Layer architecture in 4-nitrophenyl and 4-chlorophenyl 3-nitrobenzene- sulfonate at 100 K

Article abstract of DOI:10.1107/S0108270104002471

The crystal and molecular structure of 4-nitrophenyl and 4-chlorophenyl 3-nitrobenzene-sulfonate were discussed. The structures of the compounds contain weak C-H···O interactions creating layers of molecules which, are arranged in an ABAB sequence. It was

Full text of DOI:10.1107/S0108270104002471

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
relative positions of the two molecular fragments in terms of
rotation about the CÐS bond connecting them. Selected
geometric parameters for both molecules are given in Table 1.
The internal geometries of the molecules of (I) and (II) are
clearly very similar and the torsion angles are entirely
consistant with the mirror-image relationship between them
noted above. The CÐC distances within the 3-nitrophenyl and
4-nitrophenyl rings of (I) are in the ranges 1.370 (8)±1.394 (6)
ISSN 0108-2701
Layer architecture in 4-nitrophenyl
and 4-chlorophenyl 3-nitrobenzene-
sulfonate at 100 K
Ê
and 1.374 (6)±1.385 (6) A, respectively, and for (II), the
corresponding ranges are 1.375 (7)±1.393 (6) and 1.366 (8)±
Ê
1.404 (7) A. In (I), atoms N1, O1 and O2 deviate by 0.014 (7),
Nagarajan Vembu,a Maruthai Nallu,a* Semih Durmus,b
Matthew Panzner,b Jered Garrisonb and Wiley J. Youngsb
Ê
0.055 (7) and 0.028 (8) A, respectively, from the C1±C6
mean plane, while atoms N2, O6 and O7 deviate by 0.085 (6),
Ê
0.164 (7) and 0.052 (7) A, respectively, from the C7±C12
mean plane. In (II), atoms N1, O1 and O2 deviate by 0.018 (8),
aDepartment of Chemistry, Bharathidasan University, Tiruchirappalli 620 024, Tamil
Nadu, India, and bDepartment of Chemistry, University of Akron, 190 East Buchtel
Commons, Akron, OH 44325-3601, USA
Ê
0.246 (9) and 0.274 (10) A, respectively, from the C1±C6
mean plane. The dihedral angles between the two aromatic
planes are 57.7 (7) and 51.0 (2)ꢀ in (I) and (II), respectively.
This is similar to the situation reported for other aromatic
sulfonates (Vembu et al., 2004a,b), but is in contrast with the
near coplanar orientation found in 2,4-dinitrophenyl 4-tol-
uenesulfonate (Vembu, Nallu, Garrison & Youngs, 2003),
Correspondence e-mail: mnalv2003@yahoo.com
Received 18 November 2003
Accepted 30 January 2004
Online 11 March 2004
The structures of the title compounds, C12H8N2O7S and
C12H8ClNO5S, contain weak CÐHÁ Á ÁO interactions creating
layers of molecules which, taking the conformation of the
molecules into account, are arranged in an ABAB sequence.
Both structures can be designated, therefore, as ordered
racemates of rotameric species.
4-methoxyphenyl
4-toluenesulfonate
(Vembu, Nallu,
Garrison, Hindi & Youngs, 2003) and 8-quinolyl 3-nitro-
benzenesulfonate (Vembu, Nallu, Spencer & Howard, 2003).
This difference arises from the synclinal C1ÐSÐO5ÐC7
torsion angles in (I) and (II) [ 62.6 (3) and 68.9 (4)ꢀ,
respectively], as distinct from the antiperiplanar/anticlinal
arrangement, e.g. 162.5 (2)ꢀ for the corresponding angle in
4-methoxyphenyl 4-toluenesulfonate, which permits the
strain-relieving near-coplanar orientation of the aromatic
species.
Comment
Aromatic sulfonates are used in detecting speci®c organic
anion-binding proteins in the liver plasma membrane (Yachi et
al., 1989) and in many other ®elds (Spungin et al., 1992;
Tharakan et al., 1992; Alford et al., 1991; Jiang et al., 1990;
Narayanan & Krakow, 1983). The present X-ray study of
compounds (I) and (II) was undertaken in order to determine
their crystal and molecular structures. This study may serve as
a forerunner both for an assessment of the biological signi®-
cance of these compounds and for studies of the quantitative
structure±activity relationships of aromatic sulfonates.
