Crystal structure of [4-(methylsulfanyl)phenyl]acetic acid

Article abstract of DOI:10.1007/s10870-009-9599-8

The title compound, C₉H₁₀O₂S, (I), crystallizes in the triclinic space group, P - 1, with unit cell parameters a = 6.2249(3), b = 7.3733(5), c = 19.5708(12), A, α = 86.746(5)°, β = 88.682(5)°, γ = 86.988(5)°, Z = 4. The molecule consists of a methyl sulfanyl group bonded to benzyl acetic acid at the 4 position crystallizing with two molecules in the asymmetric unit. The carboxylic acid group from the acetic acid moiety in these two molecules forms a classic O-H???O hydrogen bonded dimer with O???O distances of 2.673(2) and 2.646(2) A, in a R₂² (8) graph-set motif which link the molecules into pairs around inversion centers in the unit cell. The dihedral angles between the mean planes of the R₂ ² (8) graph-set motif with the mean planes of the two nearby benzyl groups within the same dimer in the unit cell are 64.1(6)° and 71.3(4)°, respectively. Within the same dimer the dihedral angle between the two benzyl groups is 45.2(1)°. The structure is supported by a weak intermolecular C-H???Cg π-ring interaction and gives support to molecular packing stability in the unit cell. Comparison to a MOPAC AM1 computational calculation provides support to these observations.

Full text of DOI:10.1007/s10870-009-9599-8

J Chem Crystallogr (2010) 40:25–28
DOI 10.1007/s10870-009-9599-8
ORIGINAL PAPER
Crystal Structure of [4-(Methylsulfanyl)Phenyl]Acetic Acid
Jerry P. Jasinski Æ Ray J. Butcher Æ M. T. Swamy Æ
B. Narayana Æ B. K. Sarojini Æ H. S. Yathirajan
Received: 7 December 2008 / Accepted: 1 August 2009 / Published online: 15 August 2009
Ó Springer Science+Business Media, LLC 2009
Abstract The title compound, C9H10O2S, (I), crystallizes
in the triclinic space group, P - 1, with unit cell parame-
˚
ters a = 6.2249(3), b = 7.3733(5), c = 19.5708(12), A,
supported by a weak intermolecular C–HÁÁÁCg p-ring
interaction and gives support to molecular packing stability
in the unit cell. Comparison to a MOPAC AM1 computa-
tional calculation provides support to these observations.
a = 86.746(5)°, b = 88.682(5)°, c = 86.988(5)°, Z = 4.
The molecule consists of a methyl sulfanyl group bonded
to benzyl acetic acid at the 4 position crystallizing with two
molecules in the asymmetric unit. The carboxylic acid
group from the acetic acid moiety in these two molecules
forms a classic O–HÁÁÁO hydrogen bonded dimer with
Keywords Acetic acid Á Methyl sulfanyl Á
Carboxylic acid Á Dimer Á R22 (8) graph-set motif Á
MOPAC
2
˚
OÁÁÁO distances of 2.673(2) and 2.646(2) A, in a R2 (8)
graph-set motif which link the molecules into pairs around
inversion centers in the unit cell. The dihedral angles
between the mean planes of the R22 (8) graph-set motif with
the mean planes of the two nearby benzyl groups within the
same dimer in the unit cell are 64.1(6)° and 71.3(4)°,
respectively. Within the same dimer the dihedral angle
between the two benzyl groups is 45.2(1)°. The structure is
Introduction
Phenylacetic acids serve as an ingredient in perfume to
provide honey-like odor. It is found as a moiety in some
alkaloids and plant hormone and is formed as catabolite of
phenylalanine. In the toluic acid nomenclature system,
phenylacetic acid is an alpha-toluic acid in which one of
the hydrogen atoms in the methyl group has been substi-
tuted for instead of a substitution in the benzene ring.
Substituted phenylacetic acid molecules at the alpha posi-
tion and phenylacetate esters can serve as a drug with a
wide variety of effects including anticholinergic, musca-
rinic antagonist as well as an antidote to cholinesterase
inhibitors or toxins. Cycloplegic and mydriatic phenyla-
cetic acid is used to prepare a nonsteroidal anti-inflam-
matory drug like diclofenac [1, 2]. It is used the
manufacture of penicillin. Mandelic acid and phenylgly-
collic acid can be produced from phenylchloracetic acid. A
related compound, indole-3-acetic acid, which promotes
cell elongation in plants, has been isolated from plants and
has served as a stimulus to search for similar compounds of
related structure thereby creating renewed interest in
substituted phenylacetic acids. Structures of few related
acids are known via: phenlyacetic acid [3], (2-ethoxy-5-
indanyl)acetic acid [4], 2-methoxy-2-phenylacetic acid [5],
J. P. Jasinski (&)
Department of Chemistry, Keene State College, 229 Main Street,
Keene, NH 03435-2001, USA
e-mail: jjasinski@keene.edu
R. J. Butcher
Department of Chemistry, Howard University,
525 College Street NW, Washington, DC 20059, USA
M. T. Swamy Á H. S. Yathirajan
Department of Studies in Chemistry, University of Mysore,
Manasagangotri, Mysore 57 006, India
B. Narayana
Department of Studies in Chemistry, Mangalore University,
Mangalagangotri, Mangalore 574 199, India
B. K. Sarojini
Department of Chemistry, P.A. College of Engineering,
Mangalore 574 153, India
123

