(4-Nitrophenylsulfinyl)acetic acid, a three-dimensional hydrogen-bonded framework built from a combination of two-centre O-H...O and C-H...O hydrogen bonds and a three-centre C-H...(O)2 hydrogen bond

Article abstract of DOI:10.1107/S0108270103001860

Molecules of the title compound, C₈H₇NO₅S, are linked into sheets by a combination of two-centre hydrogen bonds, one of type O-H...O [H...O = 1.81 A, O...O = 2.648 (2) A and O-H...O = 173°] and three of type C-H...O [H...O

Full text of DOI:10.1107/S0108270103001860

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organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
bond, a rather unusual three-centre CÐHÁ Á Á(O)2 hydrogen
bond in which the two O-atom acceptors are bonded to C and
S, respectively.
ISSN 0108-2701
(4-Nitrophenylsulfinyl)acetic acid, a
three-dimensional hydrogen-bonded
framework built from a combination
of two-centre OÐHÁ Á ÁO and
CÐHÁ Á ÁO hydrogen bonds and a
three-centre CÐHÁ Á Á(O)2 hydrogen
bond
The single OÐHÁ Á ÁO hydrogen bond in (II) generates
continuous chains, rather than the usual R22(8) dimer so
characteristic of carboxylic acids. Carboxyl atom O4 in the
molecule at (x, y, z) acts as hydrogen-bond donor to sulfoxide
1
3
atom O5 in the molecule at ( x, + y,
C(6) chain running parallel to the [010] direction and gener-
z), so producing a
2
2
Christopher Glidewell,a* John N. Low,b Janet M. S.
Skakleb and James L. Wardellc
3
4
ated by the 21 screw axis along (0, y, ). Three CÐHÁ Á ÁO
hydrogen bonds link these C(6) chains into sheets. Atom C5 at
(x, y, z) acts as hydrogen-bond donor to nitro atom O1 at
aSchool of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST,
Scotland, bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old
1
2
c
(1 x, 12 + y,
parallel to [010] but this time is generated by the 21 screw axis
z), so producing a C(5) chain that is also
Â
Aberdeen AB24 3UE, Scotland, and Instituto de Quõmica, Departamento de
Â
Ã
Quõmica Inorganica, Universidade Federal do Rio de Janeiro, 21945-970 Rio de
along (12, y, ). The combination of these two chain motifs
1
Janeiro, RJ, Brazil
4
Correspondence e-mail: cg@st-andrews.ac.uk
suf®ces to generate a sheet parallel to (101) that is reinforced
by a second CÐHÁ Á ÁO hydrogen bond. Atom C6 at (x, y, z)
acts as donor to nitro atom O2 at (x, 1 + y, z), so generating by
translation a C(6) chain that is again parallel to [010]. The
(101) sheet thus consists of alternating strips of edge-fused
R33(12) rings, which are generated by screw axes at (21, y, 14 ) and
translation-related sites, and similar strips of edge-fused
R33(22) rings, which are generated by screw axes along (0, y, 34 )
and translation-related sites (Fig. 2). Further reinforcement of
the sheets is provided by another type of CÐHÁ Á ÁO hydrogen
bond, in which the methylene C atom acts as the donor. Atom
C7 in molecule at (x, y, z) acts as donor, via H72, to carboxyl
atom O3 in the molecule at ( x, 12 + y, 23 z), so producing a
C(4) chain generated by the 21 screw axis along (0, y, 34 ) (Fig.
3).
Received 16 January 2003
Accepted 20 January 2003
Online 18 February 2003
Molecules of the title compound, C8H7NO5S, are linked into
sheets by a combination of two-centre hydrogen bonds, one of
Ê
Ê
type OÐHÁ Á ÁO [HÁ Á ÁO = 1.81 A, OÁ Á ÁO = 2.648 (2) A and
OÐHÁ Á ÁO = 173ꢀ] and three of type CÐHÁ Á ÁO [HÁ Á ÁO =
Ê
Ê
2.40±2.48 A, CÁ Á ÁO = 3.206 (3)±3.391 (3) A and CÐHÁ Á ÁO =
131±160ꢀ]. These sheets are linked by an unusual three-centre
Ê
CÐHÁ Á Á(O)2 hydrogen bond [HÁ Á ÁO = 2.46 and 2.56 A,
Ê
CÁ Á ÁO = 3.289 (3) and 3.351 (3) A, and CÐHÁ Á ÁO = 141 and
137ꢀ], in which the two acceptors are carboxyl and sulfoxide
O atoms.
Two (101) sheets pass through each unit cell, and adjacent
sheets are linked by a chain along [001] that is generated by a
nearly planar three-centre CÐHÁ Á Á(O)2 hydrogen bond; the
sum of the angles at the H atom is 357ꢀ. Atom C7 in the
molecule at (x, y, z) acts, via H71, as hydrogen-bond donor to
both carboxyl atom O3 and sulfoxide atom O5, which are both
Comment
In (4-nitrophenylsulfanyl)acetic acid, O2NC6H4SCH2COOH,
(I), the molecules are linked by paired OÐHÁ Á ÁO hydrogen
bonds into dimers. These are further linked by CÐHÁ Á ÁO
hydrogen bonds to form molecular ladders, which are them-
selves weakly linked into sheets by aromatic ꢀ±ꢀ-stacking
interactions (Glidewell et al., 2002). Oxidation of this acid at
the
S atom to give (4-nitrophenylsul®nyl)acetic acid,
O2NC6H4S(O)CH2COOH, (II), which contains three poten-
tial acceptors of hydrogen bonds (O C, O S and O N),
provides many other possibilities for the supramolecular
aggregation, including the possible formation of OÐ
HÁ Á ÁO S and CÐHÁ Á ÁO S hydrogen bonds. We report here
the molecular and supramolecular structure of (II) (Fig. 1),
which contains, in addition to an OÐHÁ Á ÁO S hydrogen
Figure 1
The molecular structure of (II), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 30% probability level.
o124 # 2003 International Union of Crystallography
DOI: 10.1107/S0108270103001860
Acta Cryst. (2003). C59, o124±o126