Weak intermolecular CÐHÁ Á ÁO interactions (Tables 2 and
3) of the type described by Desiraju & Steiner (1999) are
present in both structures. In the structure of (I), the contacts
C6ÐH6Á Á ÁO3i, C8ÐH8Á Á ÁO6ii and C12ÐH12Á Á ÁO4iii (the ®rst
three entries in Table 2) interconnect the molecules to form
layers parallel to (001), as shown in Fig. 3. The molecules
within any one layer are identical in conformation and
The molecules of (I) and (II) are shown in Figs. 1 and 2,
respectively. Ignoring the difference in the nature of the
para-substituent of the phenol ring, viz. NO2 for (I) and Cl for
(II), it is readily seen that the molecules of (I) and (II) are
mirror images of one another. The mirror-image relationship
is clearly brought about by rotational isomerism, i.e. the
Figure 1
A view of a molecule of (I), showing the atom-numbering scheme. Non-H
atoms are shown as 50% probability displacement ellipsoids.
o248 # 2004 International Union of Crystallography
DOI: 10.1107/S0108270104002471
Acta Cryst. (2004). C60, o248±o251

organic compounds
1
2
3
2
orientation, because they are all related to one another by
either cell translation or C-centring. For the layer shown,
which contains the molecule in the asymmetric unit, the
conformation of the molecules is, for convenience, designated
as rotamer A. The neighbouring layers are related by the
operation of the c glide of the space group Cc and the mol-
ecules within the layers are therefore of the other rotameric
form, rotamer B. Thus, the layers of molecules are stacked in
the c direction in an ABAB sequence when the conformation
of the molecules is taken into account. For all layers, one
surface is entirely occupied by the 4-nitrophenyl (phenol)
rings, while the 3-nitrophenyl (sulfonate) rings protrude from
the other surface and always in the positive c direction (Fig. 4).
Further, the interface between neighbouring layers is always
the same and brings about, in addition to the C5ÐH5Á Á ÁO7iv
interaction (the fourth entry in Table 2), a number of close
contacts between non-H atoms, of which O6Á Á ÁC4(x
,
y,
2 + z) of 3.132 (6) A and O2Á Á ÁC10(x, 1 y, z 12) of
1
Ê
Ê
3.152 (6) A are the shortest.
The structure of (II) contains nominally similar layers of
molecules, again parallel to (001) (Fig. 5). Intermolecular
Figure 4
The unit cell of (I) viewed along a, showing the ABAB layer sequence.
Intermolecular interactions at the layer interface as described in the text
are represented by dashed lines. Non-H atoms are shown as 50%
probability displacement ellipsoids and the H atoms involved in the CÐ
HÁ Á ÁO contacts are drawn as small spheres of arbitrary radii. Selected
atoms are labelled. [Symmetry codes: (i) x, 2 y, 12 + z; (ii) x, y, 1 + z; (iii)
12 + x, y 12, z; (iv) 12 + x, 23 y, 21 + z; (v) 21 + x, y 12, 1 + z; (vi) x, y 1, z;
(vii) x, 1 y, 12 + z; (viii) x, y 1, 1 + z.]
Figure 2
A view of a molecule of (II), showing the atom-numbering scheme. Non-
H atoms are shown as 50% probability displacement ellipsoids.
Figure 3
Part of a layer of molecules of (I) parallel to (001). Non-H atoms are
Figure 5
shown as 50% probability displacement ellipsoids and those H atoms
involved in CÐHÁ Á ÁO contacts (dashed lines) are drawn as small spheres
Part of a layer of molecules of (II) parallel to (001). Non-H atoms are
shown as 50% probability displacement ellipsoids and H atoms involved
in CÐHÁ Á ÁO contacts (dashed lines) are drawn as small spheres of
arbitrary radii. Selected atoms are labelled. [Symmetry codes: (i) 1 + x, y,
z; (ii) x, 1 + y, z; (iii) 1 + x, 1 + y, z.]
1
2
of arbitrary radii. Selected atoms are labelled. [Symmetry codes: (i) x
,
y + 12, z; (ii) 1 + x, y, z; (iii) x 21, y 21, z; (iv) 12 + x, 21 + y, z; (v) 12 + x,
12, z.]
y
ꢁ
Acta Cryst. (2004). C60, o248±o251
Nagarajan Vembu et al.
C12H8N2O7S and C12H8ClNO5S o249

organic compounds
Rotational isomerism is present in both structures but the
structures are completely ordered and may be designated as
fully ordered racemates of rotameric species.
