supplementary materials
2-[(2-Carboxyphenyl)sulfanyl]acetic acid
The title compound, C9H8O4S, affords a zigzig chain in the crystal structure by intermolecular O-H
O hydrogen bonds. The molecular geometry suggests that extensive but not uniform ![[pi]](/logos/entities/pi_rmgif.gif)
-electron delocalization is present in the benzene ring and extends over the exocyclic C-S and C-C bonds.
To an aqueous solution of 2-thiobenzoic acid (1.54 g, 10.0 mmol) and NaOH (0.80 g, 20.0 mmol) were sequentially added the aqueous solution of chloroactic acid
(2.835 g, 30.0 mmol) and NaOH (1.400 g, 35.0 mmol). After stirring for 4 h at
353 K under nitrogen atmosphere, the mixture was cooled to room temperature
slowly. Adjusted the pH to 2 by adding 1.0 mol/L HCl, the pink deposit
appeared rapidly. The solids were filtered and washed with water. The single
crystals suitable for X-ray diffraction were obtained by the recrystallization
of sieved solid in the ethanol.
The H atoms bonded to C atoms were positioned geometrically [aromatic C—H =
0.93 Å and aliphatic C—H = 0.97 Å, Uiso(H) =
1.2Ueq(C)]. The H atoms bonded to O atoms were located in a
difference Fourier map and refined freely.
Data collection: APEX2 (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
2-[(2-Carboxyphenyl)sulfanyl]acetic acid
top
Crystal data top
| C9H8O4S | Z = 2 |
| Mr = 212.22 | F(000) = 220 |
| Triclinic, P1 | Dx = 1.517 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 5.1786 (5) Å | Cell parameters from 5343 reflections |
| b = 9.2973 (9) Å | θ = 2.1–27.7° |
| c = 10.4776 (11) Å | µ = 0.33 mm−1 |
| α = 69.980 (4)° | T = 296 K |
| β = 81.959 (6)° | Block, colourless |
| γ = 79.732 (6)° | 0.33 × 0.24 × 0.15 mm |
| V = 464.69 (8) Å3 | |
Data collection top
Bruker APEXII
diffractometer | 2110 independent reflections |
| Radiation source: fine-focus sealed tube | 1941 reflections with I > 2σ(I) |
| graphite | Rint = 0.024 |
| ω scans | θmax = 27.7°, θmin = 2.1° |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | h = −6→6 |
| Tmin = 0.910, Tmax = 0.952 | k = −12→11 |
| 6609 measured reflections | l = −13→12 |
Refinement top
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.074 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.222 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.19 | w = 1/[σ2(Fo2) + (0.0736P)2 + 1.2589P]
where P = (Fo2 + 2Fc2)/3 |
| 2110 reflections | (Δ/σ)max < 0.001 |
| 133 parameters | Δρmax = 0.65 e Å−3 |
| 2 restraints | Δρmin = −0.34 e Å−3 |
Crystal data top
| C9H8O4S | γ = 79.732 (6)° |
| Mr = 212.22 | V = 464.69 (8) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 5.1786 (5) Å | Mo Kα radiation |
| b = 9.2973 (9) Å | µ = 0.33 mm−1 |
| c = 10.4776 (11) Å | T = 296 K |
| α = 69.980 (4)° | 0.33 × 0.24 × 0.15 mm |
| β = 81.959 (6)° | |
Data collection top
Bruker APEXII
diffractometer | 1941 reflections with I > 2σ(I) |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | Rint = 0.024 |
| Tmin = 0.910, Tmax = 0.952 | θmax = 27.7° |
| 6609 measured reflections | Standard reflections: 0 |
| 2110 independent reflections | |
