S-[4-(Trimethylammonio)phenyl] thiosulfate, an aromatic organic thiosulfate

Article abstract of DOI:10.1107/S010827010401443X

The title compound, C₉H₁₃NO₃S₂, exists as a zwitterion with crystallographic mirror symmetry. The central S atom of the S₂O₃ group adopts a slightly distorted tetrahedral coordination geometry. The S-S bond length is 2.1137 (7) A, while the S-O bond lengths are in the range 1.4417 (12)-1.457 (2) A. The zwitterions in the crystal adopt a head-to-tail arrangement, which leads to the formation of a three-dimensional network through C-H ... O hydrogen bonds.

Full text of DOI:10.1107/S010827010401443X

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
has been isolated in ammonium salts, for example, bis-
(adamantanium) thiosulfate (Jiang et al., 1998) and bis-
(tetraethylammonium) thiosulfate dihydrate (Leyten et al.,
1988).
ISSN 0108-2701
S-[4-(Trimethylammonio)phenyl]
thiosulfate, an aromatic organic
thiosulfate
The compound that is most closely comparable to (I) is
zwitterionic 4-(trimethylammonio)benzenesulfonate, (II)
(Even et al., 1999), which is obtained from the thermally
induced rearrangement of methyl 4-(dimethylamino)-
benzenesulfonate (Kusto et al., 1999). The rearrangement has
been investigated theoretically (Oda & Sato, 1998) and the
driving force has been attributed to the large electric dipolar
interactions among the zwitterions in the resulting product
(Oda & Sato, 1997). Compound (II) exhibits three phases, viz.
Pcn2 at low temperature, Pca21 at room temperature and P42/
ncm at high temperature (Boese et al., 1999). For the low-
temperature phase, the SÐO distances in the two independent
Jin-Xiang Chen,a Qing-Feng Xu,a Yong Zhang,a
Sharifuddin M. Zain,b Seik Weng Ngb and Jian-Ping
Langa,c
*
aSchool of Chemistry and Chemical Engineering, Suzhou University, 1 Shizi Street,
Suzhou 215006, Jiangsu, People's Republic of China, bDepartment of Chemistry,
University of Malaya, 50603 Kuala Lumpur, Malaysia, and cState Key Laboratory of
Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese
Academy of Sciences, Shanghai 200032, Jiangsu, People's Republic of China
Correspondence e-mail: jplang@suda.edu.cn
Received 11 May 2004
Accepted 14 June 2004
Online 21 July 2004
Ê
molecules [1.448 (3)±1.458 (3) A; Boese et al., 1999] suggest
delocalization of the negative charge over the SO3 unit.
Compound (I), which crystallizes with imposed mirror
symmetry, may be viewed as an arylated thiosulfate product.
Atom S1 in the S2O3 group has a slightly distorted tetrahedral
coordination geometry; the mean OÐSÐO angle (113.98ꢀ;
Table 1) is consistent with those reported for the thiosulfate
complexes [CoCl2(en)2](HOCH2)S2O3 (en is ethylenedi-
The title compound, C9H13NO3S2, exists as a zwitterion with
crystallographic mirror symmetry. The central S atom of the
S2O3 group adopts a slightly distorted tetrahedral coordina-
Ê
tion geometry. The SÐS bond length is 2.1137 (7) A, while the
Ê
SÐO bond lengths are in the range 1.4417 (12)±1.457 (2) A.
amine; 112.8ꢀ; Foust
& Janickis, 1980) and Me2HN-
The zwitterions in the crystal adopt a head-to-tail arrange-
ment, which leads to the formation of a three-dimensional
network through CÐHÁ Á ÁO hydrogen bonds.
(CH2S2O3)2Na (113.6ꢀ; Zhang et al., 1985), and slightly greater
than those in the (Me4N)2[Co(S2O3)2(H2O)4] complex (110.8ꢀ;
Alan & Michael, 1999). The S1ÐS2 distance in (I)
Ê
[2.1137 (7) A] is appreciably longer than those of coordi-
nated thiosulfate ions that exhibit monodentate bonding
through the S atoms only, such as in (Me4N)2[Co(S2O3)2-
Ê
(H2O)4] [2.011 (2) A] and trans-(Me4N)2[Ni(S2O3)2(H2O)4]
Ê
[2.014 (1) A; Alan & Michael, 1999], but slightly shorter than
Ê
the SÐS bond distance (2.155 A) of HSSO3 (Karol & Ralf,
1992) and similar to the values for free alkyl thiosulfate ions,
Ê
such as Me2HN(CH2S2O3)2Na [2.082 (1) A; Zhang et al.,
Comment
Zwitterionic organic compounds having a negatively charged
thiolate end readily coordinate to metal ions to form metal
thiolates (Ahmed et al., 1998). One such reactant, 4-(tri-
methylammonio)benzenethiol hexa¯uorophosphate, reacts
with metal ions to form cluster complexes (Chen et al., 2004).
The ready synthesis of such cluster complexes prompted an
attempt at preparing a silver cluster complex, but the reaction
with silver bromide in the presence of 4,40-bipyridyl disul®de
furnished instead the title compound, (I) (Fig. 1), which is yet
another zwitterionic compound. The structure of (I) is a rare
example of an organic thiosulfate, these being limited to one
aromatic (Boese et al., 1999) and six aliphatic examples (Cruz
et al., 1995; Foust & Janickis, 1980; Keefe & Stewart, 1972;
Okaya, 1966; Steudel et al., 1993; Zhang et al., 1985). In all of
these, an ammonium ( NH3 or >NH2) group interacts with
the thiosulfate group through hydrogen bonds, and the SÐO
distances in the thiosulfate unit are similar to one another, in
agreement with the delocalized nature of this group; for
example, in CH3NH2CH(CH3)CH(C6H5)S2O3, the three SÐO
distances are essentially identical [1.445 (2), 1.448 (2) and
Ê
1985] and [CoCl2(en)2]HOCH2S2O3 [2.0779 (15) A; Foust &
Figure 1
An ORTEPII (Johnson, 1976) plot of (I), with displacement ellipsoids at
the 50% probability level. H atoms are drawn as spheres of arbitrary
radii.
Ê
1.456 (2) A; Cruz et al., 1995]. The simple thiosulfate ion
o572 # 2004 International Union of Crystallography
DOI: 10.1107/S010827010401443X
Acta Cryst. (2004). C60, o572±o574