Experimental
The title compounds were prepared by the addition of a solution of
3-nitrobenzenesulfonyl chloride (1.1 g, 5 mmol) dissolved in acetone
(5 ml) to a solution of the appropriate phenol (5 mmol) dissolved in
NaOH (4 ml, 5%, 5 g/100 ml) and thorough shaking of the mixture.
The precipitated solid products [1.2 g, 3.7 mmol, yield 74% for (I);
1.0 g, 3.2 mmol, yield 64% for (II)] were recrystallized from ethanol.
Compound (I)
Crystal data
C12H8N2O7S
Mr = 324.26
Monoclinic, Cc
Mo Kꢂ radiation
Cell parameters from 1812
re¯ections
ꢃ = 3.5±26.2ꢀ
Ê
a = 7.891 (2) A
1
Ê
b = 8.798 (3) A
Figure 6
ꢄ = 0.29 mm
T = 100 (2) K
Ê
c = 18.829 (6) A
The unit cell of (II) viewed along a. Intermolecular interactions, one
within the layers and the others at the layer interfaces, are represented by
dashed lines. Non-H atoms are shown as 50% probability displacement
ellipsoids and H atoms involved in the CÐHÁ Á ÁO contacts are drawn as
small spheres of arbitrary radii. Selected atoms are labelled. [Symmetry
codes: (i) 1 + x, y, z; (ii) x, 1 + y, z; (iii) x, 1 y, z; (iv) 1 x, y,
ꢁ = 94.597 (5)ꢀ
V = 1303.1 (7) A
Block, colourless
0.30 Â 0.10 Â 0.10 mm
3
Ê
Z = 4
Dx = 1.653 Mg m
3
1
z; (v) x, 1 y, 1 z; (vi) 1 x, 1 y, 1 z; (vii) 1 + x, y, 1 + z.]
Table 1
Selected geometric parameters (A, ) for (I) and (II).
ꢀ
Ê
contacts within these layers are typi®ed by the contacts C4Ð
H4Á Á ÁO3v, C8ÐH8Á Á ÁO2vi and C9ÐH9Á Á ÁO3vii (the ®rst three
entries in Table 3). The molecules within the layer are iden-
tical in conformation and orientation, because they are related
to one another purely by cell translation. In this case, while
one surface of the layer is populated by the 3-nitrophenyl
group, it is now the 4-chlorophenyl group which protrudes
from the other surface (Fig. 6), the converse of the situation in
the layers of (I) described above. The stacking of the layers in
the c direction once again induces an ABAB pattern when the
conformation of the molecules within the layers is taken into
account, but the inversion in conformation from one layer to
the next is now brought about by the operation of crystal-
lographic centres of symmetry. The stacking of the layers
(Fig. 6) now creates two distinct forms of interface between
them. In the ®rst, at or near z = 12, the interface is between the
3-nitrophenyl surfaces of a pair of layers. This permits the
further interaction C6ÐH6Á Á ÁO4viii (Table 3). At this inter-
face, there is no signi®cant overlap or ꢀ±ꢀ interaction between
the phenyl rings. It is only at the other interface between the
layers, at z = 0 and 1, that ꢀ±ꢀ interaction occurs, where it
involves centrosymmetrically related pairs of 4-chlorophenyl
rings, with a centroid±centroid separation and perpendicular
(I), X = NO2
(II), X = Cl
SÐO3
SÐO4
SÐO5
SÐC1
C3ÐN1
N1ÐO1
N1ÐO2
O5ÐC7
C10ÐX
XÐO6
XÐO7
1.422 (3)
1.429 (3)
1.579 (3)
1.743 (5)
1.479 (6)
1.215 (6)
1.221 (5)
1.419 (5)
1.473 (5)
1.218 (5)
1.227 (5)
1.430 (4)
1.424 (4)
1.589 (4)
1.756 (6)
1.474 (7)
1.230 (5)
1.224 (6)
1.430 (6)
1.763 (6)
O3ÐSÐO4
O3ÐSÐO5
O4ÐSÐO5
O3ÐSÐC1
O4ÐSÐC1
O5ÐSÐC1
C7ÐO5ÐS
O1ÐN1ÐO2
O1ÐN1ÐC3
O2ÐN1ÐC3
O6ÐXÐO7
O6ÐXÐC10
O7ÐXÐC10
120.86 (18)
