4-(3-Fluoro-anilino)thieno[2,3-b]pyridine-6-carb-oxy-lic acid.

In the title compound, C(14)H(9)FN(2)O(2)S, the thieno[2,3-b]pyridine residue is almost planar (r.m.s. deviation = 0.0194 Å), with the carb-oxy-lic acid group [dihedral angle = 11.9 (3)°] and the benzene ring [71.1 (4)°] being twisted out of this plane to different extents. An intra-molecular N-H⋯O(carbon-yl) hydrogen bond closes an S(6) ring. Supra-molecular chains along [01-1] mediated by O-H⋯N(pyridine) hydrogen bonds feature in the crystal. A three-dimensional architecture is completed by π-π inter-actions occurring between the benzene ring and the two rings of the thieno[2,3-b]pyridine residue [centroid-centroid distances = 3.6963 (13) and 3.3812 (13) Å]. The F atom is disordered over the two meta sites in a near statistical ratio [0.545 (5):0.455 (5)].

Related literature

For the biological activity of 4-(aryl­amino)­thieno[2,3-b]pyridine-5-carb­oxy­lic acids, see: Bernardino et al. (2007 ▶); Pinheiro et al. (2008 ▶). For the synthesis, see: Leal et al. (2008 ▶).

Experimental

Crystal data

C14H9FN2O2S

M = 288.29

Orthorhombic,

a = 17.0666 (6) Å

b = 8.7147 (3) Å

c = 7.9931 (2) Å

V = 1188.82 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.29 mm−1

T = 120 K

0.66 × 0.24 × 0.17 mm

Data collection

Bruker–Nonius Roper CCD camera on κ-goniostat diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T min = 0.788, T max = 1.000

10259 measured reflections

2643 independent reflections

2376 reflections with I > 2σ(I)

R int = 0.058

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.087

S = 1.06

2643 reflections

197 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.20 e Å−3

Δρmin = −0.42 e Å−3

Absolute structure: Flack (1983 ▶), 1181 Friedel pairs

Flack parameter: 0.15 (9)

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812027195/hb6844sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812027195/hb6844Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812027195/hb6844Isup3.cml

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

C14H9FN2O2S	F(000) = 592
Mr = 288.29	Dx = 1.611 Mg m−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 1601 reflections
a = 17.0666 (6) Å	θ = 1.0–27.5°
b = 8.7147 (3) Å	µ = 0.29 mm−1
c = 7.9931 (2) Å	T = 120 K
V = 1188.82 (7) Å3	Blade, dark-orange
Z = 4	0.66 × 0.24 × 0.17 mm

Bruker–Nonius Roper CCD camera on κ-goniostat diffractometer	2643 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	2376 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
Detector resolution: 9.091 pixels mm-1	θmax = 27.5°, θmin = 3.5°
φ & ω scans	h = −22→22
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	k = −11→11
Tmin = 0.788, Tmax = 1.000	l = −10→9
10259 measured reflections

