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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 Å, O...O = 2.648 (2) Å and O-H...O = 173°] and three of type C-H...O [H...O = 2.40-2.48 Å, C...O = 3.206 (3)-3.391 (3) Å and C-H...O = 131-160°]. These sheets are linked by an unusual three-centre C-H...(O)2 hydrogen bond [H...O = 2.46 and 2.56 Å, C...O = 3.289 (3) and 3.351 (3) Å, and C-H...O = 141 and 137°], in which the two acceptors are carboxyl and sulfoxide O atoms.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103001860/sk1614sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103001860/sk1614Isup2.hkl
Contains datablock I

CCDC reference: 208017

Comment top

In (4-nitrophenylsulfanyl)acetic acid, O2NC6H4SCH2COOH, (I), the molecules are linked by paired O—H···O hydrogen bonds into dimers. These are further linked by C—H···O hydrogen bonds to form molecular ladders, which are themselves weakly linked into sheets by aromatic ππ-stacking interactions (Glidewell et al., 2002). Oxidation of this acid at the S atom to (4-nitrophenylsulfinyl)acetic acid, O2NC6H4S(O)CH2COOH, (II), which contains three potential acceptors of hydrogen bonds [OC, OS and ON], provides many other possibilities for the supramolecular aggregation, including the possible formation of O—H···OS and C—H···OS hydrogen bonds. Here we report the molecular and supramolecular structure of (II) (Fig. 1), which contains, in addition to an O—H···OS hydrogen bond, a rather unusual three-centre C—H···(O)2 hydrogen bond in which the two oxygen acceptors are bonded to C and S, respectively.

The single O—H···O hydrogen bond in (II) generates continuous chains, rather than the usual R22(8) dimer so characteristic of carboxylic acids. The carboxyl atom O4 in the molecule at (x, y, z) acts as hydrogen-bond donor to the sulfoxide atom O5 in the molecule at (-x, 0.5 + y, 1.5 − z), so producing a C(6) chain running parallel to the [010] direction and generated by the 21 screw axis along (0, y, 3/4). Three C—H···O hydrogen bonds link these C(6) chains into sheets. Atom C5 at (x, y, z) acts as hydrogen-bond donor to nitro O1 at (1 − x, 0.5 + y, 0.5 − z), so producing a C(5) chain that is also parallel to [010] but this time is generated by the 21 screw axis along (1/2, y, 1/4). The combination of these two chain motifs suffices to generate a sheet parallel to (101) that is reinforced by a second C—H···O hydrogen bond. Atom C6 at (x, y, z) acts as donor to the 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 (1/2, y, 1/4) and translation-related sites, and similar strips of edge-fused R33(22) rings, which are generated by screw axes along (0, y, 3/4) and translation-related sites (Fig. 2). Further reinforcement of the sheets is provided by another type of C—H···O hydrogen bond, in which the methylene C atom acts as the donor. Atom C7 in the molecule at (x, y, z) acts as donor, via H72, to the carboxyl atom O3 in the molecule at (-x, −0.5 + y, 1.5 − z), so producing a C(4) chain generated by the 21 screw axis along (0, y, 3/4) (Fig. 3).

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 C—H···(O)2 hydrogen bond. The sum of the angles at H is 357°. 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, both in the molecule at (x, 1.5 − y, −0.5 + 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 = 0.75. This chain contains the uncommon supramolecular synthon A (see Scheme), in which a C—H bond acts as donor concurrently to carboxyl and sulfoxide O atoms.

The combination of the (101) sheets and the [001] chains is sufficient to generate a single three-dimensional framework. However, in contrast to the supramolecular structure of (I), there are no ππ- stacking interactions in (II). Note that while the sulfoxide O in (II) participates in the O—H···O hydrogen bond in preference to the other potential acceptors in the carboxyl and nitro groups, the C—H···O hydrogen bonds utilize all three types of O acceptor (Table 2).

