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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) Å, while the S—O bond lengths are in the range 1.4417 (12)–1.457 (2) Å. 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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010401443X/jz1631sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010401443X/jz1631Isup2.hkl
Contains datablock I

CCDC reference: 248161

Comment top

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, trimethylammoniophenyl-4-thiol hexafluorophosphate, reacts with metal ions to form cluster complexes (Chen et al., 2004). The ready synthesis of such cluster complexes prompted a similar attempt at preparing a silver cluster complex, but the reaction with silver bromide in the presence of 4,4'-bipyridyldisulfide 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 thiosulfulate, these being limited to one aromatic (Boese et al., 1999) and six aliphatic (Cruz et al., 1995; Foust & Janickis, 1980; Keefe & Stewart, 1972; Okaya, 1996; Steudel et al., 1993; Zhang et al., 1985) examples. In all of these, an ammonium (+NH3 or +NH2) group interacts with the thiosulfate group through hydrogen bonds, and the sulfur–oxygen 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 distances are essentially identical [1.445 (2), 1.448 (2) and 1.456 (2) Å; Cruz et al., 1995]. The simple thiosulfate ion has been isolated in ammonium salts, for example, bis(adamantanium) thiosulfate (Jiang et al., 1998) and bis(tetraethylammonium) thiosulfate dihydrate (Leyten et al., 1988).

The most closely comparible compound is zwitterionic trimethylammoniophenyl-4-sulfonate, which is obtained from the thermally induced rearrangement of methyl dimethylaminophenyl-4-sulfonate (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). The compound 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 sulfur–oxygen distances in the two independent molecules [1.448 (3)–1.458 (3) Å; 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 O—S—O angle (113.98 °) is consistent with those reported for the thiosulfate complexes [Co(en)2Cl2](HOCH2)S2O3 (112.8 °; Foust & Janickis, 1980) and Me2HN(CH2S2O3)2Na (113.6 °; Zhang et al., 1985), and slightly greater than those in the (Me4N)2[Co(H2O)4(S2O3)2] complex (110.8 °; Alan et al., 1999). The S1—S2 distance [2.1137 (7) Å] is appreciably longer than those of coordinated thiosulfate ions that exhibit monodentate bonding through the S atoms only, such as (Me4N)2[Co(H2O)4(S2O3)2] [2.011 (2) Å] and trans- (Me4N)2[Ni(H2O)4(S2O3)2] [2.014 (1) Å; Alan et al., 1999], but slightly shorter than the S—S bond distance (2.155 Å) of HSSO3 (Karol & Ralf, 1992) and similar to the values for free alkyl thiosulfate ions, such as Me2HN(CH2S2O3)2Na [2.082 (1) Å; Zhang et al., 1985] and [Co(en)2Cl2](HOCH2)S2O3 [2.0779 (15) Å; Foust & Janickis, 1980]. The S—O distances in the S2O3 group range from 1.4417 (12) to 1.457 (2) Å, which indicates some S—O multiple-bond character [cf. Me2HN(CH2S2O3)2Na (1.433–1.455 Å; Zhang et al., 1985)], with the bonding is delocalized between atom S1 and the three O atoms. The mean S—O distance (1.446 Å) is comparable to those found in [Co(en)2Cl2](HOCH2)S2O3 (1.449 Å) and Me2HN(CH2S2O3)2Na (1.444 Å). The S2—C1 bond distance [1.776 (2) Å] is slightly shorter than those reported in other thiosulfate complexes, such as [Co(en)2Cl2](HOCH2)S2O3 [1.829 (4) Å] and Me2HN(CH2S2O3)2Na [1.814 (3) Å and 1.816 Å]. Ammonium atom N1 is sp3-hybridized, forming a cationic charge center, and all N—C bond lengths and C—N—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 α phase of trimethylammoniophenyl-4-sulfonate is aligned along a crytallographic axis (calculated dipole moment = 24.97 D; Sarma & Dunitz, 1990).

Experimental top

Trimethylammoniumphenyl-4-thiol hexafluorophosphate was synthesized according to the literature procedure (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 resulted after the mixture had been stirred briefly was treated with 4,4'-dipyridyldisulfide (0.044 g, 0.2 mmol) in acetonitrile (2 ml). Prismatic colorless crystals 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 reaction is reproducible. The dipole moments of trimethylammoniophenyl-4-sulfonate and trimethylammoniophenyl-4-thiosulfate were computed at PM3 level by using HYPERCHEM (Hypercube, 2001).