26
J Chem Crystallogr (2010) 40:25–28
p-nitrophenylacetic acid [6], indoprofen: 2-[4-(1-oxo-2-
isoindolinyl)phenyl]propionic acid [7], [4-(phenoxy-
methyl)phenyl]acetic acid [8], [4-(benzyloxy)phenyl]acetic
acid [9] and 3-(2-furyl)-2-phenylpropenoic acid [10]. A
new derivative, [4-(methylsulfanyl)phenyl]acetic acid, (I),
is synthesized and its crystal structure is reported here.
sulphuric acid diluted with 14 mL water). The reaction
mixture was diluted with 30 mL water and cooled to
273 K. The separated solid was filtered and recrystallized
from acetone. mp: 370–371 K. Composition for C9H10O2S:
Found (Calculated): C: 59.27 (59.32); H: 5.49 (5.53); S:
17.53% (17.59%).
Structure Determination and Refinement
Experimental
X-ray data for (I) was collected with an Oxford Diffraction
[4-(Methylsulfanyl)phenyl]acetonitrile (4.89 g, 0.03 mol)
was refluxed for 1 h with dilute sulfuric acid (15 mL conc.
Gemini R CCD area detector using CrysAlisPro software
˚
and graphite-monochromated Mo-Ka (k = 0.71073 A) at
Fig. 1 ORTEP drawing of (I) showing the atom numbering scheme
of the asymmetric unit containing two molecules and 50% probability
displacement ellipsoids of non-H atoms. Dashed lines indicate
intermolecular hydrogen bonds between carboxyl acceptor atoms
O(1) and O(2) (O(1)ÁÁÁH(2B)–O(2)) which form an R22 (8) graph-set
motif arrangement
Fig. 2 The molecular packing for (I) viewed down the b axis. Dashed
lines indicate both intermolecular hydrogen bonds between carboxyl
acceptor atoms O(1A)ÁÁÁO(2B) and O(1B)ÁÁÁO(2A) (O(2B)ÁÁÁH(1A)–
O(1A) and (O(2A)ÁÁÁH(1B)–O(1B)) forming a dimer and weak
intermolecular C–HÁÁÁO interactions (C(2A)–H(2AA)ÁÁÁO(2B)#1;
C(2A)–H(2AB)ÁÁÁO(2B)#2; C(2B)–H(2BA)ÁÁÁO(2A); C(2B)–H(2BB)
ÁÁÁO(2A)#3 where #1 = -1 ? x, -1 ? y, z; #2 = x, -1 ? y, z;
#3 = 1 ? x, y, z) which provide support for the classic O–HÁÁÁO
hydrogen bonded dimer molecules to become arranged into chains
along the (101) plane of the unit cell
123