Within the molecule of (II), the lengths of the three bonds to S (Table 1) are all typical of their types (Allen et al., 1987). The two C—O 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 round the S atom is sharply pyramidal, the torsion angles C1—S1—C7—C8 and S1—C7—C8—O3/)4 indicate that the molecular fragment running from C1 to the carboxyl O atoms O3 and O4 is nearly planar. By contrast, the torsion angle C7—S1—C1—C2 indicates that the aryl ring is nearly orthogonal to the plane of the side chain, while the dihedral angle between the nitro group and the aryl ring is only 5.2 (2) Å.

Experimental top

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-nitrophenylsulfinyl)acetic acid (III), from which (II) is readily separable by fractional crystallization from ethanol.

Refinement top

Compound (II) is monoclinic and the space group P21/c was uniquely assigned from the systematic absences. H atoms were treated as riding with O—H distances of 0.84 Å and C—H distances of 0.95 Å (aromatic) or 0.99 Å (CH2).

Computing details top

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 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 ($) or ampersand (&) are at the symmetry positions (-x, 0.5 + y, 1.5 − x), (1 − x, 0.5 + y, 0.5 − z), (x, 1 + y, z) and (1 + x, y, −1 + z), respectively.
[Figure 3] Fig. 3. Part of the crystal structure of (II), showing the formation of a C(4) chain along [010]. Atoms marked with an asterisk (*), hash (#) or dollar sign ($) are at the symmetry positions (-x, 0.5 + y, 1.5 − z), (-x, −0.5 + y, 1.5 − z) and (x, −1 + y, z), respectively.
[Figure 4] Fig. 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 symmetry positions (x, 1.5 − y, −0.5 + z) and (x, y, −1 + z), respectively.
(4-Nitrophenylsulfinyl)acetic acid top
Crystal data top
C8H7NO5SF(000) = 472
Mr = 229.22Dx = 1.628 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2124 reflections
a = 13.7110 (7) Åθ = 3.2–27.5°
b = 7.3037 (3) ŵ = 0.35 mm1
c = 9.3537 (4) ÅT = 120 K
β = 93.088 (2)°Plate, colourless
V = 935.33 (7) Å30.20 × 0.15 × 0.02 mm
Z = 4
Data collection top
KappaCCD
diffractometer
2124 independent reflections
Radiation source: Rotating Anode1588 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.056
ϕ scans, and ω scans with κ offsetsθmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan
DENZO-SMN (Otwinowski & Minor, 1997)
h = 1517
Tmin = 0.923, Tmax = 0.993k = 98
7061 measured reflectionsl = 1112
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0526P)2 + 0.33P]
where P = (Fo2 + 2Fc2)/3
2124 reflections(Δ/σ)max < 0.001
144 parametersΔρmax = 0.79 e Å3
0 restraintsΔρmin = 0.35 e Å3
Crystal data top
C8H7NO5SV = 935.33 (7) Å3
Mr = 229.22Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.7110 (7) ŵ = 0.35 mm1
b = 7.3037 (3) ÅT = 120 K
c = 9.3537 (4) Å0.20 × 0.15 × 0.02 mm
