2-[1-(phenylsulfonyl)ethyl]benzoic acid and 2-[1-(phenylsulfonyl)propyl]-benzoic acid

Article abstract of DOI:10.1107/S0108270102004389

Molecular conformation of 2-[1-(phenylsufonyl)ethyl]benzoic acid and 2-[1-(phenylsulfonyl)propyl]-benzoic acid in solid state was investigated by carrying out X-ray study. The molecular structures were stabilized by intramolecular C-H·O hydrogen bonds. The crystal packing was stabilized by a single O-H·O hydrogen bond in both compounds. The hydrogen bond formed a cyclic dimer, with graph-set descriptor R²₂(8), about a centre of symmetry.

Full text of DOI:10.1107/S0108270102004389

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
Benedetti, 1992). The conformation about the S atom deter-
mines whether the pharmacological activity of the compound
is mild or strong (McKenna et al., 1989). In order to obtain
detailed information on their molecular conformation in the
solid state, the present X-ray study on the title sulfones has
been carried out and the results are presented here.
ISSN 0108-2701
2-[1-(Phenylsulfonyl)ethyl]benzoic
acid and 2-[1-(phenylsulfonyl)propyl]-
benzoic acid
Figs. 1 and 2 show the molecular structures of (I) and (II),
respectively, with the atom-numbering schemes. In both
compounds, the CÐO distances are as expected. The SÐCPh
Ê
Ê
distances [1.766 (2) A in (I) and 1.767 (2) A in (II)] compare
Ê
well with the literature value of 1.763 (9) A for CarÐSO2ÐC
Ê
(Allen et al., 1987). The S1ÐC8 distances [1.806 (2) A for (I)
K. Sethu Sankar,a D. Velmurugan,a*
B. T. S. Thirumamagal,b S. Shanmuga Sundara Raj,c
H.-K. Func and Jib-Kim Moond
Ê
and 1.813 (2) A for (II)] are longer than the literature value of
3
1.786 (18) A for Csp ÐSO2ÐC (Allen et al., 1987). The mean
Ê
Ê
O distance of 1.436 (2) A agrees well with the reported
S
Ê
aDepartment of Crystallography and Biophysics, University of Madras, Guindy
Campus, Chennai 600 025, India, bDepartment of Organic Chemistry, University of
Madras, Guindy Campus, Chennai 600 025, India, cSchool of Physics, Universiti
Sains Malaysia, 11800 USM, Penang, Malaysia, and dDepartment of Physics,
Soonchunbyang University, PO Box 97, Asan, Chungnam 336-600, South Korea
Correspondence e-mail: d_velu@yahoo.com
value of 1.436 (2) A (Bocelli & Rizzoli, 1990; Jeyakanthan &
Velmurugan, 1998).
The angular disposition of the bonds about atom S1 in (I)
and (II) shows signi®cant deviation from that of a regular
tetrahedron, with the largest deviation being in the OÐSÐO
angle for both (I) and (II). In both compounds, the widening
of the O4ÐS1ÐO2 angle [to 118.6 (1)ꢀ in (I) and 118.4 (1)ꢀ in
(II)], and the resulting narrowing of CÐSÐC from the ideal
tetrahedral value [C10ÐS1ÐC8 to 102.6 (1)ꢀ in (I) and C11Ð
Received 6 February 2002
Accepted 7 March 2002
Online 11 April 2002
In the title acids, C15H14O4S, (I), and C16H16O4S, (II),
respectively, the angle between the planes of the benzene
ring and the carboxyl group is 13.7 (1)ꢀ for (I) and 21.3 (1)ꢀ for
(II). The molecular structures are stabilized by intramolecular
CÐHÁ Á ÁO hydrogen bonds. The crystal packing is stabilized
by a single OÐHÁ Á ÁO hydrogen bond in both compounds, in
Ê
which the O and H atoms are ordered; HÁ Á ÁO 1.87 A for (I)
Ê
Ê
Ê
and 1.83 A for (II), OÁ Á ÁO 2.680 (2) A for (I) and 2.652 (3) A
for (II), and OÐHÁ Á ÁO 172ꢀ for (I) and 175ꢀ for (II). The
hydrogen bond forms a cyclic dimer, with graph-set descriptor
R22(8), about a centre of symmetry.
