2,2′-Thio­dibenzoic acid

In the title mol­ecule, C₁₄H₁₀O₄S, all bond lengths and angles are normal. In the crystal structure, strong inter­molecular O—H...O hydrogen bonds between the carboxyl groups link the mol­ecules into zigzag chains extending along the c axis.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.077
• wR factor = 0.149
• Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level B
ABSTM02_ALERT_3_B  The ratio of expected to reported Tmax/Tmin(RR') is < 0.75
            Tmin and Tmax reported:      0.621     0.924
            Tmin(prime) and Tmax expected:      0.852     0.924
            RR(prime) =      0.729
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_B Tmax/Tmin Range Test RR' too Large .............       0.73

Alert level C
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          6

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

---

S1. Comment

The current interest focused on the crystal engineering of coordination polymeric frameworks not only stems from their potential properties as functional solid materials, in host–guest chemistry, ion exchange, catalysis and for the development of optical, magnetic and electronic devices, but also from their intriguing variety of architectures and topologies (Chui et al., 1999; Matsumoto et al., 1999). Some organic S-donors, such as thiosalicylic acid or related species, attracted our attention for the process of constructing coordination polymers. However, an unexpected organic ligand was obtained as a result of the desulfurization of the thiosalicylic acid ligand. We report here the synthesis and crystal structure of the title compound, C₁₄H₁₀O₄S, (I).

In (I) (Fig. 1), the bond lengths and angles (Table 1) are normal. In the crystal structure, strong intermolecular O—H···O hydrogen bonds between the carboxyl groups (Table 2) link the molecules into zigzag chains extending along the c axis (Fig. 2).

S2. Experimental

CuCl₂·2H₂O (0.17 g, 1 mmol), thiosalicylic acid (0.15 g, 1 mmol), and NaOH (0.04 g, 1 mmol), were mixed in water (15 ml) and heated at 433 K for 3 d in a sealed 25 ml Teflon-lined stainless steel vessel under autogenous pressure. After cooling to room temperature at a rate of 5 K h⁻¹, yellow block crystals were isolated, washed with water and dried in air.

S3. Refinement

The C-bound H atoms were positioned geometrically and refined as riding on their parent atoms, with C—H = 0.93 Å and U_iso = 1.5U_eq(C). The carboxy H atoms were located in a difference Fourier map and refined isotropically.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART and SAINT (Siemens, 1996); data reduction: XPREP (Siemens, 1996); program(s) used to solve structure: SHELXTL (Siemens, 1996); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and ORTEP-3 in WinGX (Farrugia, 1999); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. View of (I), showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. The one-dimensional zigzag chains of hydrogen-bonded (dashed lines) molecules extending along the c axis. C-bound H atoms have been omitted for clarity.

2,2'-Thiodibenzoic acid

Crystal data

C14H10O4S	F(000) = 568
Mr = 274.29	Dx = 1.436 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.9126 (6) Å	Cell parameters from 2271 reflections
b = 6.4708 (2) Å	θ = 2.9–25.0°
c = 14.4664 (7) Å	µ = 0.26 mm^−1
β = 103.134 (2)°	T = 293 K
V = 1268.28 (9) Å^3	Prism, yellow
Z = 4	0.60 × 0.36 × 0.30 mm