Refinement top

H atoms were located from a difference Fourier map and their positions were refined freely [C—H6 = 0.90 (2)–0.97 (4) Å], along with isotropic displacement parameters.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. An ORTEPII (Johnson, 1976) plot of C9H13NO3S2, with displacement ellipsoids at the 50% probability level. H atoms are drawn as spheres of arbitrary radii.
4-(Trimethylammonio)phenyl-4-thiosulfate top
Crystal data top
C9H13NO3S2F(000) = 260
Mr = 247.32Dx = 1.531 Mg m3
Orthorhombic, Pmn21Mo Kα radiation, λ = 0.71070 Å
Hall symbol: p 2ac -2Cell parameters from 2404 reflections
a = 9.0937 (11) Åθ = 3.6–27.5°
b = 5.6809 (6) ŵ = 0.48 mm1
c = 10.3830 (11) ÅT = 193 K
V = 536.39 (10) Å3Prism, colorless
Z = 20.30 × 0.30 × 0.25 mm
Data collection top
Rigaku Mercury
diffractometer
1291 independent reflections
Radiation source: fine-focus sealed tube1263 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.020
Detector resolution: 7.31 pixels mm-1θmax = 27.5°, θmin = 3.6°
ω scansh = 1110
Absorption correction: multi-scan
(Jacobson, 1998)
k = 77
Tmin = 0.869, Tmax = 0.889l = 1313
5598 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.023All H-atom parameters refined
wR(F2) = 0.060 w = 1/[σ2(Fo2) + (0.0351P)2 + 0.1062P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
1291 reflectionsΔρmax = 0.20 e Å3
107 parametersΔρmin = 0.26 e Å3
8 restraintsAbsolute structure: Flack (1983), 604 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.02 (8)
Crystal data top
C9H13NO3S2V = 536.39 (10) Å3
Mr = 247.32Z = 2
Orthorhombic, Pmn21Mo Kα radiation
a = 9.0937 (11) ŵ = 0.48 mm1
b = 5.6809 (6) ÅT = 193 K
c = 10.3830 (11) Å0.30 × 0.30 × 0.25 mm
Data collection top
Rigaku Mercury
diffractometer
1291 independent reflections
Absorption correction: multi-scan
(Jacobson, 1998)
1263 reflections with I > 2σ(I)
Tmin = 0.869, Tmax = 0.889Rint = 0.020
5598 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.023All H-atom parameters refined
wR(F2) = 0.060Δρmax = 0.20 e Å3
S = 1.06Δρmin = 0.26 e Å3
1291 reflectionsAbsolute structure: Flack (1983), 604 Friedel pairs
107 parametersAbsolute structure parameter: 0.02 (8)
8 restraints
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.50000.38765 (11)0.49997 (4)0.02167 (15)
S20.50000.63423 (9)0.34752 (5)0.02380 (15)
O10.36708 (14)0.2514 (2)0.48708 (14)0.0361 (3)
O20.50000.5471 (4)0.60992 (18)0.0304 (4)
N10.50000.0100 (3)0.12406 (17)0.0180 (4)
C10.50000.4377 (4)0.2145 (2)0.0192 (5)
C20.63165 (18)0.3659 (3)0.15927 (17)0.0227 (4)
C30.63226 (17)0.2256 (3)0.05058 (17)0.0236 (3)
C40.50000.1583 (3)0.0050 (2)0.0179 (4)
C50.50000.2466 (4)0.0864 (3)0.0307 (6)
C60.6330 (2)0.0554 (3)0.20634 (16)0.0272 (4)
H20.721 (3)0.422 (4)0.192 (2)0.042 (6)*
H30.720 (3)0.183 (4)0.014 (2)0.034 (5)*
H5A0.582 (3)0.272 (4)0.035 (2)0.043 (6)*
H6A0.714 (2)0.002 (3)0.164 (2)0.035 (5)*
H5B0.50000.334 (5)0.167 (4)0.045 (9)*
H6B0.639 (2)0.220 (4)0.228 (2)0.037 (6)*
H6C0.622 (2)0.021 (3)0.281 (2)0.028 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0214 (3)0.0295 (3)0.0142 (3)0.0000.0000.0017 (2)
S20.0300 (3)0.0230 (3)0.0184 (3)0.0000.0000.0022 (3)
O10.0379 (7)0.0444 (7)0.0260 (6)0.0174 (6)0.0006 (6)0.0000 (7)
O20.0297 (9)0.0431 (11)0.0182 (9)0.0000.0000.0047 (8)
N10.0206 (8)0.0179 (8)0.0156 (8)0.0000.0000.0009 (7)
C10.0229 (11)0.0204 (11)0.0143 (10)0.0000.0000.0018 (9)
C20.0178 (8)0.0292 (9)0.0212 (8)0.0013 (6)0.0042 (7)0.0025 (6)
C30.0178 (8)0.0308 (8)0.0222 (7)0.0054 (6)0.0006 (6)0.0031 (6)
C40.0214 (9)0.0191 (9)0.0131 (9)0.0000.0000.0034 (10)
C50.0472 (17)0.0195 (12)0.0255 (13)0.0000.0000.0037 (10)
C60.0263 (8)0.0368 (9)0.0184 (8)0.0016 (8)0.0063 (6)0.0015 (8)
Geometric parameters (Å, º) top
S1—O11.4417 (12)C2—C31.382 (2)
S1—O1i1.4417 (12)C2—H20.93 (3)
S1—O21.457 (2)C3—C41.387 (2)
S1—S22.1137 (7)C3—H30.91 (2)
S2—C11.776 (2)C4—C3i1.387 (2)
N1—C41.496 (3)C5—H5A0.92 (3)
N1—C6i1.5027 (19)C5—H5B0.97 (4)
N1—C61.5027 (19)C6—H6A0.91 (2)
N1—C51.509 (3)C6—H6B0.97 (2)
C1—C2i1.388 (2)C6—H6C0.90 (2)
C1—C21.388 (2)
O1—S1—O1i113.95 (11)C3—C2—H2119.4 (14)
O1—S1—O2113.99 (7)C1—C2—H2119.8 (14)
O1i—S1—O2113.99 (7)C2—C3—C4119.66 (15)
O1—S1—S2106.64 (6)C2—C3—H3119.7 (14)
O1i—S1—S2106.64 (6)C4—C3—H3120.6 (14)
O2—S1—S2100.06 (9)C3—C4—C3i120.2 (2)
C1—S2—S199.55 (8)C3—C4—N1119.90 (11)
C4—N1—C6i111.92 (11)C3i—C4—N1119.90 (11)
C4—N1—C6111.92 (11)N1—C5—H5A107.3 (14)
C6i—N1—C6107.15 (18)N1—C5—H5B106 (2)
C4—N1—C5109.26 (17)H5A—C5—H5B114.6 (16)
C6i—N1—C5108.23 (12)N1—C6—H6A109.0 (13)
C6—N1—C5108.23 (12)N1—C6—H6B110.4 (14)
C2i—C1—C2119.1 (2)H6A—C6—H6B112.7 (18)
C2i—C1—S2120.37 (11)N1—C6—H6C108.7 (13)
C2—C1—S2120.37 (11)H6A—C6—H6C110.4 (18)
C3—C2—C1120.66 (16)H6B—C6—H6C106 (2)
O1—S1—S2—C161.05 (6)C2—C3—C4—C3i2.0 (3)
O1i—S1—S2—C161.05 (6)C2—C3—C4—N1178.87 (16)
O2—S1—S2—C1180.0C6i—N1—C4—C3150.58 (17)
S1—S2—C1—C2i92.06 (19)C6—N1—C4—C330.3 (2)
S1—S2—C1—C292.06 (19)C5—N1—C4—C389.57 (16)
C2i—C1—C2—C30.2 (4)C6i—N1—C4—C3i30.3 (2)
S2—C1—C2—C3175.72 (15)C6—N1—C4—C3i150.58 (17)
C1—C2—C3—C40.9 (3)C5—N1—C4—C3i89.57 (16)
Symmetry code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5B···O2ii0.97 (4)2.42 (4)3.363 (3)165 (3)
C6—H6A···O1iii0.91 (2)2.55 (2)3.406 (2)158.0 (16)
C2—H2···O2iv0.93 (3)2.69 (3)3.4244 (17)136.5 (17)
Symmetry codes: (ii) x, y1, z1; (iii) x+1/2, y, z1/2; (iv) x+1/2, y+1, z1/2.

