2-(Phenyl-sulfan-yl)pyridine-3-carboxylic acid.

The title compound, C(12)H(9)NO(2)S, belongs to the nitro-gen-containing group of heterocyclic organic compounds and crystallized with two mol-ecules per asymmetric unit. In the crystal, both molecules form inversion dimers linked by pairs of O-H-O hydrogen bonds. Weak symmetry-related C-H-O inter-actions link the carboxyl dimers along b axis. The dihedral angle between the two aromatic rings in the two mol-ecules are 55.75 (14) and 58.33 (13)°.

Related literature

For the pharmacological effects of heteroaromatic anti­tumor compounds: Denny et al. (1982 ▶); Fujiwara (1997 ▶); Antonini & Martelli (1992 ▶); Cholody et al. (1992 ▶). For the title compound as an inter­mediate for heterocycles, see: Khan et al. (2008a ▶,b ▶). For the synthesis, see: Mann & Reid (1952 ▶).

Experimental

Crystal data

C12H9NO2S

M = 231.26

Triclinic,

a = 7.2201 (4) Å

b = 7.6653 (4) Å

c = 19.9537 (11) Å

α = 97.895 (3)°

β = 98.520 (3)°

γ = 91.661 (3)°

V = 1080.41 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.28 mm−1

T = 296 K

0.21 × 0.09 × 0.06 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.911, T max = 0.983

23200 measured reflections

5397 independent reflections

2766 reflections with I > 2/s(I)

R int = 0.063

Refinement

R[F 2 > 2σ(F 2)] = 0.073

wR(F 2) = 0.224

S = 1.09

5397 reflections

292 parameters

H-atom parameters constrained

Δρmax = 0.59 e Å−3

Δρmin = −0.53 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809038586/hg2570sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809038586/hg2570Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C12H9NO2S	Z = 4
Mr = 231.26	F(000) = 480
Triclinic, P1	Dx = 1.422 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2201 (4) Å	Cell parameters from 3133 reflections
b = 7.6653 (4) Å	θ = 2.9–23.8°
c = 19.9537 (11) Å	µ = 0.28 mm−1
α = 97.895 (3)°	T = 296 K
β = 98.520 (3)°	Needle, white
γ = 91.661 (3)°	0.21 × 0.09 × 0.06 mm
V = 1080.41 (10) Å3

Bruker Kappa APEXII CCD diffractometer	5397 independent reflections
Radiation source: fine-focus sealed tube	2766 reflections with I > 2/s(I)
graphite	Rint = 0.063
φ and ω scans	θmax = 28.4°, θmin = 1.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→9
Tmin = 0.911, Tmax = 0.983	k = −10→10
23200 measured reflections	l = −26→26

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.073	H-atom parameters constrained
wR(F2) = 0.224	w = 1/[σ2(Fo2) + (0.1023P)2 + 0.1581P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max < 0.001
5397 reflections	Δρmax = 0.59 e Å−3
292 parameters	Δρmin = −0.52 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.045 (5)

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.

