 2 and 3
only. Atoms are depicted as in Fig. 8. Atoms marked with a star (*) are at
the symmetry position (x, 1 + y, z).
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Acta Cryst. (2000). B56, 893±905
Glidewell et al. 2-Nitrophenylthiolates 903

research papers
sheets formed in the structure of (6), those in (7) are not
interwoven: they are, however, extensively linked to form a
continuous framework, by no fewer than four further types of
CÐHÁ Á ÁO hydrogen bond involving all three independent
molecules as both donors and acceptors.
Paired CÐHÁ Á ÁO hydrogen bonds involving molecules of
types 1 and 2 link each sheet to its two neighbours. Atom C13
at (x, y, z) acts as a donor to sulfone O3 at (1 x, y, 1 z),
4
thus generating an R4 (14) ring centred at (12, 0, 21): atom C46 at
(x, y, z) acts as a donor to nitro O222 at (2 x, 1 y, 1 z),
4
thus generating an R4 (34) ring centred at (1.5, , ). Propa-
1
1
2
2
gation of these two motifs links the adjacent (100) sheets by
means of a chain of fused rings running in the [110] direction
(Fig. 16). Finally, C56 and C63, both at (x, y, z), act as donors,
respectively, to O622 and to O5 both at (2 x, 2 y, 2 z),
2
2
thus producing concentric R2 (18) and R2 (14) rings, centred
at (1, 1, 1) and linking an adjacent pair of sheets (Fig. 17).
3.2.5. General comments on the hydrogen bonding. It
remains dif®cult to predict the outcome of hydrogen bonding
in this series of compounds. For example, while CÐHÁ Á ÁO
hydrogen bonding in the 2,20-dinitro compound (5) leads to
the formation of chains, in the isomeric 4,40-dinitro compound
the hydrogen bonds lead to the formation of sheets (Wardell et
al., 2000). Similarly, (5) and (6) differ only in the presence in
(6) of the tri¯uoromethyl groups, which play no direct role in
the supramolecular aggregation: nonetheless, in (6) the
hydrogen-bonded structure is two-dimensional, whereas in (5)
it is only one-dimensional. However, in both of the thio-
sulfonates (7) and 2-O2NC6H4SSO2C6H4CH3, there are three-
dimensional arrays of hydrogen bonds, even
Figure 16
4
4
Part of the crystal structure of (7), showing the R4 (14) and R4 (34) rings
which link adjacent (100) sheets. Atoms are depicted as in Fig. 8. The
atoms marked with a star (*) or a hash (#) are at the symmetry positions
(1 x, y, 1 z) and (2 x, 1 y, 1 z), respectively.
though the latter ester contains only one nitro
group per molecule, as opposed to two per mole-
cule in (7). In both esters the dominant hydrogen-
bond acceptors are the sulfone O atoms: indeed in
2-O2NC6H4SSO2C6H4CH3 the nitro group does
not participate in the hydrogen-bonding scheme.
4. Concluding comments
The conformational results reported here for
compounds (1)±(7) and for related compounds
discussed earlier are all consistent with the
hypothesis that, in the absence of any speci®c
intermolecular interactions such as hydrogen
bonds, the conformation observed in the solid state
will always correspond to the global energy
minimum, as calculated for isolated molecules,
while the presence of such interactions is a neces-
sary but not suf®cient condition for the observa-
tion of local-minimum conformers. In all these
compounds, there is close but subtle interplay
between the intramolecular conformation and the
supramolecular aggregation.
Figure 17
2
2
Part of the crystal structure of (7), showing concentric R2 (14) and R2 (34) rings which
link adjacent (100) sheets. Atoms are depicted as in Fig. 8. The atoms marked with a
star (*) are at the symmetry position (2 x, 2 y, 2 z).
X-ray data were collected at the EPSRC X-ray
Crystallographic Service, University of South-
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904 Glidewell et al. 2-Nitrophenylthiolates
Acta Cryst. (2000). B56, 893±905

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Cryst. C56, 692±694.
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The authors thank the staff for all their help and advice. The
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