Data collection

Siemens SMART CCD area-detector diffractometer	2250 independent reflections
Radiation source: fine-focus sealed tube	2023 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ϕ and ω scans	θmax = 25.0°, θmin = 2.9°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −16→15
Tmin = 0.621, Tmax = 0.924	k = −7→7
4026 measured reflections	l = −10→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.077	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.149	H atoms treated by a mixture of independent and constrained refinement
S = 1.33	w = 1/[σ^2(Fo^2) + (0.0139P)^2 + 2.6198P] where P = (Fo^2 + 2Fc^2)/3
2250 reflections	(Δ/σ)max < 0.001
176 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.7911 (3)	0.9401 (7)	0.5776 (3)	0.0424 (10)
C2	0.8744 (3)	0.5359 (7)	0.7679 (3)	0.0493 (11)
H2A	0.8717	0.5091	0.8301	0.074*
H3A	0.5401	0.3997	0.7725	0.080*
H4A	0.9578	0.3472	0.5950	0.078*
H5A	0.8936	0.6467	0.5232	0.067*
H6A	0.5407	0.8264	0.9696	0.076*
H7A	0.9434	0.2711	0.7482	0.079*
H8A	0.4761	0.5302	0.8943	0.085*
H9A	0.6699	0.5607	0.7282	0.059*
H1A	0.804 (5)	1.117 (11)	0.480 (5)	0.079 (2)*
H10A	0.665 (5)	1.235 (10)	1.038 (5)	0.10 (2)*
C3	0.5670 (3)	0.5190 (7)	0.8041 (3)	0.0534 (12)
C4	0.9261 (3)	0.4397 (7)	0.6275 (3)	0.0519 (12)
C5	0.8873 (3)	0.6180 (7)	0.5846 (3)	0.0451 (10)
C6	0.5673 (3)	0.7732 (8)	0.9212 (3)	0.0507 (11)
C7	0.9188 (3)	0.3949 (7)	0.7195 (4)	0.0527 (11)
C8	0.5283 (3)	0.5971 (8)	0.8764 (4)	0.0567 (12)
C9	0.6454 (3)	0.6150 (7)	0.7778 (3)	0.0462 (10)
C10	0.6829 (3)	1.0702 (7)	0.9440 (3)	0.0428 (10)
C11	0.6878 (3)	0.7907 (6)	0.8243 (3)	0.0375 (9)
C12	0.8338 (3)	0.7175 (6)	0.7251 (3)	0.0389 (9)
C13	0.6463 (3)	0.8768 (7)	0.8965 (3)	0.0399 (10)
C14	0.8381 (3)	0.7581 (6)	0.6306 (3)	0.0377 (9)
S1	0.79263 (8)	0.91010 (18)	0.79606 (8)	0.0454 (3)
O1	0.8348 (2)	1.0021 (5)	0.5108 (2)	0.0566 (9)
O2	0.7170 (2)	1.0242 (5)	0.5914 (2)	0.0583 (9)
O3	0.6450 (3)	1.1204 (7)	1.0166 (3)	0.0680 (11)
O4	0.7454 (2)	1.1767 (5)	0.9194 (2)	0.0508 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.040 (2)	0.049 (3)	0.039 (2)	−0.004 (2)	0.0113 (18)	0.000 (2)
C2	0.048 (3)	0.054 (3)	0.048 (2)	−0.002 (2)	0.017 (2)	0.011 (2)
C3	0.042 (2)	0.048 (3)	0.067 (3)	−0.006 (2)	0.005 (2)	−0.007 (2)
C4	0.044 (3)	0.050 (3)	0.063 (3)	0.000 (2)	0.015 (2)	−0.012 (2)
C5	0.043 (2)	0.051 (3)	0.042 (2)	−0.004 (2)	0.0121 (18)	−0.007 (2)
C6	0.039 (2)	0.061 (3)	0.057 (3)	0.002 (2)	0.022 (2)	−0.002 (2)
C7	0.043 (2)	0.043 (3)	0.072 (3)	0.003 (2)	0.014 (2)	0.007 (2)
C8	0.043 (3)	0.060 (3)	0.071 (3)	−0.010 (2)	0.022 (2)	0.000 (3)
C9	0.039 (2)	0.051 (3)	0.048 (2)	−0.004 (2)	0.0109 (19)	−0.008 (2)
C10	0.042 (2)	0.046 (3)	0.042 (2)	0.007 (2)	0.0127 (18)	−0.001 (2)
C11	0.029 (2)	0.046 (2)	0.036 (2)	0.0012 (18)	0.0065 (16)	0.0045 (19)
C12	0.035 (2)	0.043 (2)	0.043 (2)	−0.0059 (18)	0.0152 (17)	−0.0023 (19)
C13	0.035 (2)	0.046 (2)	0.040 (2)	0.0029 (18)	0.0107 (17)	0.0044 (19)
C14	0.033 (2)	0.041 (2)	0.040 (2)	−0.0054 (18)	0.0100 (17)	−0.0069 (18)
S1	0.0535 (7)	0.0459 (6)	0.0434 (6)	−0.0085 (5)	0.0246 (5)	−0.0057 (5)
O1	0.070 (2)	0.057 (2)	0.0523 (18)	0.0128 (17)	0.0345 (16)	0.0139 (16)
O2	0.0525 (19)	0.072 (2)	0.0572 (19)	0.0159 (17)	0.0261 (15)	0.0213 (17)
O3	0.068 (2)	0.075 (3)	0.074 (2)	−0.019 (2)	0.0437 (19)	−0.030 (2)
O4	0.063 (2)	0.0481 (18)	0.0467 (17)	−0.0075 (16)	0.0243 (15)	−0.0059 (15)