Experimental details

Crystal data
Chemical formulaC9H13NO3S2
Mr247.32
Crystal system, space groupOrthorhombic, Pmn21
Temperature (K)193
a, b, c (Å)9.0937 (11), 5.6809 (6), 10.3830 (11)
V3)536.39 (10)
Z2
Radiation typeMo Kα
µ (mm1)0.48
Crystal size (mm)0.30 × 0.30 × 0.25
Data collection
DiffractometerRigaku Mercury
diffractometer
Absorption correctionMulti-scan
(Jacobson, 1998)
Tmin, Tmax0.869, 0.889
No. of measured, independent and
observed [I > 2σ(I)] reflections
5598, 1291, 1263
Rint0.020
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.060, 1.06
No. of reflections1291
No. of parameters107
No. of restraints8
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.20, 0.26
Absolute structureFlack (1983), 604 Friedel pairs
Absolute structure parameter0.02 (8)

Computer programs: CrystalClear (Rigaku/MSC, 2001), CrystalClear, CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.

Selected geometric parameters (Å, º) top
S1—O11.4417 (12)N1—C61.5027 (19)
S1—O21.457 (2)N1—C51.509 (3)
S1—S22.1137 (7)C1—C21.388 (2)
S2—C11.776 (2)C2—C31.382 (2)
N1—C41.496 (3)C3—C41.387 (2)
O1—S1—O2113.99 (7)C6—N1—C5108.23 (12)
O1—S1—S2106.64 (6)C2—C1—S2120.37 (11)
O2—S1—S2100.06 (9)C3—C2—C1120.66 (16)
C1—S2—S199.55 (8)C2—C3—C4119.66 (15)
C4—N1—C6111.92 (11)C3—C4—N1119.90 (11)
C4—N1—C5109.26 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5B···O2i0.97 (4)2.42 (4)3.363 (3)165 (3)
C6—H6A···O1ii0.91 (2)2.55 (2)3.406 (2)158.0 (16)
C2—H2···O2iii0.93 (3)2.69 (3)3.4244 (17)136.5 (17)
Symmetry codes: (i) x, y1, z1; (ii) x+1/2, y, z1/2; (iii) x+1/2, y+1, z1/2.
 

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