J Chem Crystallogr (2010) 40:25–28
27
200(2) K. The structure was solved by direct methods
using SHELXS97 [11] and all of the non-hydrogen atoms
were refined anisotropically by full-matrix least-squares on
F2 using SHELXL97 [11]. The hydrogen atoms were
placed in their calculated positions and included in the
refinement using the riding model. An absorption correc-
tion was performed using CrysAlis RED and all calcula-
tions, including Figs. 1 and 2, were performed using
SHELXTL [12]. Crystal and experimental data for (I) are
listed in Table 1. Scheme 1 for the molecular structure of
(I) is shown. Bond lengths and bond angles are all within
expected ranges, Table 2 [13].
Results and Discussion
The title compound, C9H10O2S, consists of a methyl sul-
fanyl group bonded to benzyl acetic acid at the 4 position
crystallizing with two molecules in the asymmetric unit.
The carboxylic acid group from the acetic acid moiety in
these two molecules forms a classic O–HÁÁÁO hydrogen
bonded dimer with O(1A)ÁÁÁO(2B) and O(1B)ÁÁÁO(2A) dis-
˚
tances of 2.673(2) and 2.646(2) A, respectively, (Table 3)
in a R22 (8) graph-set motif [14] which link the molecules
into pairs around inversion centers in the unit cell (Fig. 1).
The O–HÁÁÁO hydrogen-bonded interactions involving these
pairs are very strong and stabilize molecular packing of
these dimers into a unique assembly. The torsion angles of
the two carboxylic acid groups that form the dimer indicate
that the plane of the R22 (8) graph-set motif deviates slightly
from planarity (O1A–C1A–C2A–C3A, 174.62(16); O2A–
C1A–C2A–C3A,-6.1(3); O1B–C1B–C2B–C3B, -177.41
(16); O2B–C1B–C2B–C3B, 2.3(3)). This is supported by
the calculation of the dihedral angle between the mean
planes of the carboxyl groups forming the dimer which is
9.7(3)°. The dihedral angles between the mean planes of the
R22 (8) graph-set motif with the mean planes of the two
nearby benzyl groups within the same dimer in the unit cell
are 64.1(6)° and 71.3(4)°, respectively. Within the same
dimer the dihedral angle between the two benzyl groups is
45.2(1)°. The distance between the centroids of adjacent
Table 1 Crystal and experimental data for (I)
Formula
C9H10O2S
182.23
Formula weight
Crystal color, habit
Crystal size (mm)
Crystal system
Space group, Z
Temperature (K)
Colorless, chunk
0.53 9 0.46 9 0.32
Triclinic
P - 1, 4
200(2)
˚
a (A)
6.2249(3)
7.3733(5)
19.5708(12)
86.746(5)
88.682(5)
86.988(5)
906.39(9)
384
˚
b (A)
2
˚
c (A)
˚
nearly parallel R2 (8) graph-set motif ‘s is 4.99(2) A with a
a (°)
b (°)
c (°)
slippage angle of 49.6(7)° providing a small effect on
molecular packing from these groups in the unit cell.
The structure is supported by a weak intermolecular
C–HÁÁÁCg2 p-ring interaction at x, -1 ? y, z, where
Cg2 = center of gravity of a benzene ring (C(3B)–
3
˚
Volume (A )
F(000)
Absorption coef (mm-1
˚
C(8B), C(8A)ÁÁÁCg2 = 3.630(9) A, C(8A)–H(18AA)ÁÁÁ
)
0.316
Dcalc (Mg m-3
)
1.352
Cg2 = 126.(1)°), and gives support to molecular packing
stability in the unit cell.
No. of reflections
[I [ 2r(I)]
7124
A MOPAC AM1 calculation was performed on the
C9H10O2S dimer with WebMO Pro [15] (AM1 (Austin
Model 1) approximation together with the Hartree-Fock
closed-shell (restricted) wavefunction was used and mini-
2hmax (°) with Mo Ka
R, Rw [I [ 2r(I)]
69.6
0.0737, 0.1760
0.602/-0.315
-3
˚
(Dq)max/min (e A
GOF on F2
)
1.037
mizations were teminnated at an r.m.s. gradient of less than
˚
0.01 kJ mol-1
A
-1). Starting geometries were taken from
Measurement
Program system
GEMINI (Oxford Diffraction 2007)
CrysAlisPro
X-ray refinement data. As a result the only bond lengths
that changed significantly were those for C(6A)–S(1A)
˚
(1.761(2) vs.(1.692) A) and C(6B)–S(1B) (1.759(2) vs.
Structure determination
Refinement
SHELXS97
Full-matrix least-squares on F2
(SHELXL97)
˚
(1.692) A) which were shortened somewhat. However, a
number of angles and torsion angles show significant dif-
ferences when compared to the values from the crystal
structure which are listed in Table 2. The angles and tor-
sion angles associated with the carboxyl group from each
molecule that form the dimer through the R22 (8) graph-set
motif have changed significantly causing an out-of-plane
twist away from planarity. The dihedral angle between the
CN
COOH
H3C
S
H3C
S
Scheme 1 Chemical synthesis of the title compound, C9H10O2S, (I)
123