	x	y	z	Uiso*/Ueq
S1	0.15013 (14)	−0.12613 (12)	0.21464 (5)	0.0407 (3)
S2	0.70162 (15)	0.36894 (12)	0.22267 (5)	0.0447 (3)
O1	0.1649 (4)	−0.2094 (3)	0.07364 (13)	0.0508 (7)
O2	0.2377 (6)	−0.0151 (4)	0.00790 (14)	0.0709 (10)
H2	0.2653	−0.1043	−0.0155	0.106*
O3	0.7077 (5)	0.2844 (3)	0.08218 (13)	0.0568 (8)
O4	0.7667 (5)	0.4795 (4)	0.01516 (15)	0.0689 (10)
H4O	0.7958	0.3911	−0.0083	0.103*
N1	0.1813 (5)	0.2239 (4)	0.23401 (15)	0.0422 (8)
N2	0.6430 (4)	0.7119 (4)	0.23511 (15)	0.0414 (8)
C1	0.1727 (5)	0.0818 (4)	0.18659 (17)	0.0341 (8)
C2	0.1832 (5)	0.0971 (5)	0.11768 (18)	0.0382 (8)
C3	0.1939 (6)	0.2639 (5)	0.1002 (2)	0.0496 (10)
H3	0.2005	0.2783	0.0551	0.059*
C4	0.1951 (6)	0.4099 (5)	0.1488 (2)	0.0521 (11)
H4	0.1978	0.5234	0.1372	0.062*
C5	0.1921 (6)	0.3809 (5)	0.2150 (2)	0.0485 (10)
H5	0.1981	0.4787	0.2486	0.058*
C6	0.1937 (6)	−0.0559 (5)	0.06520 (18)	0.0413 (9)
C7	0.1766 (5)	−0.0719 (5)	0.30494 (18)	0.0380 (8)
C8	0.3176 (6)	−0.1484 (5)	0.34292 (19)	0.0490 (10)
H8	0.4002	−0.2190	0.3214	0.059*
C9	0.3357 (7)	−0.1189 (7)	0.4143 (2)	0.0656 (13)
H9	0.4306	−0.1709	0.4403	0.079*
C10	0.2159 (8)	−0.0149 (7)	0.4461 (2)	0.0738 (15)
H10	0.2290	0.0048	0.4936	0.089*
C11	0.0762 (7)	0.0605 (6)	0.4077 (2)	0.0665 (14)
H11	−0.0053	0.1320	0.4295	0.080*
C12	0.0542 (6)	0.0326 (5)	0.3379 (2)	0.0509 (10)
H12	−0.0426	0.0836	0.3125	0.061*
C13	0.6743 (5)	0.5728 (5)	0.19104 (18)	0.0357 (8)
C14	0.6895 (5)	0.5891 (5)	0.12249 (18)	0.0373 (8)
C15	0.6724 (6)	0.7539 (5)	0.1026 (2)	0.0457 (10)
H15	0.6818	0.7686	0.0577	0.055*
C16	0.6416 (6)	0.8959 (5)	0.1483 (2)	0.0463 (10)
H16	0.6317	1.0081	0.1358	0.056*
C17	0.6261 (5)	0.8659 (5)	0.2134 (2)	0.0442 (9)
H17	0.6017	0.9612	0.2444	0.053*
C18	0.7230 (6)	0.4371 (5)	0.07237 (18)	0.0416 (9)
C19	0.7107 (5)	0.4283 (5)	0.31237 (18)	0.0380 (8)
C20	0.5879 (6)	0.3405 (6)	0.3442 (2)	0.0492 (10)
H20	0.4968	0.2604	0.3184	0.059*
C21	0.5999 (7)	0.3716 (7)	0.4149 (2)	0.0658 (13)
H21	0.5161	0.3128	0.4363	0.079*
C22	0.7329 (8)	0.4871 (7)	0.4529 (2)	0.0717 (14)
H22	0.7415	0.5066	0.5004	0.086*
C23	0.8545 (7)	0.5748 (6)	0.4213 (2)	0.0683 (14)
H23	0.9445	0.6552	0.4476	0.082*
C24	0.8463 (6)	0.5467 (6)	0.3516 (2)	0.0528 (11)
H24	0.9308	0.6064	0.3308	0.063*