103.33 (17)
109.07 (17)
110.76 (19)
107.8 (2)
103.60 (18)
122.3 (3)
124.8 (4)
116.8 (4)
118.4 (5)
123.2 (4)
118.5 (4)
118.3 (3)
119.7 (3)
103.8 (2)
109.9 (2)
109.6 (2)
108.8 (2)
103.9 (2)
120.3 (3)
124.1 (5)
117.8 (5)
118.1 (4)
O3ÐSÐC1ÐC2
O4ÐSÐC1ÐC2
O5ÐSÐC1ÐC2
O3ÐSÐC1ÐC6
O4ÐSÐC1ÐC6
O5ÐSÐC1ÐC6
SÐO5ÐC7ÐC12
SÐO5ÐC7ÐC8
C1ÐSÐO5ÐC7
O3ÐSÐO5ÐC7
O4ÐSÐO5ÐC7
33.1 (4)
167.4 (3)
77.1 (4)
148.4 (3)
14.1 (4)
101.4 (4)
99.3 (4)
86.6 (4)
62.6 (3)
178.2 (3)
52.1 (3)
23.0 (5)
155.5 (4)
87.5 (4)
157.2 (4)
24.7 (5)
92.3 (4)
110.6 (5)
74.0 (5)
68.9 (4)
176.5 (4)
47.3 (4)
Ê
distance between the ring planes of 3.725 and 3.415 A,
respectively. This is the only signi®cant intermolecular inter-
action at this interface. This layer sequence can also be
thought of in terms of double layers centred on the face-to-
face interface at z = 12, which then interact with the creation of
the ꢀ±ꢀ interactions at z = 0 and 1.
ꢁ
o250 Nagarajan Vembu et al.
C12H8N2O7S and C12H8ClNO5S
Acta Cryst. (2004). C60, o248±o251

organic compounds
Data collection
Re®nement
Bruker SMART 1000 CCD area-
detector diffractometer
' and ! scans
5467 measured re¯ections
2971 independent re¯ections
2534 re¯ections with I > 2ꢅ(I)
Rint = 0.078
max = 28.3ꢀ
h = 10 ! 10
k = 11 ! 11
l = 24 ! 24
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.065
wR(F2) = 0.183
S = 1.00
1713 re¯ections
w = 1/[ꢅ2(Fo2) + (0.1188P)2]
where P = (Fo2 + 2Fc2)/3
(Á/ꢅ)max < 0.001
ꢃ
3
Ê
Áꢆmax = 0.48 e A
3
Ê
0.38 e A
Áꢆmin
=
182 parameters
Only H-atom U values re®ned
Re®nement
All H atoms were included in calculated positions, with CÐH
Ê
distances of 0.95 A, and re®ned with a riding model. Their displace-
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.061
wR(F2) = 0.139
S = 1.06
2971 re¯ections
(Á/ꢅ)max < 0.001
3
Ê
Áꢆmax = 0.57 e A
3
Ê
0.30 e A
ment parameters were tied to a common free variable, which was
re®ned.
Áꢆmin
=
Absolute structure: Flack (1983);
1406 Friedel pairs
Flack parameter = 0.08 (12)
For both compounds, data collection: SMART-NT (Bruker, 1998);
cell re®nement: SMART-NT; data reduction: SAINT-NT (Bruker,
1998); program(s) used to solve structure: SHELXTL (Sheldrick,
1998); program(s) used to re®ne structure: SHELXTL; molecular
graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to
prepare material for publication: SHELXTL and PLATON (Spek,
2003).
200 parameters
Only H-atom U values re®ned
w = 1/[ꢅ2(Fo2) + (0.0665P)2]
2
where P = (Fo + 2Fc2)/3
Table 2
Hydrogen-bonding geometry (A, ) for (I).
ꢀ
Ê
NV thanks the University Grants Commission±SERO,
Government of India, for the award of a Faculty Improvement
Programme Grant (TFTNBD097 dt., 07.07.99). This research
was supported in part by grants to WJY from the US National
Science Foundation and the Ohio Board of Regents. The
authors wish to thank the referee and the co-editor for
extensive helpful suggestions.
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
C6ÐH6Á Á ÁO3i
C12ÐH12Á Á ÁO4ii
C8ÐH8Á Á ÁO6iii
C5ÐH5Á Á ÁO7iv
0.95
0.95
0.95
0.95
2.45
2.30
2.45
2.43
3.100 (5)
3.197 (5)
3.350 (5)
3.184 (6)
126
158
158
136
1
2
1
2
Symmetry codes: (i)
1
x
;
‡ y; z; (ii)
x
12; y 12; z; (iii) 1 ‡ x; y; z; (iv)
x; 2 y; z
.