Comment
The title compounds, (I) and (II), are potential intermediates
for the synthesis of 2-alkylbenzoic acid starting from o-toluic
acid. Sulfates, sulfones, thiols, sulfonamides and sulfoxides are
some of the compounds that belong to this class, and many of
these exhibit insecticidal, germicidal or antimicrobial activities
(Krishnaiah et al., 1995; De Benedetti et al., 1985; Dupont et
al., 1978). Sulfur-containing compounds, for the most part, act
as simple narcotics (Schultz et al., 2001). A series of acyclic
sulfones have been identi®ed as high-af®nity selective
Figure 1
A view of the molecular structure of (I) showing the atom-numbering
scheme. Displacement ellipsoids are drawn at the 50% probability level
and H atoms are shown as small spheres of arbitrary radii.
Figure 2
5-HT(2A) receptor antagonists (Fletcher et al., 2002). para-
Amino,para-phenyl sulfones are well known as antibacterial
and antileprotic agents (McCullough & Maren, 1973; De
A view of the molecular structure of (II) showing the atom-numbering
scheme. Displacement ellipsoids are drawn at the 50% probability level
and H atoms are shown as small spheres of arbitrary radii.
Acta Cryst. (2002). C58, o257±o259
DOI: 10.1107/S0108270102004389
# 2002 International Union of Crystallography o257

organic compounds
bulkier nature of the propyl group in (II) compared with the
ethyl group in (I).
In addition to van der Waals interactions, there is one OÐ
HÁ Á ÁO intermolecular hydrogen bond in both compounds.
Each of the hydrogen bonds in (I) and (II) participates in an
eight-membered cyclic dimer arrangement, as shown in the
packing diagrams (Figs. 3 and 4), with an R22(8) ring descriptor
(Bernstein et al., 1995). A similar pattern is observed for
2-(isopropylthio)benzoic acid (Gerkin, 1999). The molecular
structures of (I) and (II) are stabilized by intramolecular CÐ
HÁ Á ÁO hydrogen bonds.
Experimental
The title compounds were prepared by the alkylation of methyl
2-phenylsulfonyl methylbenzoate with the corresponding alkyl
iodides in the presence of sodium hydride in dry dimethyl sulfoxide at
room temperature. The ester group suffered hydrolysis under the
reaction conditions. Compounds (I) and (II) were recrystallized from
ethyl acetate and hexane by slow evaporation.
Figure 3
The crystal structure of (I) viewed along b, with the hydrogen bonds
shown as dashed lines.
Compound (I)
Crystal data
3
C15H14O4S
Mr = 290.32
Monoclinic, P21=c
Ê
a = 12.8969 (3) A
Dx = 1.432 Mg m
Mo Kꢁ radiation
Cell parameters from 7690
re¯ections
ꢂ = 2.9±28.4ꢀ
ꢃ = 0.25 mm
T = 293 (2) K
Ê
b = 8.5064 (1) A
1
Ê
c = 13.0472 (3) A
ꢀ = 109.803 (1)ꢀ
V = 1346.71 (5) A
Z = 4
3
Ê
Block, colourless
0.38 Â 0.28 Â 0.24 mm
Data collection
Siemens SMART CCD area-
detector diffractometer
! scans
9552 measured re¯ections
3352 independent re¯ections
2293 re¯ections with I > 2ꢄ(I)
Rint = 0.050
ꢂmax = 28.3ꢀ
h = 17 ! 16
k = 9 ! 11
l = 13 ! 17
Figure 4
The crystal structure of (II) viewed along a, with the hydrogen bonds
shown as dashed lines.