	U11	U22	U33	U12	U13	U23
S1	0.0630 (7)	0.0289 (5)	0.0303 (5)	0.0032 (4)	0.0088 (4)	0.0027 (4)
S2	0.0728 (7)	0.0313 (5)	0.0326 (5)	0.0075 (5)	0.0147 (5)	0.0060 (4)
O1	0.092 (2)	0.0293 (15)	0.0329 (15)	0.0027 (13)	0.0166 (14)	0.0041 (12)
O2	0.148 (3)	0.0337 (16)	0.0387 (17)	0.0088 (18)	0.0413 (19)	0.0042 (13)
O3	0.111 (2)	0.0291 (15)	0.0366 (16)	0.0060 (14)	0.0284 (15)	0.0063 (12)
O4	0.137 (3)	0.0358 (16)	0.0428 (18)	0.0118 (18)	0.0420 (19)	0.0057 (13)
N1	0.062 (2)	0.0298 (17)	0.0348 (18)	0.0000 (14)	0.0090 (15)	0.0022 (14)
N2	0.056 (2)	0.0325 (17)	0.0378 (18)	0.0111 (14)	0.0137 (15)	0.0047 (14)
C1	0.041 (2)	0.0320 (19)	0.0291 (19)	0.0071 (15)	0.0034 (15)	0.0037 (15)
C2	0.054 (2)	0.0300 (19)	0.0309 (19)	0.0066 (16)	0.0075 (16)	0.0034 (15)
C3	0.078 (3)	0.034 (2)	0.040 (2)	0.0069 (19)	0.016 (2)	0.0065 (18)
C4	0.084 (3)	0.028 (2)	0.048 (3)	0.0085 (19)	0.016 (2)	0.0099 (18)
C5	0.068 (3)	0.029 (2)	0.046 (2)	0.0008 (18)	0.013 (2)	−0.0059 (18)
C6	0.065 (3)	0.032 (2)	0.029 (2)	0.0089 (17)	0.0106 (17)	0.0056 (16)
C7	0.053 (2)	0.0293 (19)	0.031 (2)	−0.0026 (16)	0.0100 (17)	0.0019 (15)
C8	0.063 (3)	0.048 (2)	0.038 (2)	0.005 (2)	0.0113 (19)	0.0104 (19)
C9	0.077 (3)	0.080 (3)	0.041 (3)	−0.003 (3)	0.003 (2)	0.021 (2)
C10	0.101 (4)	0.087 (4)	0.032 (2)	−0.020 (3)	0.020 (3)	0.000 (3)
C11	0.087 (4)	0.060 (3)	0.054 (3)	−0.001 (3)	0.035 (3)	−0.010 (2)
C12	0.063 (3)	0.048 (2)	0.045 (2)	0.004 (2)	0.020 (2)	0.0043 (19)
C13	0.044 (2)	0.0323 (19)	0.0295 (19)	0.0029 (15)	0.0065 (15)	0.0008 (15)
C14	0.052 (2)	0.0310 (19)	0.0305 (19)	0.0016 (16)	0.0122 (16)	0.0042 (15)
C15	0.067 (3)	0.032 (2)	0.041 (2)	0.0050 (18)	0.0151 (19)	0.0080 (17)
C16	0.064 (3)	0.032 (2)	0.048 (2)	0.0099 (18)	0.016 (2)	0.0126 (18)
C17	0.060 (2)	0.030 (2)	0.043 (2)	0.0088 (17)	0.0143 (18)	−0.0001 (17)
C18	0.063 (3)	0.032 (2)	0.032 (2)	0.0039 (17)	0.0154 (18)	0.0047 (17)
C19	0.052 (2)	0.033 (2)	0.0301 (19)	0.0079 (16)	0.0102 (16)	0.0056 (16)
C20	0.056 (3)	0.053 (3)	0.039 (2)	−0.001 (2)	0.0074 (19)	0.0115 (19)
C21	0.074 (3)	0.087 (4)	0.044 (3)	0.006 (3)	0.023 (2)	0.024 (3)
C22	0.093 (4)	0.090 (4)	0.033 (2)	0.012 (3)	0.014 (3)	0.005 (3)
C23	0.079 (3)	0.072 (3)	0.046 (3)	0.004 (3)	−0.008 (2)	0.001 (2)
C24	0.064 (3)	0.053 (3)	0.042 (2)	−0.004 (2)	0.009 (2)	0.009 (2)

