S-(4-Nitrophenyl) 4-nitrobenzene-thiosulfonate

Article abstract of DOI:10.1107/S0108270110027678

The title compound, C₁₂H₈N₂O ₆S₂, (I), is a positional isomer of S-(2-nitro-phenyl) 2-nitrobenzenethiosulfonate [Glidewell, Low & Wardell (2000). Acta Cryst. B56, 893-905], (II). The most obvious difference between the two isomers is the rotation of the nitro groups with respect to the planes of the adjacent aryl rings. In (I), the nitro groups are only slightly rotated out of the plane of the adjacent aryl ring [2.4 (6) and 6.7 (7)°], while in (II) the nitro groups are rotated by between 37 and 52°, in every case associated with S - S - C - C torsion angles close to 90°. Other important differences between the isomers are the C - S - S(O₂) - C torsion angle [78.39 (2)° for (I) and 69.8 (3)° for (II) (mean)] and the dihedral angles between the aromatic rings [12.3 (3)° for (I) and 28.6 (3)° for (II) (mean)]. There are two types of C - H...O hydrogen bond in the structure [C...O = 3.262 (7) A and C - H...O = 144°; C...O = 3.447 (7) A and C - H...O = 166°] and these link the molecules into a two-dimensional framework. The hydrogen-bond-acceptor properties differ between the two isomers.

Full text of DOI:10.1107/S0108270110027678

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
The molecular structure of (I) is shown in Fig. 1 and
selected geometric parameters are given in Table 1.
Compound (I) is a positional isomer of S-(2-nitrophenyl)
2-nitrobenzenethiosulfonate, (II), which crystallizes with Z = 3
ISSN 0108-2701
˚
and S—S bond distances in the range 2.070 (2)–2.076 (2) A
(Glidewell et al., 2000). The two isomers exhibit important
differences with respect to bonding geometries and confor-
mation. The S—S bond distance in (I) is somewhat longer than
that in (II). The S—S distances vary upon oxidation of the
S-(4-Nitrophenyl) 4-nitrobenzene-
thiosulfonate
S-atom centers in the order S—S < SO —S (Aucott et al.,
2
a
a
b
Iv a´ n Brito, * Joselyn Albanez, Michael Bolte and
2005). A survey of C—S—S—C fragments (Allen et al., 1987)
found that S—S bond distances are bimodally distributed: for
c
Alejandro C a´ rdenas
ꢀ
torsion angles in the ranges 75–105 and 0–20 , the mean S—S
a
Departamento de Qu ´ı mica, Facultad de Ciencias B a´ sicas, Universidad de
˚
bond distances are 2.031 (15) and 2.07 (2) A, respectively.
b
Antofagasta, Casilla 170, Antofagasta, Chile, Institut f u¨ r Anorganische Chemie der
Goethe-Universit a¨ t Frankfurt, Max-von-Laue-Strasse 7, D-60438 Frankfurt am Main,
c
Germany, and Departamento de F ´ı sica, Facultad de Ciencias B a´ sicas, Universidad
de Antofagasta, Casilla 170, Antofagasta, Chile
Correspondence e-mail: ivanbritob@yahoo.com
Received 17 June 2010
Accepted 12 July 2010
Online 11 August 2010
The title compound, C H N O S , (I), is a positional isomer
2
12
8
6 2
of S-(2-nitrophenyl) 2-nitrobenzenethiosulfonate [Glidewell,
Low & Wardell (2000). Acta Cryst. B56, 893–905], (II). The
most obvious difference between the two isomers is the
rotation of the nitro groups with respect to the planes of the
adjacent aryl rings. In (I), the nitro groups are only slightly
rotated out of the plane of the adjacent aryl ring [2.4 (6) and
ꢀ
The nitro groups are rotated by 6.7 (7) and 2.4 (6) in (I),
while in (II) the nitro groups are rotated by between 37 and
ꢀ
52 , in every case associated with S—S—C—C torsion angles
close to 90 , and at the same time the SO C H O N group is
ꢀ
ꢀ
6
.7 (7) ], while in (II) the nitro groups are rotated by between
ꢀ
2
6
4
2
also displaced from the C S plane. In general, this conforma-
6
37 and 52 , in every case associated with S—S—C—C torsion
angles close to 90 . Other important differences between the
ꢀ
tion is observed where there are intermolecular C—Hꢁ ꢁ ꢁO
hydrogen bonds in the crystal structure, although this is not a
sufficient condition for the occurrence of the twisted con-
former (Aupers et al., 1999; Kucsman et al., 1984; Low, Storey
ꢀ
isomers are the C—S—S(O )—C torsion angle [78.39 (2) for
2
ꢀ
(
I) and 69.8 (3) for (II) (mean)] and the dihedral angles
ꢀ
ꢀ
between the aromatic rings [12.3 (3) for (I) and 28.6 (3) for
II) (mean)]. There are two types of C—Hꢁ ꢁ ꢁO hydrogen
et al., 2000). Other important differences between the isomers
ꢀ
(
˚
are the C—S—S(O
ꢀ
2
)—C torsion angle [78.39 (2) for (I) and
69.8 (3) for (II) (mean)] and the torsion angles between the
bond in the structure [Cꢁ ꢁ ꢁO = 3.262 (7) A and C—Hꢁ ꢁ ꢁO =
ꢀ
˚
ꢀ
1
44 ; Cꢁ ꢁ ꢁO = 3.447 (7) A and C—Hꢁ ꢁ ꢁO = 166 ] and these
ꢀ
ꢀ
aromatic rings [12.3 (3) for (I) and 28.6 (3) for (II) (mean)].