28
J Chem Crystallogr (2010) 40:25–28
˚
Table 2 Selected geometric parameters for (I) (A, °)
C(1A)–O(1A)
1.317(2)
(1.358)a
(1.357)a
(1.498)a
(1.692)a
(117.01)a
(113.20)a
(129.76)a
(106.08)a
(142.21)a
(-39.94)a
(178.73)a
C(1A)–O(2A)
1.219(2)
(1.238)a
(1.237)a
(1.501)a
(1.692)a
(117.29)a
(113.46)a
(129.22)a
(105.95)a
(136.67)a
(-45.47)a
(0.63)a
C(1B)–O(1B)
1.322(2)
C(1B)–O(2B)
1.216(2)
C(1A)–C(2A)
1.504(3)
C(1B)–C(2B)
1.500(3)
C(6A)–S(1A)
1.761(2)
C(6B)–S(1B)
1.759(2)
O(1A)–C(1A)–O(2A)
O(1A)–C(1A)–C(2A)
O(2A)–C(1A)–C(2A)
C(6A)–S(1A)–C(9A)
O(1A)–C(1A)–C(2A)–C(3A)
O(2A)–C(1A)–C(2A)–C(3A)
C(5A)–C(6A)–S(1A)–C(9A)
a
123.15(18)
113.22(16)
123.62(18)
103.95(12)
174.62(16)
-6.1(3)
O(1B)–C(1B)–O(2B)
O(1B)–C(1B)–C(2B)
O(2B)–C(1B)–C(2B)
C(6B)–S(1B)–C(9B)
O(1B)–C(1B)–C(2B)–C(3B)
O(2B)–C(1B)–C(2B)–C(3B)
C(5B)–C(6B)–S(1B)–C(9)
122.98(18)
112.71(16)
124.31(18)
103.98(12)
-100.6(3)
145.55(18)
-173.23(18)
-172.71(16)
˚
MOPAC computation results (A, °) [15]
˚
Table 3 Hydrogen bonds for (I) (A and °)
Cambridge Crystallographic Date Center, CCDC: 26091.
Copies of this information may be obtained free of charge
from the Director, CCDC, 12 Union Road, Cambridge,
CB2 1EZ (fax: ?44-1223-336033; email: deposit@ccdc.
cam.uk or at: http://www.ccdc.cam.ac.uk).
D–HÁÁÁA
d(D–H) d(HÁÁÁA) d(DÁÁÁA) \(DHA)
O(1A)–H(1A)ÁÁÁO(2B)
O(1B)–H(1B)ÁÁÁO(2A)
0.84
0.84
1.84
1.81
2.47
2.54
2.50
2.49
2.673(2) 174.8
2.646(2) 175.4
3.461(1) 175.1
3.406(4) 146.1
3.475(5) 167.1
3.454(7) 164.1
C(2A)–H(2AA)ÁÁÁO(2B)#1 0.99
C(2A)–H(2AB)ÁÁÁO(2B)#2 0.99
Acknowledgments MTS thanks the University of Mysore for use of
their research facilities. RJB acknowledges the NSF MRI pro-
gram (grant No. CHE-0619278) for funds to purchase an X-ray
diffractometer.
C(2B)–H(2BA)ÁÁÁO(2A)
C(2B)–H(2BB)ÁÁÁO(2A)#3 0.99
0.99
Symmetry transformations used to generate equivalent atoms: #1 -
1 ? x, -1 ? y, z; #2 x, -1 ? y, z; #3 1 ? x, y, z
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Supporting Information Available
X-ray crystallographic files, in Cif format, for the structure
determinations of (I) (711542) has been deposited with the
123