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organic compounds
3
2
in the molecule at (x,
y,
12 + z), so producing a
C(4)C(4)[R21(6)] chain of rings (Fig. 3) running parallel to
[001] and generated by the c-glide plane at y = 34 (Fig. 4). This
chain contains the uncommon supramolecular synthon (A)
(see Scheme), in which a CÐH bond acts as donor concur-
rently to carboxyl and sulfoxide O atoms.
Figure 4
Part of the crystal structure of (II), showing the formation of a chain of
rings along [001]. Atoms marked with an asterisk (*) or hash (#) are at the
3
symmetry positions (x,
y, 12 + z) and (x, y, 1 + z), respectively.
2
The combination of the (101) sheets and the [001] chains is
suf®cient to generate a single three-dimensional framework.
However, in contrast to the supramolecular structure of (I),
there are no ꢀ±ꢀ-stacking interactions in (II). Note that while
the sulfoxide O atom in (II) participates in an OÐHÁ Á ÁO
hydrogen bond in preference to the other potential acceptors
in the carboxyl and nitro groups, the CÐHÁ Á ÁO hydrogen
bonds utilize all three types of O acceptor (Table 2).
Figure 2
Part of the crystal structure of (II), showing the formation of a (101)
hydrogen-bonded sheet built from R33(12) and R33(22) rings. Atoms
marked with an asterisk (*), hash (#), dollar sign ($) or ampersand (&)
are at the symmetry positions ( x, 12 + y,
z), (1 x, 12 + y,
z),
3
1
2
2
(x, 1 + y, z) and (1 + x, y, 1 + z), respectively.
Within the molecule of (II), the lengths of the three bonds
to the S atom (Table 1) are all typical of their types (Allen et
al., 1987). The two CÐO distances in the carboxyl group are
entirely consistent with the location of the acid H atom as
deduced from a difference map. Although the coordination
around the S atom is sharply pyramidal, torsion angles C1Ð
S1ÐC7ÐC8 and S1ÐC7ÐC8ÐO3/4 indicate that the mole-
cular fragment running from C1 to the carboxyl O atoms O3
and O4 is nearly planar. By contrast, torsion angle C7ÐS1Ð
C1ÐC2 indicates that the aryl ring is nearly orthogonal to the
plane of the side chain, while the dihedral angle between the
Ê
nitro group and the aryl ring is only 5.2 (2) A.
Experimental
Compound (I) was prepared by the reaction of 4-nitrobenzenethiol
with chloroacetic acid in the presence of triethylamine. Compound (I)
was then oxidized using 30% aqueous hydrogen peroxide in a two-
phase water/dichloromethane system, thus producing a mixture of
(II) and (4-nitrophenylsul®nyl)acetic acid, (III). Compound (II) was
readily separable from this mixture by fractional crystallization from
ethanol.
Figure 3
Part of the crystal structure of (II), showing the formation of a C(4) chain
along [010]. Atoms marked with an asterisk (*), hash (#) or dollar sign ($)
3
3
2
are at the symmetry positions ( x, 12 + y,
(x, 1 + y, z), respectively.
z), ( x, 12 + y,
z) and
2
ꢁ
Acta Cryst. (2003). C59, o124±o126
Christopher Glidewell et al. C8H7NO5S o125