The molecules in (I) are linked into a continuous two-
dimensional framework by means of C—Hꢁ ꢁ ꢁO hydrogen
bonds. The C—Hꢁ ꢁ ꢁO(S) hydrogen bonds connect the mol-
link the molecules into a two-dimensional framework. The
hydrogen-bond-acceptor properties differ between the two
isomers.
Comment
This paper forms part of our continuing study of the synthesis
and structural characterization of divalent sulfur compounds
(Brito et al., 2008, and references therein). The title
compound, (I), was isolated during attempts to synthesize
sulfenamides by a condensation reaction between 4-nitro-
benzenesulfenyl chloride, (III), and secondary amines.
Compound (III) was purchased from Aldrich (purity 95%,
CAS No. 937–32-6). Impurities were not identified in the
technical information accompanying the compound, but we
believe that (I) was probably an impurity in the commercial
sample of (III). To our knowledge, compound (I) is not
commercially available. We report here the structure of (I),
Figure 1
A displacement ellipsoid plot (50% probability level) of (I), showing the
atom-numbering scheme.
4-O NC H SSO C H O N-4.
2 6 4 2 6 4 2
o466 # 2010 International Union of Crystallography
doi:10.1107/S0108270110027678
Acta Cryst. (2010). C66, o466–o468

organic compounds
ecules to form chains running along the diagonal between the
a and b axes. Pairs of these chains, which are perpendicular to
each other, are further connected by C—Hꢁ ꢁ ꢁO(N) hydrogen
bonds (Table 2 and Fig. 2).
The aromatic C—H bonds between the nitro and sulfone
groups (C13—H13 and C15—H15) are expected to be the
most acidic bonds in the molecule and thus to show the highest
propensity for C—Hꢁ ꢁ ꢁO hydrogen-bond formation. Each
molecule in (I) acts as a twofold donor at (x, y, z) and as a
twofold acceptor; sulfone atom O1S acts as a single acceptor
and nitro group atom O11 as an acceptor of hydrogen bonds at
benzenethiosulfonate (refcode FUQMIN; Glidewell et al.,
2000), S-(2-nitrophenyl) p-toluenethiosulfonate (refcode
LIYQOZ; Low, Glidewell &Wardell, 2000) and bis[2-(N,N-
dipropylcarbamoyl)phenyl] thiosulfinate (refcode NAJBIJ;
Kim et al., 1996), with an average S—SO2 distance of
˚
2.087 (4) A (restraints used in the search: only three-dimen-
sional coordinates available; no private communication; only
one sulfone group and no cyclic disulfide). The O—S—O
angle is much larger than the ideal tetrahedral values,
doubtless as a consequence of both the substantial negative
charge on the geminal O atoms (Table 1), which is observed
also in (II) as well as in the seven compounds found in the
search of the CSD described above, and the ꢀ-bonding/double
1
2
1
2
(
ꢂx + 2, y ꢂ , ꢂz + ) and (x ꢂ 1, y + 1, z), respectively, while
in (II) both of the sulfone O atoms acts as hydrogen-bond
acceptors. The nitro group O atoms of the S-(4-nitrophenyl)
fragment are not involved. The hydrogen-bond acceptor
properties differ between the isomers.
S
O bonds.