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)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.087	w = 1/[σ2(Fo2) + (0.0375P)2 + 0.2847P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
2643 reflections	Δρmax = 0.20 e Å−3
197 parameters	Δρmin = −0.42 e Å−3
3 restraints	Absolute structure: Flack (1983), 1181 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.15 (9)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	Occ. (<1)
S1	0.02466 (3)	0.49277 (6)	0.56709 (9)	0.02149 (14)
O1	0.26956 (9)	0.89190 (18)	1.0209 (2)	0.0246 (4)
H1O	0.2865 (16)	0.959 (2)	1.090 (3)	0.037*
O2	0.17443 (8)	1.06688 (18)	1.0208 (2)	0.0254 (4)
N1	0.15569 (10)	0.5951 (2)	0.7157 (2)	0.0185 (4)
N2	0.03616 (11)	0.9821 (2)	0.9068 (3)	0.0214 (4)
H2N	0.0711 (11)	1.041 (3)	0.956 (3)	0.026*
C1	0.18990 (13)	0.7023 (2)	0.8094 (3)	0.0184 (5)
H1	0.2445	0.6918	0.8298	0.022*
C2	0.15232 (12)	0.8288 (2)	0.8800 (2)	0.0161 (4)
C3	0.07089 (13)	0.8526 (2)	0.8490 (3)	0.0167 (4)
C4	0.03239 (12)	0.7380 (2)	0.7525 (3)	0.0154 (4)
C5	−0.04725 (13)	0.7259 (2)	0.6927 (3)	0.0190 (5)
H5	−0.0872	0.7977	0.7195	0.023*
C6	−0.05889 (12)	0.6029 (2)	0.5952 (3)	0.0214 (5)
H6	−0.1081	0.5784	0.5464	0.026*
C7	0.07779 (12)	0.6170 (2)	0.6923 (3)	0.0172 (4)
C8	0.19891 (12)	0.9401 (3)	0.9793 (3)	0.0198 (5)
C9	−0.04436 (13)	1.0256 (3)	0.9067 (3)	0.0197 (5)
C10	−0.06524 (14)	1.1599 (3)	0.8256 (3)	0.0222 (5)
H10	−0.0279	1.2153	0.7613	0.027*
C12	−0.19667 (14)	1.1360 (3)	0.9319 (4)	0.0341 (6)
H12	−0.2487	1.1741	0.9406	0.041*
C14	−0.09947 (13)	0.9457 (3)	1.0002 (3)	0.0245 (5)
H14	−0.0857	0.8531	1.0554	0.029*
C11	−0.14136 (15)	1.2115 (3)	0.8400 (3)	0.0315 (6)	0.545 (5)
C13	−0.17454 (14)	1.0032 (3)	1.0113 (3)	0.0310 (6)	0.545 (5)
H13	−0.2122	0.9491	1.0761	0.037*	0.545 (5)
F1	−0.16627 (15)	1.3395 (3)	0.7761 (3)	0.0330 (9)	0.545 (5)
C11'	−0.14136 (15)	1.2115 (3)	0.8400 (3)	0.0315 (6)	0.455 (5)
H11	−0.1559	1.3032	0.7838	0.038*	0.455 (5)
C13'	−0.17454 (14)	1.0032 (3)	1.0113 (3)	0.0310 (6)	0.455 (5)
F1'	−0.23113 (18)	0.9534 (4)	1.1023 (4)	0.0392 (12)	0.455 (5)

