2-nitrophenyl 4-nitrophenyl disulfide

Article abstract of DOI:10.1107/S0108270102011344

The structure of the title compound, C₁₂H₈N₂O₄S₂, contains no direction-specific intermolecular interactions, i.e. no C-H...O hydrogen bonds, no aromatic π-π-stacking interactions and no C-H...π(arene

Full text of DOI:10.1107/S0108270102011344

organic compounds
ꢀ
Acta Crystallographica Section C
Crystal Structure
Communications
torsion angle is close to 180 , consistent (Low et al., 2000) with
the near coplanarity of the 2-nitro group and the C11±C16
ring.
ISSN 0108-2701
2
-Nitrophenyl 4-nitrophenyl disulfide
a
b
Christopher Glidewell, * John N. Low, Janet M. S.
b
c
Skakle and James L. Wardell
a
School of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST,
b
Scotland, Department of Chemistry, University of Aberdeen, Meston Walk, Old
c
Aberdeen AB24 3UE, Scotland, and Instituto de Qu Âõ mica, Departamento de
Qu Âõ mica Inorg aà nica, Universidade Federal do Rio de Janeiro, 21945-970 Rio de
Janeiro, RJ, Brazil
Correspondence e-mail: cg@st-andrews.ac.uk
Received 20 June 2002
Accepted 25 June 2002
Online 20 July 2002
The structure of the title compound, C H N O S , contains
2
1
2
8
4 2
no direction-speci®c intermolecular interactions, i.e. no CÐ
HÁ Á ÁO hydrogen bonds, no aromatic ꢀ±ꢀ-stacking interactions
and no CÐHÁ Á Áꢀ(arene) interactions. This behaviour is
compared with the three known symmetrical isomers of
bis(nitrophenyl) disul®de, having the nitro groups on the two
However, the striking feature of the structure of (IV) is the
complete absence of CÐHÁ Á ÁO hydrogen bonds and of both
aromatic ꢀ±ꢀ-stacking interactions and CÐHÁ Á Áꢀ(arene)
interactions, so that there are no direction-speci®c inter-
molecular interactions. By not forming CÐHÁ Á ÁO hydrogen
bonds, (IV) resembles (III), rather than (I) and (II). The
supramolecular structures of (I)±(IV), as de®ned by the
direction-speci®c intermolecular interactions, are thus three-,
two-, one- and zero-dimensional, respectively, with very
modest changes in molecular constitution leading to signi®-
cant changes in the supramolecular aggregation.
2-, 3- or 4-positions, all of which exhibit direction-speci®c
supramolecular aggregation.
Comment
In bis(4-nitrophenyl) disul®de, (4-O NC H ) S , (I), where the
2
6
4 2 2
molecules lie across twofold rotation axes in space group C2/c,
a single CÐHÁ Á ÁO hydrogen bond suf®ces to link the mol-
ecules into sheets, which are then linked by aromatic ꢀ±ꢀ-
stacking interactions to give a three-dimensional framework
structure (Wardell et al., 2000). In the isomeric bis(2-nitro-
phenyl) disul®de, (II), the molecules are linked into chains by
a single CÐHÁ Á ÁO hydrogen bond, and the chains are further
linked into sheets by means of aromatic ꢀ±ꢀ-stacking inter-
actions (Glidewell et al., 2000). The structure of bis(3-nitro-
phenyl) disul®de, (III), on the other hand, contains no CÐ
HÁ Á ÁO hydrogen bonds, but the molecules are nonetheless
linked into chains by aromatic ꢀ±ꢀ-stacking interactions
The absence of any CÐHÁ Á ÁO hydrogen bonds in (III) and
(IV) is highly unusual, as such interactions are generally the
dominant feature of the crystal structures of compounds
containing nitroarenethiolate,
O NC H SX, fragments
2 6 4
(Kucsman et al., 1984; Aupers et al., 1999; Low et al., 2000;
Glidewell et al., 2000), as well as those of simple nitrobenzenes
(Boonstra, 1963; Trotter & Williston, 1966; Choi & Abel, 1972;
Herbstein & Kapon, 1990; Boese et al., 1992; Sekine et al.,
1994).
(
Cannon et al., 2000).
Intrigued by the different supramolecular structures
adopted by the isomers (I)±(III), we have now investigated the
intermediate' isomer 2-nitrophenyl 4-nitrophenyl disul®de,
IV). The intramolecular dimensions and overall molecular
`
(
conformation of (IV) are comparable with those in (I)±(III),
with both nitro groups in (IV) nearly coplanar with the
adjacent aryl rings (Fig. 1). Also noteworthy are the CÐCÐC,
CÐCÐS and CÐCÐN angles at the ipso positions (Table 1),
where the CÐCÐC angles, in particular, are consistent with
the electron-donating and electron-withdrawing properties of
thiolate and nitro substituents, respectively (Domenicano &
Murray-Rust, 1979). We also note that the S2ÐS1ÐC11ÐC12
Figure 1
A view of the molecule of (IV) showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 30% probability level.
Acta Cryst. (2002). C58, o485±o486
DOI: 10.1107/S0108270102011344
# 2002 International Union of Crystallography o485