β = 93.088 (2)°
Data collection top
KappaCCD
diffractometer
2124 independent reflections
Absorption correction: multi-scan
DENZO-SMN (Otwinowski & Minor, 1997)
1588 reflections with I > 2σ(I)
Tmin = 0.923, Tmax = 0.993Rint = 0.056
7061 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.110H-atom parameters constrained
S = 1.02Δρmax = 0.79 e Å3
2124 reflectionsΔρmin = 0.35 e Å3
144 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.20558 (4)0.65399 (7)0.71021 (6)0.01954 (18)
O50.17742 (11)0.5651 (2)0.84711 (16)0.0220 (4)
C10.26862 (16)0.4852 (3)0.6118 (2)0.0183 (5)
C20.25576 (16)0.2990 (3)0.6365 (2)0.0205 (5)
C30.30936 (16)0.1737 (3)0.5611 (2)0.0195 (5)
C40.37325 (15)0.2402 (3)0.4635 (2)0.0186 (5)
N40.43007 (13)0.1080 (2)0.3832 (2)0.0208 (4)
O10.49132 (13)0.1682 (2)0.30462 (18)0.0303 (4)
O20.41335 (12)0.0562 (2)0.39842 (18)0.0263 (4)
C50.38575 (16)0.4248 (3)0.4366 (2)0.0206 (5)
C60.33308 (17)0.5492 (3)0.5133 (2)0.0216 (5)
C70.09633 (16)0.6606 (3)0.5930 (2)0.0205 (5)
C80.03000 (17)0.8074 (3)0.6458 (3)0.0238 (5)
O30.05419 (13)0.9127 (3)0.74139 (19)0.0369 (5)
O40.05533 (12)0.8082 (2)0.57336 (19)0.0294 (4)
H20.21110.25830.70390.016 (6)*
H30.30240.04580.57600.026 (7)*
H50.42930.46510.36750.023 (6)*
H60.34090.67700.49880.033 (7)*
H710.11350.68780.49380.040 (8)*
H720.06290.54040.59340.027 (7)*
H40.09060.89140.60490.080 (13)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0199 (3)0.0199 (3)0.0189 (3)0.0001 (2)0.0027 (2)0.0021 (2)
O50.0233 (9)0.0261 (9)0.0167 (8)0.0001 (6)0.0015 (7)0.0008 (6)
C10.0177 (11)0.0195 (11)0.0174 (11)0.0009 (8)0.0005 (9)0.0038 (9)
C20.0198 (11)0.0242 (12)0.0177 (12)0.0047 (9)0.0034 (9)0.0003 (9)
C30.0244 (12)0.0160 (10)0.0178 (11)0.0026 (8)0.0011 (9)0.0000 (9)
C40.0191 (11)0.0199 (11)0.0167 (11)0.0014 (8)0.0013 (9)0.0032 (9)
N40.0205 (10)0.0221 (10)0.0196 (10)0.0027 (8)0.0003 (8)0.0002 (8)
O10.0337 (10)0.0279 (9)0.0307 (10)0.0043 (7)0.0160 (8)0.0019 (7)
O20.0278 (9)0.0183 (9)0.0327 (10)0.0023 (6)0.0005 (7)0.0015 (7)
C50.0189 (11)0.0228 (12)0.0204 (12)0.0043 (9)0.0038 (9)0.0012 (9)
C60.0225 (12)0.0177 (11)0.0247 (13)0.0013 (8)0.0036 (10)0.0004 (9)
C70.0214 (12)0.0238 (12)0.0163 (11)0.0016 (8)0.0021 (9)0.0004 (9)
C80.0247 (13)0.0261 (12)0.0206 (12)0.0019 (9)0.0019 (10)0.0021 (10)
O30.0361 (11)0.0425 (10)0.0313 (10)0.0134 (8)0.0047 (8)0.0128 (9)
O40.0233 (9)0.0333 (10)0.0310 (10)0.0051 (7)0.0026 (8)0.0009 (8)
Geometric parameters (Å, º) top
S1—C11.789 (2)C4—C51.384 (3)
S1—C71.809 (2)C4—N41.472 (3)
S1—O51.5045 (16)N4—O11.227 (2)
C8—O31.212 (3)N4—O21.231 (2)
C8—O41.320 (3)C5—C61.385 (3)
C1—C61.392 (3)C5—H50.95
C1—C21.392 (3)C6—H60.95
C2—C31.390 (3)C7—C81.507 (3)
C2—H20.95C7—H710.99
C3—C41.387 (3)C7—H720.99
C3—H30.95O4—H40.84
O5—S1—C1107.08 (10)O2—N4—C4118.25 (18)
O5—S1—C7106.57 (10)C4—C5—C6118.2 (2)
C1—S1—C796.54 (10)C4—C5—H5120.9