S1—C1	1.771 (4)	C9—C10	1.360 (7)
S1—C7	1.773 (4)	C9—H9	0.9300
S2—C13	1.769 (4)	C10—C11	1.365 (7)
S2—C19	1.776 (4)	C10—H10	0.9300
O1—C6	1.228 (4)	C11—C12	1.365 (6)
O2—C6	1.306 (4)	C11—H11	0.9300
O2—H2	0.8200	C12—H12	0.9300
O3—C18	1.218 (4)	C13—C14	1.411 (5)
O4—C18	1.308 (4)	C14—C15	1.379 (5)
O4—H4O	0.8200	C14—C18	1.478 (5)
N1—C5	1.315 (5)	C15—C16	1.367 (5)
N1—C1	1.334 (4)	C15—H15	0.9300
N2—C17	1.315 (5)	C16—C17	1.369 (5)
N2—C13	1.333 (4)	C16—H16	0.9300
C1—C2	1.409 (5)	C17—H17	0.9300
C2—C3	1.374 (5)	C19—C20	1.376 (5)
C2—C6	1.472 (5)	C19—C24	1.386 (5)
C3—C4	1.374 (5)	C20—C21	1.386 (5)
C3—H3	0.9300	C20—H20	0.9300
C4—C5	1.372 (5)	C21—C22	1.354 (7)
C4—H4	0.9300	C21—H21	0.9300
C5—H5	0.9300	C22—C23	1.366 (7)
C7—C8	1.372 (5)	C22—H22	0.9300
C7—C12	1.387 (5)	C23—C24	1.371 (6)
C8—C9	1.397 (5)	C23—H23	0.9300
C8—H8	0.9300	C24—H24	0.9300
C1—S1—C7	103.18 (16)	C11—C12—C7	119.9 (4)
C13—S2—C19	103.20 (16)	C11—C12—H12	120.1
C6—O2—H2	109.5	C7—C12—H12	120.1
C18—O4—H4O	109.5	N2—C13—C14	121.1 (3)
C5—N1—C1	118.8 (3)	N2—C13—S2	117.3 (3)
C17—N2—C13	118.6 (3)	C14—C13—S2	121.6 (3)
N1—C1—C2	121.4 (3)	C15—C14—C13	117.9 (3)
N1—C1—S1	116.8 (3)	C15—C14—C18	119.8 (3)
C2—C1—S1	121.8 (3)	C13—C14—C18	122.3 (3)
C3—C2—C1	117.6 (3)	C16—C15—C14	120.5 (4)
C3—C2—C6	119.1 (3)	C16—C15—H15	119.8
C1—C2—C6	123.1 (3)	C14—C15—H15	119.8
C2—C3—C4	120.7 (4)	C15—C16—C17	117.2 (3)
C2—C3—H3	119.6	C15—C16—H16	121.4
C4—C3—H3	119.6	C17—C16—H16	121.4
C5—C4—C3	117.1 (4)	N2—C17—C16	124.7 (3)
C5—C4—H4	121.5	N2—C17—H17	117.6
C3—C4—H4	121.5	C16—C17—H17	117.6
N1—C5—C4	124.3 (3)	O3—C18—O4	122.1 (3)
N1—C5—H5	117.8	O3—C18—C14	123.5 (3)
C4—C5—H5	117.8	O4—C18—C14	114.3 (3)
O1—C6—O2	121.9 (3)	C20—C19—C24	119.4 (4)
O1—C6—C2	123.8 (3)	C20—C19—S2	117.8 (3)
O2—C6—C2	114.2 (3)	C24—C19—S2	122.5 (3)
C8—C7—C12	119.6 (4)	C19—C20—C21	120.0 (4)
C8—C7—S1	117.3 (3)	C19—C20—H20	120.0
C12—C7—S1	122.9 (3)	C21—C20—H20	120.0
C7—C8—C9	119.3 (4)	C22—C21—C20	120.4 (4)
C7—C8—H8	120.3	C22—C21—H21	119.8
C9—C8—H8	120.3	C20—C21—H21	119.8
C10—C9—C8	120.6 (5)	C21—C22—C23	119.7 (4)
C10—C9—H9	119.7	C21—C22—H22	120.2
C8—C9—H9	119.7	C23—C22—H22	120.2