Geometric parameters (Å, º)

C1—O2	1.223 (5)	C6—C13	1.401 (6)
C1—O1	1.315 (5)	C6—H6A	0.9297
C1—C14	1.475 (6)	C7—H7A	0.9312
C2—C7	1.378 (6)	C8—H8A	0.9311
C2—C12	1.387 (6)	C9—C11	1.384 (6)
C2—H2A	0.9300	C9—H9A	0.9300
C3—C8	1.376 (7)	C10—O4	1.225 (5)
C3—C9	1.381 (6)	C10—O3	1.318 (5)
C3—H3A	0.9313	C10—C13	1.462 (6)
C4—C5	1.363 (6)	C11—C13	1.417 (5)
C4—C7	1.388 (6)	C11—S1	1.778 (4)
C4—H4A	0.9312	C12—C14	1.406 (5)
C5—C14	1.394 (6)	C12—S1	1.790 (4)
C5—H5A	0.9298	O1—H1A	0.92 (7)
C6—C8	1.361 (7)	O3—H10A	0.82 (7)
O2—C1—O1	122.2 (4)	C3—C8—H8A	120.4
O2—C1—C14	124.1 (4)	C3—C9—C11	120.8 (4)
O1—C1—C14	113.7 (4)	C3—C9—H9A	119.6
C7—C2—C12	121.2 (4)	C11—C9—H9A	119.7
C7—C2—H2A	119.4	O4—C10—O3	122.1 (4)
C12—C2—H2A	119.4	O4—C10—C13	122.6 (4)
C8—C3—C9	121.0 (4)	O3—C10—C13	115.2 (4)
C8—C3—H3A	119.5	C9—C11—C13	118.8 (4)
C9—C3—H3A	119.5	C9—C11—S1	121.8 (3)
C5—C4—C7	120.4 (4)	C13—C11—S1	119.4 (3)
C5—C4—H4A	119.9	C2—C12—C14	119.3 (4)
C7—C4—H4A	119.7	C2—C12—S1	119.0 (3)
C4—C5—C14	121.3 (4)	C14—C12—S1	121.1 (3)
C4—C5—H5A	119.4	C6—C13—C11	118.3 (4)
C14—C5—H5A	119.3	C6—C13—C10	120.0 (4)
C8—C6—C13	122.0 (4)	C11—C13—C10	121.7 (4)
C8—C6—H6A	119.0	C5—C14—C12	118.5 (4)
C13—C6—H6A	118.9	C5—C14—C1	118.6 (4)
C2—C7—C4	119.2 (4)	C12—C14—C1	123.0 (4)
C2—C7—H7A	120.3	C11—S1—C12	102.46 (19)
C4—C7—H7A	120.4	C1—O1—H1A	111 (5)
C6—C8—C3	119.1 (4)	C10—O3—H10A	111 (4)
C6—C8—H8A	120.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O4^i	0.92 (7)	1.70 (7)	2.621 (4)	177 (7)
O3—H10A···O2^ii	0.82 (7)	1.82 (7)	2.640 (5)	175 (7)

Symmetry codes: (i) x, −y+5/2, z−1/2; (ii) x, −y+5/2, z+1/2.