organic compounds
Table 1
Selected geometric parameters (A, ).
Janickis, 1980]. The SÐO distances in the S2O3 group in (I)
Ê
range from 1.4417 (12) to 1.457 (2) A, which indicates some
ꢀ
Ê
Ê
SÐO multiple-bond character [cf. 1.433±1.455 A in
Me2HN(CH2S2O3)2Na; Zhang et al., 1985], with the bonding
delocalized between atom S1 and the three O atoms. The
S1ÐO1
S1ÐO2
S1ÐS2
S2ÐC1
N1ÐC4
1.4417 (12)
1.457 (2)
2.1137 (7)
1.776 (2)
1.496 (3)
N1ÐC6
N1ÐC5
C1ÐC2
C2ÐC3
C3ÐC4
1.5027 (19)
1.509 (3)
1.388 (2)
1.382 (2)
1.387 (2)
Ê
mean SÐO distance in (I) (1.446 A) is comparable to those
Ê
found in [CoCl2(en)2]HOCH2S2O3 (1.449 A) and Me2-
Ê
HN(CH2S2O3)2Na (1.444 A). The S2ÐC1 bond distance
Ê
[1.776 (2) A] is slightly shorter than those reported in other
thiosulfate complexes, such as [CoCl2(en)2]HOCH2S2O3
O1ÐS1ÐO2
O1ÐS1ÐS2
O2ÐS1ÐS2
C1ÐS2ÐS1
C4ÐN1ÐC6
C4ÐN1ÐC5
113.99 (7)
106.64 (6)
100.06 (9)
99.55 (8)
111.92 (11)
109.26 (17)
C6ÐN1ÐC5
C2ÐC1ÐS2
C3ÐC2ÐC1
C2ÐC3ÐC4
C3ÐC4ÐN1
108.23 (12)
120.37 (11)
120.66 (16)
119.66 (15)
119.90 (11)
Ê
[1.829 (4) A] and Me2HN(CH2S2O3)2Na [1.814 (3) A and
Ê
3
1.816 A]. Ammonium atom N1 is sp hybridized, forming a
Ê
cationic charge center, and all NÐC bond lengths and CÐNÐ
C angles are normal.
The zwitterions in the crystal stack in a head-to-tail manner,
parallel to the polar c axis, via hydrogen bonds from the
methyl H atoms to the O atoms of the S2O3 group (Table 2),
thereby forming a three-dimensional network.
The dipole moment lies approximately along the vector
from the N atom to the single-bonded O atom (dipole
moment = 26.78 D) but is not parallel to the c axis. In contrast,
the dipole moment of the ꢀ phase of 4-(trimethylammonio)-
benzenesulfonate is aligned along a crystallographic axis
(calculated dipole moment = 24.97 D; Sarma & Dunitz, 1990).
Table 2
Hydrogen-bonding geometry (A, ).
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
C5ÐH5BÁ Á ÁO2i
C6ÐH6AÁ Á ÁO1ii
C2ÐH2Á Á ÁO2iii
0.97 (4)
0.91 (2)
0.93 (3)
2.42 (4)
2.55 (2)
2.69 (3)
3.363 (3)
3.406 (2)
3.4244 (17)
165 (3)
158.0 (16)
136.5 (17)
1
1
.
Symmetry codes: (i) x; y 1; z 1; (ii) ‡ x; y; z 12; (iii) 21 ‡ x; 1 y; z
2
2
Re®nement
Re®nement on F2
R[F2 > 2ꢃ(F2)] = 0.023
wR(F2) = 0.060
S = 1.06
1291 re¯ections
w = 1/[ꢃ2(F2o) + (0.0351P)2
+ 0.1062P]
where P = (F2o + 2Fc2)/3
(Á/ꢃ)max < 0.001
Experimental
3
Ê
4-(Trimethylammonio)benzenethiol hexa¯uorophosphate was syn-
thesized according to the procedure of DePamphilis et al. (1974). The
resulting compound (0.125 g, 0.4 mmol) in methanol (5 ml) was
neutralized with excess triethylamine (0.25 ml); the solution was then
reacted with silver bromide powder (0.038 g, 0.2 mmol). The clear