Refinement top
| R[F2 > 2σ(F2)] = 0.074 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.222 | Δρmax = 0.65 e Å−3 |
| S = 1.19 | Δρmin = −0.34 e Å−3 |
| 2110 reflections | Absolute structure: ? |
| 133 parameters | Flack parameter: ? |
| 2 restraints | Rogers parameter: ? |
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| | x | y | z | Uiso*/Ueq | |
| S1 | 0.2028 (2) | 0.36823 (12) | 0.11601 (11) | 0.0417 (3) | |
| O1 | −0.0678 (11) | 0.4660 (9) | 0.3612 (6) | 0.116 (2) | |
| O2 | 0.2828 (9) | 0.5474 (7) | 0.3870 (5) | 0.0891 (16) | |
| H2 | 0.173 (12) | 0.569 (10) | 0.449 (6) | 0.107* | |
| O3 | 0.2508 (7) | −0.1074 (4) | 0.1122 (4) | 0.0549 (9) | |
| H3 | 0.127 (8) | −0.107 (7) | 0.067 (5) | 0.066* | |
| O4 | 0.0891 (7) | 0.1410 (4) | 0.0369 (3) | 0.0506 (8) | |
| C1 | 0.4065 (8) | 0.0579 (5) | 0.2004 (4) | 0.0383 (9) | |
| C2 | 0.5712 (9) | −0.0691 (6) | 0.2747 (5) | 0.0482 (10) | |
| H2A | 0.5667 | −0.1659 | 0.2682 | 0.058* | |
| C3 | 0.7421 (10) | −0.0540 (7) | 0.3583 (5) | 0.0571 (12) | |
| H3A | 0.8511 | −0.1398 | 0.4081 | 0.068* | |
| C4 | 0.7485 (10) | 0.0890 (7) | 0.3665 (5) | 0.0571 (13) | |
| H4A | 0.8638 | 0.1000 | 0.4221 | 0.068* | |
| C5 | 0.5879 (9) | 0.2166 (6) | 0.2942 (5) | 0.0465 (10) | |
| H5A | 0.5959 | 0.3124 | 0.3018 | 0.056* | |
| C6 | 0.4120 (8) | 0.2051 (5) | 0.2093 (4) | 0.0365 (8) | |
| C7 | 0.2342 (8) | 0.0364 (5) | 0.1093 (4) | 0.0402 (9) | |
| C8 | 0.2613 (11) | 0.5208 (5) | 0.1742 (5) | 0.0488 (11) | |
| H8A | 0.4498 | 0.5209 | 0.1687 | 0.059* | |
| H8B | 0.1864 | 0.6192 | 0.1130 | 0.059* | |
| C9 | 0.1482 (10) | 0.5076 (6) | 0.3179 (5) | 0.0504 (11) | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| S1 | 0.0549 (7) | 0.0366 (5) | 0.0400 (6) | −0.0082 (4) | −0.0092 (4) | −0.0178 (4) |
| O1 | 0.093 (3) | 0.210 (7) | 0.109 (4) | −0.084 (4) | 0.041 (3) | −0.121 (5) |
| O2 | 0.076 (3) | 0.149 (5) | 0.077 (3) | −0.034 (3) | 0.002 (2) | −0.075 (3) |
| O3 | 0.064 (2) | 0.0412 (17) | 0.073 (2) | 0.0014 (15) | −0.0322 (18) | −0.0301 (16) |
| O4 | 0.063 (2) | 0.0398 (16) | 0.060 (2) | −0.0022 (14) | −0.0285 (16) | −0.0241 (15) |
| C1 | 0.040 (2) | 0.043 (2) | 0.038 (2) | −0.0067 (17) | −0.0030 (16) | −0.0202 (17) |
| C2 | 0.052 (3) | 0.046 (2) | 0.050 (3) | −0.004 (2) | −0.012 (2) | −0.020 (2) |
| C3 | 0.056 (3) | 0.062 (3) | 0.055 (3) | 0.000 (2) | −0.021 (2) | −0.020 (2) |
| C4 | 0.046 (3) | 0.077 (3) | 0.060 (3) | −0.005 (2) | −0.020 (2) | −0.033 (3) |
| C5 | 0.042 (2) | 0.058 (3) | 0.054 (3) | −0.012 (2) | −0.0053 (19) | −0.033 (2) |
| C6 | 0.0368 (19) | 0.044 (2) | 0.0344 (19) | −0.0082 (16) | −0.0008 (15) | −0.0194 (16) |
| C7 | 0.043 (2) | 0.041 (2) | 0.045 (2) | −0.0066 (17) | −0.0047 (17) | −0.0241 (18) |
| C8 | 0.067 (3) | 0.038 (2) | 0.050 (2) | −0.016 (2) | −0.008 (2) | −0.0189 (19) |
| C9 | 0.058 (3) | 0.047 (2) | 0.060 (3) | −0.010 (2) | −0.009 (2) | −0.032 (2) |
Geometric parameters (Å, °) top
| S1—C6 | 1.768 (4) | C2—C3 | 1.385 (6) |
| S1—C8 | 1.809 (4) | C2—H2A | 0.9300 |
| O1—C9 | 1.224 (7) | C3—C4 | 1.368 (8) |
| O2—C9 | 1.251 (6) | C3—H3A | 0.9300 |