Re®nement
S1ÐC8 to 105.2 (1)ꢀ in (II)], are attributed to the Thorpe±
Ingold effect (Bassindale, 1984). The dihedral angles between
the carboxyl group and the C1±C6 phenyl ring are 13.7 (1) and
21.3 (1)ꢀ in (I) and (II), respectively. In both compounds, the
orientation of the carboxyl group with respect to the phenyl
ring is in¯uenced by C6ÐH6Á Á ÁO3 and C8ÐH8Á Á ÁO1 inter-
actions (Tables 2 and 4). The interplanar angle between the
phenyl rings in (I) is 9.2 (1)ꢀ. In the case of (II), this angle
increases to 22.5 (1)ꢀ, due to the bulkier nature of the propyl
group compared with the ethyl group. By changing the ethyl
substituent for propyl, the space group is changed and the
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.049
wR(F2) = 0.124
S = 0.94
3352 re¯ections
183 parameters
H-atom parameters constrained
w = 1/[ꢄ2(Fo2) + (0.0693P)2]
where P = (Fo2 + 2Fc2)/3
(Á/ꢄ)max = 0.001
3
Ê
Áꢅmax = 0.30 e A
3
Ê
0.57 e A
Áꢅmin
=
Table 1
Selected geometric parameters (A, ) for (I).
ꢀ
Ê
S1ÐO4
S1ÐO2
1.434 (2)
1.434 (2)
O1ÐC7
C7ÐO3
1.218 (2)
1.309 (2)
3
Ê
volume per molecule increases by 26.9 A , corresponding to
O4ÐS1ÐC10
O2ÐS1ÐC10
O4ÐS1ÐC8
O2ÐS1ÐC8
O1ÐC7ÐO3
108.48 (9)
108.3 (1)
110.14 (9)
107.45 (9)
121.5 (2)
O1ÐC7ÐC1
O3ÐC7ÐC1
C2ÐC8ÐS1
C9ÐC8ÐS1
125.3 (2)
113.2 (2)
108.5 (1)
110.8 (1)
an increase of 7.98%.
The slight increases in the C7ÐC1ÐC2 [123.4 (2)ꢀ in (I)
and 123.5 (2)ꢀ in (II)] and C1ÐC2ÐC8 [123.7 (2)ꢀ in (I) and
123.1 (2)ꢀ in (II)] angles in both compounds, from the ideal
value of 120ꢀ, can be attributed to the steric interaction of the
C7 and C8 substituents. The slight difference in the C2ÐC8Ð
C9 bond angle between (I) and (II) is due to the slightly
O4ÐS1ÐC8ÐC2
O2ÐS1ÐC8ÐC2
O4ÐS1ÐC8ÐC9
75.2 (1)
55.3 (1)
51.0 (2)
O2ÐS1ÐC8ÐC9
O4ÐS1ÐC10ÐC15
O2ÐS1ÐC10ÐC15
178.6 (1)
15.3 (2)
145.2 (2)
ꢁ
o258 K. Sethu Sankar et al.
C15H14O4S and C16H16O4S
Acta Cryst. (2002). C58, o257±o259

organic compounds
Table 2
Hydrogen-bonding and short-contact geometry (A, ) for (I).
Table 4
Hydrogen-bonding and short-contact geometry (A, ) for (II).
ꢀ
ꢀ
Ê
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
C6ÐH6Á Á ÁO3
C8ÐH8Á Á ÁO1
O3ÐH3Á Á ÁO1i
0.93
0.98
0.82
2.32
2.10
1.87
2.665 (2)
2.895 (2)
2.680 (2)
102
138
172
C6ÐH6Á Á ÁO3
C8ÐH8Á Á ÁO1
C16ÐH16Á Á ÁO4
O3ÐH3Á Á ÁO1i
0.93
0.98
0.93
0.82
2.36
2.15
2.50
1.83
2.695 (3)
2.917 (3)
2.887 (3)
2.652 (3)
101
134
105
175
Symmetry code: (i) 1 x; y; z.
Symmetry code: (i) 1 x; 1 y; 1 z.
For compound (I), data collection: SMART (Siemens, 1996); cell
re®nement: SAINT (Siemens, 1996); data reduction: SAINT. For
compound (II), data collection: CAD-4 Software (Enraf±Nonius,
1989); cell re®nement: CAD-4 Software; data reduction: SDP (Frenz,
1989). For both compounds, program(s) used to solve structure:
SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:
SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP
(Zsolnai, 1997); software used to prepare material for publication:
SHELX97 and PARST (Nardelli, 1995).