The molecular conformation of (I) can be described by four
independent torsion angles. The S—S—C—C angles are all
close to 90 (Fig. 1 and Table 1), so that the projection of the
S—S bond is approximately normal to both aryl rings. The
conformation about the central S—S bond in (I) has one of the
S—O bonds antiperiplanar to the remote C1–C6 aryl ring.
Experimental
All reactions were carried out under an atmosphere of purified
nitrogen. Solvents were dried and distilled prior to use. Equimolar
quantities of 4-nitrobenzenesulfenyl chloride (0.01 mol) and
secondary amines (diethylamine, dicyclohexylamine, dibenzylamine,
morpholine, dipropylamine) (0.01 mol) in dichloromethane solution
were reacted in the presence of an excess of triethylamine. Crystals
suitable for X-ray analysis were grown by slow evaporation from
dichloromethane solution at room temperature. The spectroscopic
properties of (I) were not determined because of the small amount of
sample available.
ꢀ
This same conformation is observed in (II) and is that usually
0
observed in S-aryl arenethiosulfonates, ArSSO Ar (Caputo et
2
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. The
S—SO2 distance is somewhat larger than that in (II)
Crystal data
˚ ˚
2.095 (2) A for (I) and 2.073 (2) A (mean) for (II)] and is
[
characteristic in esters of this type.
˚
V = 1340.0 (2) A
3
C
12
H N O
8 2 6
S
2
M
r
= 340.32
Orthorhombic, P2 2 2
Z = 4
Mo Kꢁ radiation
A search of the Cambridge Structural Database (CSD;
Version 5.31; Allen 2002) for phenylthiolate fragments
C H SX (X = SO C H ; y = 0, 1) yielded seven structures:
1
1
1
˚
ꢂ1
a = 5.2585 (7) A
b = 6.0483 (5) A
˚
c = 42.133 (4) A
ꢂ = 0.43 mm
T = 173 K
˚
6
5ꢂy
2
6
5ꢂy
0.32 ꢃ 0.12 ꢃ 0.12 mm
benzenethiosulfonic acid phenyl ester (CSD refcode
BILCII10; Caputo et al., 1984), S-(p-tolyl) p-toluenethio-
sulfonate (refcode BILCOO01; Ferguson et al., 2000),
p-tolylthiosulfonic acid p-tolyl ester (refcode BILCOO10;
Caputo et al., 1984), di(p-bromophenyl) thiosulfonate (refcode
BPTSLF; Noordik & Vos, 1967), S-(2-nitrophenyl) 2-nitro-
Data collection
Stoe IPDS II two-circle
diffractometer
Absorption correction: multi-scan
5902 measured reflections
2453 independent reflections
1791 reflections with I > 2ꢃ(I)
(
MULABS; Spek, 2009;
Blessing, 1995)
min = 0.875, Tmax = 0.950
Rint = 0.096
T
Table 1
Selected geometric parameters (A, ).
˚
ꢀ
S1—O1S
S1—O2S
S1—C11
S1—S2
S2—C1
C4—N1
1.431 (5)
1.440 (4)
1.767 (6)
2.095 (2)
1.801 (5)
1.478 (7)
N1—O1
N1—O2
C14—N11
N11—O11
N11—O12
1.216 (6)
1.230 (6)
1.466 (8)
1.228 (7)
1.217 (7)
O1S—S1—O2S
O1S—S1—C11
O2S—S1—C11
O1S—S1—S2
O2S—S1—S2
C11—S1—S2
C1—S2—S1
121.0 (3)
107.5 (3)
109.4 (2)
107.92 (17)
103.46 (19)
106.77 (19)
99.05 (18)
O1—N1—O2
O1—N1—C4
O2—N1—C4
O12—N11—O11
O12—N11—C14
O11—N11—C14
123.4 (5)
118.5 (5)
118.0 (5)
123.1 (6)
118.5 (5)
118.4 (6)
Figure 2
The C—Hꢁ ꢁ ꢁO(S) hydrogen bonds connect the molecules to form chains
running along the [110] diagonal between the a and b axes. Pairs of these
chains, which are perpendicular to each other, are further connected by
C—Hꢁ ꢁ ꢁO(N) hydrogen bonds.
S1—S2—C1—C2
S1—S2—C1—C6
86.1 (5)
ꢂ96.1 (4)
S2—S1—C11—C12
S2—S1—C11—C16
ꢂ90.6 (4)
86.8 (4)
ꢄ
Acta Cryst. (2010). C66, o466–o468
Brito et al.