organic compounds
Much effort continues to be expended in attempts to
compute, using a variety of ab initio, semi-empirical and
heuristic methods, the structures of simple molecular
compounds (Lommerse et al., 2000; Motherwell, 2001).
However, the unexpected differences between the crystal
structures of members of simple series of isomeric compounds,
such as compounds (I)±(IV), and other series where hard
Compound (IV) crystallized in the monoclinic system; space group
1
/c was uniquely assigned from the systematic absences. H atoms
P2
were treated as riding atoms, with CÐH distances of 0.93 A.
Ê
Data collection: SMART (Bruker, 1998); cell re®nement: SAINT
Bruker, 2000); data reduction: SAINT; program(s) used to solve
(
structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne
structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
PLATON (Spek, 2002); software used to prepare material for
publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).
(
Braga et al., 1995) hydrogen bonds are absent, as reported
elsewhere (Farrell et al., 2002; Glidewell et al., 2002), together
with the entire phenomenon of polymorphism, in particular
the rather frequent observation of concomitant polymorphism
JNL thanks NCR Self-Service, Dundee, for grants which
have provided computing facilities for this work. JLW thanks
CNPq and FAPERJ for ®nancial support.
(
Bernstein et al., 1999), raise at least the suspicion that, for
systems characterized by weak and/or long-range inter-
molecular forces, the crystal structures may, in general, be
intrinsically non-computable.
Experimental
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: GG1120). Services for accessing these data are
described at the back of the journal.
A sample of the title compound was obtained by reaction of equi-
molar quantities of 2-nitrobenzenesulfenyl chloride and (4-nitro-
benzenethiolato)triphenylstannane in chloroform solution. Crystals
of (IV) suitable for single-crystal X-ray diffraction were grown by
slow evaporation of a solution in ethanol [m.p. 429±431 K; literature
m.p. 429 K (Lukashevich & Sergeeva, 1949)].
References
Crystal data
Aupers, J. H., Cox, P. J., Doidge-Harrison, S. M. S. V., Howie, R. A., Low, J. N.
& Wardell, J. L. (1999). Main Group Chem. 3, 23±42.
Bernstein, J., Davey, R. J. & Henck, J.-O. (1999). Angew. Chem. Int. Ed. 38,
�
3
C
12 8
H N
O S
2 4 2
D
x
= 1.579 Mg m
r
M = 308.34
Mo Kꢂ radiation
Cell parameters from 4661
re¯ections
3440±3461.
Monoclinic, P2 =c
1
Ê
a = 11.4923 (6) A
Boese, R., Bl aÈ ser, D., Nussbaumer, M. & Krygowski, T. M. (1992). Struct.
Chem. 3, 363±368.
Boonstra, E. G. (1963). Acta Cryst. 16, 816±823.
Braga, D., Grepioni, F., Biradha, K., Pedireddi, V. R. & Desiraju, G. R. (1995).
J. Am. Chem. Soc. 117, 3156±3166.
Ê
b = 7.9061 (4) A
ꢀ
ꢃ = 2.9±32.5
ꢄ = 0.43 mm
T = 298 (2) K
Ê
ꢀ
� 1
c = 14.3117 (7) A
ꢁ
= 94.3350 (10)
Ê
3
V = 1296.63 (11) A
Z = 4
Block, colourless
0.33 Â 0.20 Â 0.12 mm
Bruker (1998). SMART. Version 5.054. Bruker AXS Inc., Madison, Wisconsin,