2
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: BM1553). Services for accessing these data are
described at the back of the journal.
Compound (II)
Crystal data
C12H8ClNO5S
Mr = 313.70
Triclinic, P1
a = 7.556 (9) A
Ê
b = 8.562 (8) A
Z = 2
Dx = 1.605 Mg m
Mo Kꢂ radiation
3
References
Ê
Cell parameters from 3154
re¯ections
Alford, R. L., Honda, S., Lawrence, C. B. & Belmont, J. W. (1991). Virology,
183, 611±619.
Bruker (1998). SMART-NT and SAINT-NT. Versions 5.0. Bruker AXS Inc.,
Madison, Wisconsin, USA.
Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond in Structural
Chemistry and Biology. New York: Oxford University Press.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
ꢃ = 2.6±28.2ꢀ
ꢄ = 0.47 mm
T = 100 (2) K
Ê
c = 10.851 (13) A
1
ꢂ = 67.86 (6)ꢀ
ꢁ = 89.93 (11)ꢀ
ꢇ = 87.01 (8)ꢀ
Block, colourless
0.46 Â 0.13 Â 0.12 mm
3
Ê
V = 649.2 (13) A
Flack, H. D. (1983). Acta Cryst. A39, 876±881.
Data collection
Jiang, F. N., Jiang, S., Liu, D., Richter, A. & Levy, J. G. (1990). J. Immunol.
Methods, 134, 139±149.
Narayanan, C. S. & Krakow, J. S. (1983). Nucleic Acids Res. 11, 2701±2716.
Bruker SMART 1000 CCD area-
detector diffractometer
' and ! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.812, Tmax = 0.945
5715 measured re¯ections
1713 independent re¯ections
1261 re¯ections with I > 2ꢅ(I)
Rint = 0.068
È
Sheldrick, G. M. (1996). SADABS. University of Gottingen, Germany.
Sheldrick, G. M. (1998). SHELXTL. University of Gottingen, Germany.
È
ꢃ
max = 28.3ꢀ
Spek, A. L. (2003). J. Appl. Cryst. 36, 7±13.
Spungin, B., Levinshal, T., Rubenstein, S. & Breitbart, H. (1992). FEBS Lett.
311, 155±160.
Tharakan, J., Highsmith, F., Clark, D. & Drohsn, W. (1992). J. Chromatogr. 595,
103±111.
h = 3 ! 9
k = 10 ! 9
l = 14 ! 8
Vembu, N., Nallu, M., Durmus, S., Panzner, M., Garrison, J. & Youngs, W. J.
(2004a). Acta Cryst. E60, o1±o3.
Vembu, N., Nallu, M., Durmus, S., Panzner, M., Garrison, J. & Youngs, W. J.
(2004b). Acta Cryst. C60, o65±o68.
Table 3
Hydrogen-bonding geometry (A, ) for (II).
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
Vembu, N., Nallu, M., Garrison, J., Hindi, K. & Youngs, W. J. (2003). Acta
Cryst. E59, o830±o832.
Vembu, N., Nallu, M., Garrison, J. & Youngs, W. J. (2003). Acta Cryst. E59,
o378±o380.
Vembu, N., Nallu, M., Spencer, E. C. & Howard, J. A. K. (2003). Acta Cryst.
E59, o1379±o1382.
C4ÐH4Á Á ÁO3v
C8ÐH8Á Á ÁO2vi
C9ÐH9Á Á ÁO3vii
C6ÐH6Á Á ÁO4viii
0.95
0.95
0.95
0.95
2.50
2.48
2.57
2.62
3.441 (8)
3.307 (8)
3.293 (8)
3.311 (7)
170
145
133
129
Yachi, K., Sugiyama, Y., Sawada, Y., Iga, T., Ikeda, Y., Toda, G. & Hanano, M.
(1989). Biochim. Biophys. Acta, 978, 1±7.
Symmetry codes: (v) x; y 1; z; (vi)
x; y; 1 z.
x
1; 1 ‡ y; z; (vii)
x
1; y; z; (viii)
ꢁ
Acta Cryst. (2004). C60, o248±o251
Nagarajan Vembu et al.
C12H8N2O7S and C12H8ClNO5S o251