S1—C1—C2121.26 (17)C6—C5—H5120.9
S1—C1—C6116.79 (16)C5—C6—C1119.4 (2)
C6—C1—C2121.9 (2)C5—C6—H6120.3
C3—C2—C1118.9 (2)C1—C6—H6120.3
C3—C2—H2120.5C8—C7—S1108.37 (15)
C1—C2—H2120.5C8—C7—H71110.0
C4—C3—C2118.25 (19)S1—C7—H71110.0
C4—C3—H3120.9C8—C7—H72110.0
C2—C3—H3120.9S1—C7—H72110.0
C5—C4—C3123.4 (2)H71—C7—H72108.4
C5—C4—N4118.19 (19)O3—C8—O4125.2 (2)
C3—C4—N4118.46 (19)O3—C8—C7123.2 (2)
O1—N4—O2123.77 (18)O4—C8—C7111.6 (2)
O1—N4—C4117.98 (18)C8—O4—H4109.5
C1—S1—C7—C8175.84 (16)C1—C2—C3—C40.3 (3)
C7—S1—C1—C287.3 (2)C2—C3—C4—C50.5 (3)
C3—C4—N4—O1175.0 (2)C2—C3—C4—N4179.92 (19)
C5—C4—N4—O15.6 (3)C5—C4—N4—O2174.3 (2)
S1—C7—C8—O37.3 (3)C3—C4—N4—O25.2 (3)
S1—C7—C8—O4174.0 (2)C3—C4—C5—C61.3 (3)
O5—S1—C1—C6155.66 (17)N4—C4—C5—C6179.29 (19)
C7—S1—C1—C694.73 (19)C4—C5—C6—C11.2 (3)
O5—S1—C1—C222.4 (2)C2—C1—C6—C50.4 (3)
C6—C1—C2—C30.4 (3)S1—C1—C6—C5178.41 (17)
S1—C1—C2—C3177.53 (16)O5—S1—C7—C874.12 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4···O5i0.841.812.648 (2)173
C5—H5···O1ii0.952.483.391 (3)160
C6—H6···O2iii0.952.403.286 (3)155
C7—H71···O3iv0.992.563.351 (3)137
C7—H71···O5iv0.992.463.289 (3)141
C7—H72···O3v0.992.473.206 (3)131
Symmetry codes: (i) x, y+1/2, z+3/2; (ii) x+1, y+1/2, z+1/2; (iii) x, y+1, z; (iv) x, y+3/2, z1/2; (v) x, y1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC8H7NO5S
Mr229.22
Crystal system, space groupMonoclinic, P21/c
Temperature (K)120
a, b, c (Å)13.7110 (7), 7.3037 (3), 9.3537 (4)
β (°) 93.088 (2)
V3)935.33 (7)
Z4
Radiation typeMo Kα
µ (mm1)0.35
Crystal size (mm)0.20 × 0.15 × 0.02
Data collection
DiffractometerKappaCCD
diffractometer
Absorption correctionMulti-scan
DENZO-SMN (Otwinowski & Minor, 1997)
Tmin, Tmax0.923, 0.993
No. of measured, independent and
observed [I > 2σ(I)] reflections
7061, 2124, 1588
Rint0.056
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.110, 1.02
No. of reflections2124
No. of parameters144
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.79, 0.35

Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO–SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999).

Selected geometric parameters (Å, º) top
S1—C11.789 (2)C8—O31.212 (3)
S1—C71.809 (2)C8—O41.320 (3)
S1—O51.5045 (16)
O5—S1—C1107.08 (10)S1—C1—C2121.26 (17)
O5—S1—C7106.57 (10)S1—C1—C6116.79 (16)
C1—S1—C796.54 (10)O1—N4—O2123.77 (18)
C1—S1—C7—C8175.84 (16)C5—C4—N4—O15.6 (3)
C7—S1—C1—C287.3 (2)S1—C7—C8—O37.3 (3)
C3—C4—N4—O1175.0 (2)S1—C7—C8—O4174.0 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4···O5i0.841.812.648 (2)173
C5—H5···O1ii0.952.483.391 (3)160
C6—H6···O2iii0.952.403.286 (3)155
C7—H71···O3iv0.992.563.351 (3)137
C7—H71···O5iv0.992.463.289 (3)141
C7—H72···O3v0.992.473.206 (3)131
Symmetry codes: (i) x, y+1/2, z+3/2; (ii) x+1, y+1/2, z+1/2; (iii) x, y+1, z; (iv) x, y+3/2, z1/2; (v) x, y1/2, z+3/2.
 

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