USA.
Data collection
Bruker (2000). SADABS (Version 2.03) and SAINT (Version 6.02a). Bruker
AXS Inc., Madison, Wisconsin, USA.
Cannon, D., Glidewell, C., Low, J. N. & Wardell, J. L. (2000). Acta Cryst. C56,
Nonius KappaCCD area-detector
diffractometer
4661 independent re¯ections
2924 re¯ections with I > 2ꢅ(I)
1267±1268.
'
and ! scans
Absorption correction: multi-scan
SADABS; Bruker, 2000)
min = 0.873, Tmax = 0.951
3 378 measured re¯ections
Rint = 0.027
Choi, C. S. & Abel, J. E. (1972). Acta Cryst. B28, 193±201.
Domenicano, A. & Murray-Rust, P. (1979). Tetrahedron Lett. pp. 2283±2286.
Farrell, D. M. M., Glidewell, C., Low, J. N., Skakle, J. M. S. & Zakaria, C. M.
ꢀ
ꢃ
max = 32.5
(
T
h = � 17 ! 15
k = � 11 ! 11
l = � 21 ! 19
(
2002). Acta Cryst. B58, 289±299.
1
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.
Glidewell, C., Howie, R. A., Low, J. N., Skakle, J. M. S., Wardell, S. M. S. V. &
Wardell, J. L. (2002). Acta Cryst. B58. In the press.
Glidewell, C., Low, J. N. & Wardell, J. L. (2000). Acta Cryst. B56, 893±905.
Herbstein, F. H. & Kapon, M. (1990). Acta Cryst. B46, 567±572.
Kucsman, A., Kapovits, I., Parkanyi, L., Argay, G. & Kalman, A. (1984). J.
Mol. Struct. 125, 331±347.
Lommerse, J. P. M., Motherwell, W. D. S., Ammon, H. L., Dunitz, J. D.,
Gavezzotti, A., Hofmann, D. W. M., Leusen, F. J. J., Mooij, W. T. M., Price,
S. L., Schweizer, B., Schmidt, M. U., van Eijck, B. P., Verwer, P. & Williams,
D. E. (2000). Acta Cryst. B56, 697±714.
Re®nement
2
Re®nement on F
2
H-atom parameters constrained
2
2
2
2
R[F > 2ꢅ(F )] = 0.039
wR(F ) = 0.105
S = 0.93
w = 1/[ꢅ (F
where P = (F
(Á/ꢅ)max < 0.001
o
) + (0.056P) ]
2
2 2
o c
+ 2F )/3
Ê
� 3
4
1
661 re¯ections
81 parameters
Áꢆmax = 0.28 e A
Áꢆmin = � 0.21 e AÊ
� 3
Table 1
Selected bond and torsion angles ( ).
Low, J. N., Storey, E. J., McCarron, M., Wardell, J. L., Ferguson, G. &
Glidewell, C. (2000). Acta Cryst. B56, 58±67.
ꢀ
Lukashevich, V. O. & Sergeeva, M. M. (1949). Zh. Obshch. Khim. 19, 1493±
1506.
Motherwell, W. D. S. (2001). Mol. Cryst. Liq. Cryst. 356, 559±567.
Sekine, A., Ohashi, Y., Yoshimura, K., Yagi, M. & Higuchi, J. (1994). Acta
Cryst. C50, 1101±1104.
C12ÐC11ÐC16
C12ÐC11ÐS1
C16ÐC11ÐS1
C11ÐC12ÐC13
C11ÐC12ÐN12
C22ÐC21ÐC26
116.33 (12)
121.77 (10)
121.88 (10)
122.12 (12)
120.57 (12)
119.95 (13)
C22ÐC21ÐS2
C26ÐC21ÐS2
C23ÐC24ÐC25
C23ÐC24ÐN24
C25ÐC24ÐN24
116.93 (10)
123.12 (11)
122.02 (13)
118.99 (13)
118.99 (12)
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
G oÈ ttingen, Germany.
Spek, A. L. (2002). PLATON. Version of April 2002. University of Utrecht,
The Netherlands.
Trotter, J. & Williston, C. S. (1966). Acta Cryst. 21, 285±288.
Wardell, J. L., Low, J. N. & Glidewell, C. (2000). Acta Cryst. C56, 679±681.
S1ÐS2ÐC21ÐC22
S2ÐS1ÐC11ÐC12
C11ÐS1ÐS2ÐC21
� 150.29 (11)
� 175.34 (10)
� 90.27 (7)
C11ÐC12ÐN12ÐO121 � 0.4 (2)
C23ÐC24ÐN24ÐO241 6.6 (2)
ꢁ
o486 Christopher Glidewell et al.
12 8 2
C H N O
S
4 2
Acta Cryst. (2002). C58, o485±o486