| O2—H2 | 0.86 (7) | C4—C5 | 1.372 (7) |
| O3—C7 | 1.315 (5) | C4—H4A | 0.9300 |
| O3—H3 | 0.85 (2) | C5—C6 | 1.399 (6) |
| O4—C7 | 1.216 (5) | C5—H5A | 0.9300 |
| C1—C2 | 1.388 (6) | C8—C9 | 1.509 (7) |
| C1—C6 | 1.409 (6) | C8—H8A | 0.9700 |
| C1—C7 | 1.476 (5) | C8—H8B | 0.9700 |
| | | |
| C6—S1—C8 | 103.4 (2) | C6—C5—H5A | 119.4 |
| C9—O2—H2 | 105 (6) | C5—C6—C1 | 117.6 (4) |
| C7—O3—H3 | 105 (4) | C5—C6—S1 | 121.8 (3) |
| C2—C1—C6 | 120.0 (4) | C1—C6—S1 | 120.6 (3) |
| C2—C1—C7 | 118.8 (4) | O4—C7—O3 | 122.1 (4) |
| C6—C1—C7 | 121.2 (4) | O4—C7—C1 | 123.9 (4) |
| C3—C2—C1 | 121.0 (4) | O3—C7—C1 | 114.1 (4) |
| C3—C2—H2A | 119.5 | C9—C8—S1 | 114.5 (3) |
| C1—C2—H2A | 119.5 | C9—C8—H8A | 108.6 |
| C4—C3—C2 | 119.1 (5) | S1—C8—H8A | 108.6 |
| C4—C3—H3A | 120.5 | C9—C8—H8B | 108.6 |
| C2—C3—H3A | 120.5 | S1—C8—H8B | 108.6 |
| C3—C4—C5 | 121.1 (4) | H8A—C8—H8B | 107.6 |
| C3—C4—H4A | 119.4 | O1—C9—O2 | 122.5 (5) |
| C5—C4—H4A | 119.4 | O1—C9—C8 | 121.3 (4) |
| C4—C5—C6 | 121.2 (4) | O2—C9—C8 | 116.1 (5) |
| C4—C5—H5A | 119.4 | | |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···O1i | 0.86 (7) | 1.92 (5) | 2.687 (6) | 149 (8) |
| O3—H3···O4ii | 0.85 (2) | 1.80 (5) | 2.634 (4) | 167 (6) |
| Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y, −z. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···O1i | 0.86 (7) | 1.92 (5) | 2.687 (6) | 149 (8) |
| O3—H3···O4ii | 0.85 (2) | 1.80 (5) | 2.634 (4) | 167 (6) |
| Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y, −z. |
Bruker (2002). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Sagatys, D. S., Smith, G., Bott, R. C. & Healy, P. C. (2003). Aust. J. Chem. 56, 941–943.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Sokolov, M., Fyodorova, N., Pervukhina, N. & Fedorov, V. (2001). Inorg. Chem. Commun. 4, 261–263.
![[Figure 1]](./at2858fig1thm.gif)
Thioacetatebenzoic acid (I) is an interesting ligand from a structural point of view since it can display a wide range of coordination patterns with metal ions. The ligand (I) belongs to dicarboxylic acids. The characteristic coordination chemistry of the rigid carboxylate system may facilitate the formation of inorganic-organic materials with high thermal stability and form large channels, while the peculiar coordination chemistry of the flexible carboxylate system employed in the self-assembly reaction has versatile coordination behavior and may be favorable for the formation of the helical structure (Sagatys et al., 2003; Sokolov et al., 2001). As shown in Fig.1, the bond lengths within the benzene ring exhibit the expected pattern with C—C bonds (1.368 (8)–1.399 (6) Å) between the single and double bonds. And the bond distance of C1—C7 (1.476 (5) Å) and S1—C6 (1.768 (4) Å) also fall between the double and single bonds. All these interatomic distances suggest that extensive but not uniform π electron delocalization is present in the benzene ring and extends over the exocyclic C—S and C—C bonds. The torsion angle of C6—S1—C8—C9 is -71.7 (4)°. O—H···O hydrogen bonds link independent molecules to form a zigzig chain.