colorless solution that formed after the mixture had been stirred
brie¯y was treated with 4,40-dipyridyl disul®de (0.044 g, 0.2 mmol) in
acetonitrile (2 ml). Prismatic colorless crystals were separated from
the orange solution after several days in about 20% yield. The
crystals were washed with ether. Analysis found: C 43.52, H 5.18, N
5.32%; calculated for C9H13NO3S2: C 43.70, H 5.28, N 5.66%. IR
(KBr, cm 1): 1488 (s), 1217 (s), 1190 (s), 1024 (s), 1009 (s), 609 (s), 525
(m). Although the compound is not the intended product, the reac-
tion is reproducible. The dipole moments of 4-(trimethylammonio)-
benzenesulfonate and (I) were computed at the PM3 level using
HyperChem (Hypercube, 2001).
Áꢄmax = 0.20 e A
3
Ê
0.26 e A
107 parameters
All H-atom parameters re®ned
Áꢄmin
=
Absolute structure: Flack (1983),
604 Friedel pairs
Flack parameter = 0.02 (8)
H atoms were located from a difference Fourier map and their
Ê
positions were re®ned freely [CÐH = 0.90 (2)±0.97 (4) A], along with
their isotropic displacement parameters.
Data collection: CrystalClear (Molecular Structure Corporation
and Rigaku, 2001); cell re®nement: CrystalClear; data reduction:
CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve
structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne
structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
ORTEPII (Johnson, 1976); software used to prepare material for
publication: SHELXL97.
The authors thank the National Natural Science Foundation
of China (grant No. 20271036), the NSF of the Education
Committee of Jiangsu Province (grant No. 02 KJB150001), the
Shanghai Institute of Organic Chemistry (grant No. 04-31), the
Key Laboratory of Organic Synthesis of Jiangsu Province
(grant No. JSK001) and the University of Malaya for
supporting this study.
Crystal data
C9H13NO3S2
Mr = 247.32
Orthorhombic, Pmn21
Ê
a = 9.0937 (11) A
Ê
b = 5.6809 (6) A
c = 10.3830 (11) A
Ê
V = 536.39 (10) A
Mo Kꢀ radiation
Cell parameters from 2404
re¯ections
ꢁ = 3.6±27.5ꢀ
1
ꢂ = 0.48 mm
T = 193 (2) K
Ê
3
Prism, colorless
0.30 Â 0.30 Â 0.25 mm
Z = 2
Dx = 1.531 Mg m
3
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: JZ1631). Services for accessing these data are
described at the back of the journal.
Data collection
Rigaku Mercury diffractometer
! scans
Absorption correction: multi-scan
(Jacobson, 1998)
Tmin = 0.869, Tmax = 0.889
5598 measured re¯ections
1291 independent re¯ections
1263 re¯ections with I > 2ꢃ(I)
Rint = 0.020
ꢁmax = 27.5ꢀ
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Jin-Xiang Chen et al. C9H13NO3S2 o573

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o574 Jin-Xiang Chen et al.
C9H13NO3S2
Acta Cryst. (2004). C60, o572±o574