C9—C10—C11	119.6 (4)	C22—C23—C24	121.3 (4)
C9—C10—H10	120.2	C22—C23—H23	119.3
C11—C10—H10	120.2	C24—C23—H23	119.3
C10—C11—C12	121.1 (4)	C23—C24—C19	119.3 (4)
C10—C11—H11	119.5	C23—C24—H24	120.4
C12—C11—H11	119.5	C19—C24—H24	120.4
C5—N1—C1—C2	2.8 (5)	C17—N2—C13—C14	0.1 (5)
C5—N1—C1—S1	−177.9 (3)	C17—N2—C13—S2	178.6 (3)
C7—S1—C1—N1	−7.2 (3)	C19—S2—C13—N2	−8.3 (3)
C7—S1—C1—C2	172.1 (3)	C19—S2—C13—C14	170.2 (3)
N1—C1—C2—C3	−2.9 (6)	N2—C13—C14—C15	0.4 (6)
S1—C1—C2—C3	177.8 (3)	S2—C13—C14—C15	−177.9 (3)
N1—C1—C2—C6	173.5 (3)	N2—C13—C14—C18	−179.6 (3)
S1—C1—C2—C6	−5.8 (5)	S2—C13—C14—C18	2.0 (5)
C1—C2—C3—C4	0.2 (6)	C13—C14—C15—C16	0.0 (6)
C6—C2—C3—C4	−176.3 (4)	C18—C14—C15—C16	−179.9 (4)
C2—C3—C4—C5	2.4 (6)	C14—C15—C16—C17	−1.0 (6)
C1—N1—C5—C4	0.1 (6)	C13—N2—C17—C16	−1.3 (6)
C3—C4—C5—N1	−2.6 (7)	C15—C16—C17—N2	1.7 (6)
C3—C2—C6—O1	−171.7 (4)	C15—C14—C18—O3	−166.9 (4)
C1—C2—C6—O1	12.0 (6)	C13—C14—C18—O3	13.2 (6)
C3—C2—C6—O2	8.6 (6)	C15—C14—C18—O4	11.6 (6)
C1—C2—C6—O2	−167.8 (4)	C13—C14—C18—O4	−168.3 (4)
C1—S1—C7—C8	−122.4 (3)	C13—S2—C19—C20	126.3 (3)
C1—S1—C7—C12	62.3 (4)	C13—S2—C19—C24	−59.6 (4)
C12—C7—C8—C9	−0.2 (6)	C24—C19—C20—C21	0.3 (6)
S1—C7—C8—C9	−175.7 (3)	S2—C19—C20—C21	174.6 (3)
C7—C8—C9—C10	−0.3 (7)	C19—C20—C21—C22	−0.5 (7)
C8—C9—C10—C11	0.3 (8)	C20—C21—C22—C23	0.7 (8)
C9—C10—C11—C12	0.3 (8)	C21—C22—C23—C24	−0.8 (8)
C10—C11—C12—C7	−0.8 (7)	C22—C23—C24—C19	0.7 (7)
C8—C7—C12—C11	0.8 (6)	C20—C19—C24—C23	−0.4 (6)
S1—C7—C12—C11	176.0 (3)	S2—C19—C24—C23	−174.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3i	0.82	1.82	2.624 (2)	168 (1)
O4—H4o···O1i	0.820	1.83000	2.642 (2)	169.62 (19)
C3—H3···O4ii	0.93	2.50	3.264 (5)	139
C4—H4···O1iii	0.93	2.55	3.458 (5)	164
C15—H15···O2ii	0.93	2.54	3.294 (5)	138
C16—H16···O3iii	0.93	2.58	3.467 (5)	160

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3i	0.82	1.82	2.624 (2)	167 (1)
O4—H4o⋯O1i	0.82	1.83	2.642 (2)	170 (1)
C3—H3⋯O4ii	0.93	2.50	3.264 (5)	139
C4—H4⋯O1iii	0.93	2.55	3.458 (5)	164
C15—H15⋯O2ii	0.93	2.54	3.294 (5)	138
C16—H16⋯O3iii	0.93	2.58	3.467 (5)	160

Symmetry codes: (i) ; (ii) ; (iii) .