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organic compounds
Crystal data
Table 2
Hydrogen-bonding geometry (A, ).
ꢀ
Ê
3
C8H7NO5S
Mr = 229.22
Monoclinic, P21=c
Ê
a = 13.7110 (7) A
Dx = 1.628 Mg m
Mo Kꢂ radiation
Cell parameters from 2124
re¯ections
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
O4ÐH4Á Á ÁO5i
C5ÐH5Á Á ÁO1ii
C6ÐH6Á Á ÁO2iii
C7ÐH71Á Á ÁO3iv
C7ÐH71Á Á ÁO5iv
C7ÐH72Á Á ÁO3v
0.84
0.95
0.95
0.99
0.99
0.99
1.81
2.48
2.40
2.56
2.46
2.47
2.648 (2)
3.391 (3)
3.286 (3)
3.351 (3)
3.289 (3)
3.206 (3)
173
160
155
137
141
131
ꢃ = 3.2±27.5ꢀ
ꢄ = 0.35 mm
T = 120 (2) K
Ê
b = 7.3037 (3) A
1
Ê
c = 9.3537 (4) A
ꢁ = 93.088 (2)ꢀ
V = 935.33 (7) A
Z = 4
3
Ê
Plate, colourless
0.20 Â 0.15 Â 0.02 mm
x; 12 ‡ y; 32 z; (ii)
1
x; 12 ‡ y; 12 z; (iii) x; 1 ‡ y; z; (iv)
Data collection
Symmetry codes: (i)
x; 32 y; z 12; (v) x; y
1
2
3
2
;
z.
Nonius KappaCCD diffractometer
' scans, and ! scans with ꢅ offsets
Absorption correction: multi-scan
(DENZO±SMN; Otwinowski &
Minor, 1997)
2124 independent re¯ections
1588 re¯ections with I > 2ꢆ(I)
Rint = 0.056
ꢃ
max = 27.5ꢀ
Data collection: KappaCCD Server Software (Nonius, 1997); cell
re®nement: DENZO±SMN (Otwinowski & Minor, 1997); data
reduction: DENZO±SMN; program(s) used to solve structure:
SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:
SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek,
2003); software used to prepare material for publication: SHELXL97
and PRPKAPPA (Ferguson, 1999).
h = 15 ! 17
Tmin = 0.923, Tmax = 0.993
7061 measured re¯ections
k = 9 ! 8
l = 11 ! 12
Re®nement
Re®nement on F2
R[F2 > 2ꢆ(F2)] = 0.043
wR(F2) = 0.110
S = 1.02
2124 re¯ections
w = 1/[ꢆ2(F2o) + (0.0526P)2
+ 0.33P]
where P = (F2o + 2Fc2)/3
(Á/ꢆ)max < 0.001
X-ray data were collected at the EPSRC X-ray Crystal-
lographic Service, University of Southampton, England; the
authors thank the staff for all their help and advice. JNL
thanks NCR Self-Service, Dundee, for grants that have
provided computing facilities for this work.
3
Ê
Áꢇmax = 0.79 e A
3
Ê
0.35 e A
144 parameters
H-atom parameters constrained
Áꢇmin
=
Compound (II) is monoclinic and the space group P21/c was
uniquely assigned from the systematic absences. H atoms were
Ê
treated as riding, with OÐH distances of 0.84 A and CÐH distances
Ê
of 0.95 (aromatic) or 0.99 A (CH2).
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK1614). Services for accessing these data are
described at the back of the journal.
Table 1
Selected geometric parameters (A, ).
ꢀ
Ê
References
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.
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.
Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2002). Acta Cryst.
C58, o201±o203.
S1ÐC1
S1ÐC7
S1ÐO5
1.789 (2)
1.809 (2)
1.5045 (16)
C8ÐO3
C8ÐO4
1.212 (3)
1.320 (3)
O5ÐS1ÐC1
O5ÐS1ÐC7
C1ÐS1ÐC7
107.08 (10)
106.57 (10)
96.54 (10)
S1ÐC1ÐC2
S1ÐC1ÐC6
O1ÐN4ÐO2
121.26 (17)
116.79 (16)
123.77 (18)
Nonius (1997). KappaCCD Server Software. Windows 3.11 Version. Nonius
BV, Delft, The Netherlands.
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.
C1ÐS1ÐC7ÐC8
C7ÐS1ÐC1ÐC2
C3ÐC4ÐN4ÐO1
175.84 (16)
87.3 (2)
175.0 (2)
C5ÐC4ÐN4ÐO1
S1ÐC7ÐC8ÐO3
S1ÐC7ÐC8ÐO4
5.6 (3)
7.3 (3)
174.0 (2)
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
È
Gottingen, Germany.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7±13.
ꢁ
o126 Christopher Glidewell et al.
C8H7NO5S
Acta Cryst. (2003). C59, o124±o126