C
12
8 2 6
H N O S
2
o467

organic compounds
Table 2
Hydrogen-bond geometry (A, ).
We thank the Spanish Research Council (CSIC) for pro-
viding us with a free-of-charge licence for the CSD System. JA
thanks the Universidad de Antofagasta for PhD fellowships.
˚
ꢀ
D—Hꢁ ꢁ ꢁA
D—H
Hꢁ ꢁ ꢁA
Dꢁ ꢁ ꢁA
D—Hꢁ ꢁ ꢁA
i
C13—H13ꢁ ꢁ ꢁO11
0.95
0.95
2.45
2.52
3.262 (7)
3.447 (7)
144
166
ii
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: EG3053). Services for accessing these data are
described at the back of the journal.
C15—H15ꢁ ꢁ ꢁO2S
1
2
1
2
Symmetry codes: (i) ꢂx þ 2; y ꢂ ; ꢂz þ ; (ii) x ꢂ 1; y þ 1; z.
References
Refinement
2
Allen, F. H. (2002). Acta Cryst. B58, 380–388.
2
˚
ꢂ3
Áꢄmax = 0.67 e A
R[F > 2ꢃ(F )] = 0.064
wR(F ) = 0.157
S = 0.97
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor,
R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Aucott, S. M., Milton, H. L., Robertson, S. D., Slawin, A. M. Z. & Woollins, J. D.
2
˚
ꢂ3
Áꢄmin = ꢂ0.37 e A
Absolute structure: Flack (1983),
948 Friedel pairs
Flack parameter: 0.06 (18)
2
453 reflections
99 parameters
(
2005). Heteroatom Chem. 16, 346–350.
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.
1
H-atom parameters constrained
&
Blessing, R. H. (1995). Acta Cryst. A51, 33–38.
Brito, I., C a´ rdenas, A., Mundaca, A., L o´ pez-Rodr ´ı guez, M. & Reyes, A.
(2008). Acta Cryst. E64, o1387.
Caputo, R., Palumbo, G., Nardelli, M. & Pelizzi, G. (1984). Gazz. Chim. Ital.
pp. 114–421.
Ferguson, G., Glidewell, C., Low, J. N. & Wardell, J. L. (2000). Acta Cryst. C56,
All H atoms could be located by difference Fourier synthesis but
were ultimately placed in calculated positions and treated as riding,
˚
with C—H distances of 0.95 A and fixed individual displacement
parameters [Uiso(H) = 1.2Ueq(C)]. The absolute structure was
determined on the basis of 950 measured Bijvoet pairs (coverage
692–694.
Flack, H. D. (1983). Acta Cryst. A39, 876–881.
9
9%). Since the molecule is achiral, the directions of the polar axes
Glidewell, C., Low, J. N. & Wardell, J. L. (2000). Acta Cryst. B56, 893–905.
Kim, W., Dannaldson, J. & Gates, K. S. (1996). Tetrahedron Lett. 37, 5337–5340.
Kucsman, A., Kapovits, I., Parkanyi, L., Argay, G. & Kalman, A. (1984). J.
Mol. Struct. 125, 331–347.
Low, J. N., Glidewell, C. & Wardell, J. L. (2000). Acta Cryst. C56, 689–691.
Low, J. N., Storey, E. J., McCarron, M., Wardell, J. L., Ferguson, G. &
Glidewell, C. (2000). Acta Cryst. B56, 58–67.
Noordik, J. H. & Vos, A. (1967). Rec. Trav. Chim. Pays-Bas (Fr.) (Rec. J. R.
Neth. Chem. Soc.), 86, 156–159.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
Stoe & Cie (2001). X-AREA and X-RED. Stoe & Cie, Darmstadt, Germany.
had been determined. Two reflections were not included in the data
set as they were either partially obscured by the beam stop or were
eliminated during data reduction.
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement:
X-AREA; data reduction: X-RED (Stoe & Cie, 2001); program(s)
used to solve structure: SHELXS97 (Sheldrick, 2008); program(s)
used to refine structure: SHELXL97 (Sheldrick, 2008); molecular
graphics: XP in SHELXTL-Plus (Release 4.1; Sheldrick, 2008);
software used to prepare material for publication: SHELXL97.
ꢄ
o468 Brito et al.
12 8 2
C H N O
S
6 2
Acta Cryst. (2010). C66, o466–o468