Compound (II)
Crystal data
C16H16O4S
Mr = 304.35
Triclinic, P1
a = 7.4805 (10) A
Ê
b = 7.5125 (9) A
Z = 2
Dx = 1.390 Mg m
Mo Kꢁ radiation
3
Ê
Cell parameters from 25
re¯ections
c = 14.4853 (18) A
ꢂ = 2.8±25.0ꢀ
ꢃ = 0.24 mm
T = 293 (2) K
Ê
1
ꢁ = 94.634 (9)ꢀ
ꢀ = 91.807 (1)ꢀ
ꢆ = 116.020 (8)ꢀ
KSS thanks UGC, India, for the award of an FIP fellowship
for 2001±2002. DV thanks DST, India. SSSR thanks Universiti
Sains Malaysia for a visiting Postdoctoral Research Fellowship
and HKF would like to thank the Malaysian Government and
Universiti Sains Malaysia for research grant R&D No. 190-
9609-2801. The authors also thank Professor P. C. Srinivasan
for providing the samples for X-ray study.
Block, colourless
0.40 Â 0.30 Â 0.26 mm
3
Ê
V = 727.09 (16) A
Data collection
Enraf±Nonius CAD-4
diffractometer
w/2ꢂ scans
2625 measured re¯ections
2518 independent re¯ections
2004 re¯ections with I > 2ꢄ(I)
Rint = 0.016
ꢂ
max = 25ꢀ
h = 8 ! 8
k = 8 ! 8
l = 0 ! 17
3 standard re¯ections
frequency: 300 min
intensity decay: 1%
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: NA1557). Services for accessing these data are
described at the back of the journal.
Re®nement
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.040
wR(F2) = 0.107
S = 1.01
2518 re¯ections
w = 1/[ꢄ2(Fo2) + (0.0549P)2
+ 0.1743P]
References
where P = (Fo2 + 2Fc2)/3
(Á/ꢄ)max < 0.001
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Int. Ed. Engl. 34, 1555±1573.
3
Ê
Áꢅmax = 0.28 e A
3
Ê
0.19 e A
192 parameters
H-atom parameters constrained
Áꢅmin
=
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Ê
All H atoms were ®xed geometrically, with CÐH = 0.93±0.98 A
Ê
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Table 3
Selected geometric parameters (A, ) for (II).
ꢀ
Ê
S1ÐO2
S1ÐO4
S1ÐC11
1.437 (2)
1.438 (2)
1.767 (2)
O1ÐC7
O3ÐC7
1.220 (3)
1.311 (2)
O4ÐS1ÐC11
O2ÐS1ÐC8
O4ÐS1ÐC8
O1ÐC7ÐO3
108.1 (1)
106.8 (1)
108.8 (1)
121.8 (2)
O1ÐC7ÐC1
O3ÐC7ÐC1
C2ÐC8ÐS1
C9ÐC8ÐS1
124.5 (2)
113.7 (2)
105.6 (1)
111.9 (1)
O2ÐS1ÐC8ÐC2
O4ÐS1ÐC8ÐC2
C11ÐS1ÐC8ÐC2
O2ÐS1ÐC8ÐC9
O4ÐS1ÐC8ÐC9
C11ÐS1ÐC8ÐC9
O2ÐS1ÐC11ÐC12
62.6 (2)
66.3 (2)
178.1 (1)
170.6 (2)
60.5 (2)
55.1 (2)
48.9 (2)
O4ÐS1ÐC11ÐC12
C8ÐS1ÐC11ÐC12
O2ÐS1ÐC11ÐC16
O4ÐS1ÐC11ÐC16
C8ÐS1ÐC11ÐC16
S1ÐC11ÐC12ÐC13
S1ÐC11ÐC16ÐC15
178.7 (2)
65.2 (2)
131.2 (2)
1.4 (2)
114.7 (2)
179.6 (2)
178.3 (2)
È
Gottingen, Germany.
Siemens (1996). SMART and SAINT. Versions 4.0. Siemens Analytical X-ray
Instruments Inc., Madison, Wisconsin, USA.
Zsolnai, L. (1997). ZORTEP. University of Heidelberg, Germany.
ꢁ
Acta Cryst. (2002). C58, o257±o259
K. Sethu Sankar et al. C15H14O4S and C16H16O4S o259