	U11	U22	U33	U12	U13	U23
S1	0.0221 (2)	0.0178 (2)	0.0245 (3)	−0.0018 (2)	−0.0014 (3)	−0.0059 (2)
O1	0.0187 (7)	0.0219 (8)	0.0332 (9)	0.0019 (6)	−0.0077 (6)	−0.0077 (7)
O2	0.0198 (8)	0.0194 (8)	0.0370 (10)	−0.0001 (6)	−0.0014 (7)	−0.0092 (7)
N1	0.0181 (9)	0.0169 (9)	0.0205 (9)	0.0010 (7)	0.0011 (7)	−0.0018 (8)
N2	0.0165 (9)	0.0178 (9)	0.0300 (11)	0.0007 (7)	−0.0026 (8)	−0.0070 (8)
C1	0.0175 (10)	0.0170 (10)	0.0208 (12)	0.0006 (8)	−0.0013 (8)	0.0037 (9)
C2	0.0162 (10)	0.0149 (9)	0.0171 (11)	−0.0008 (8)	−0.0004 (8)	−0.0001 (8)
C3	0.0198 (11)	0.0139 (10)	0.0163 (10)	−0.0010 (8)	0.0016 (8)	0.0019 (9)
C4	0.0194 (10)	0.0147 (10)	0.0123 (10)	0.0002 (8)	0.0006 (8)	0.0015 (8)
C5	0.0172 (10)	0.0201 (11)	0.0197 (11)	0.0003 (8)	−0.0007 (8)	0.0030 (9)
C6	0.0203 (10)	0.0213 (10)	0.0226 (12)	−0.0011 (8)	−0.0030 (9)	−0.0002 (9)
C7	0.0204 (10)	0.0145 (10)	0.0165 (10)	−0.0013 (8)	0.0003 (8)	0.0006 (8)
C8	0.0184 (11)	0.0211 (11)	0.0199 (12)	−0.0006 (9)	−0.0015 (9)	−0.0005 (9)
C9	0.0178 (10)	0.0219 (11)	0.0194 (11)	0.0016 (9)	−0.0033 (8)	−0.0071 (9)
C10	0.0214 (12)	0.0197 (11)	0.0256 (12)	−0.0001 (10)	−0.0029 (9)	−0.0040 (10)
C12	0.0170 (11)	0.0419 (15)	0.0434 (15)	0.0045 (11)	−0.0050 (11)	−0.0252 (13)
C14	0.0249 (12)	0.0257 (11)	0.0230 (12)	−0.0059 (10)	0.0003 (10)	−0.0021 (10)
C11	0.0325 (14)	0.0242 (12)	0.0379 (15)	0.0084 (11)	−0.0111 (12)	−0.0113 (11)
C13	0.0208 (12)	0.0425 (16)	0.0296 (14)	−0.0062 (10)	0.0022 (10)	−0.0162 (12)
F1	0.0327 (16)	0.0212 (14)	0.0452 (18)	0.0071 (12)	−0.0064 (12)	0.0067 (12)
C11'	0.0325 (14)	0.0242 (12)	0.0379 (15)	0.0084 (11)	−0.0111 (12)	−0.0113 (11)
C13'	0.0208 (12)	0.0425 (16)	0.0296 (14)	−0.0062 (10)	0.0022 (10)	−0.0162 (12)
F1'	0.0281 (18)	0.046 (2)	0.044 (2)	−0.0163 (14)	0.0099 (15)	−0.0147 (18)

S1—C7	1.731 (2)	C6—H6	0.9500
S1—C6	1.733 (2)	C9—C14	1.388 (3)
O1—C8	1.319 (3)	C9—C10	1.384 (3)
O1—H1O	0.852 (10)	C10—C11'	1.380 (3)
O2—C8	1.227 (3)	C10—C11	1.380 (3)
N1—C1	1.332 (3)	C10—H10	0.9500
N1—C7	1.356 (3)	C12—C11'	1.365 (4)
N2—C3	1.356 (3)	C12—C11	1.365 (4)
N2—C9	1.426 (3)	C12—C13'	1.373 (4)
N2—H2N	0.881 (10)	C12—C13	1.373 (4)
C1—C2	1.394 (3)	C12—H12	0.9500
C1—H1	0.9500	C14—C13'	1.378 (3)
C2—C3	1.427 (3)	C14—C13	1.378 (3)
C2—C8	1.484 (3)	C14—H14	0.9500
C3—C4	1.422 (3)	C11—F1	1.298 (4)
C4—C7	1.394 (3)	C13—H13	0.9500
C4—C5	1.445 (3)	C11'—H11	0.9500
C5—C6	1.340 (3)	C13'—F1'	1.284 (4)
C5—H5	0.9500
C7—S1—C6	90.55 (10)	C11'—C10—C9	118.6 (2)
C8—O1—H1O	104.9 (19)	C11—C10—C9	118.6 (2)
C1—N1—C7	114.12 (18)	C11'—C10—H10	120.7
C3—N2—C9	129.99 (18)	C11—C10—H10	120.7
C3—N2—H2N	110.0 (17)	C9—C10—H10	120.7
C9—N2—H2N	119.9 (17)	C11'—C12—C11	0.0 (3)
N1—C1—C2	125.5 (2)	C11'—C12—C13'	117.7 (2)
N1—C1—H1	117.3	C11—C12—C13'	117.7 (2)
C2—C1—H1	117.3	C11'—C12—C13	117.7 (2)
C1—C2—C3	119.5 (2)	C11—C12—C13	117.7 (2)
C1—C2—C8	119.12 (19)	C13'—C12—C13	0.0 (2)
C3—C2—C8	121.30 (19)	C11'—C12—H12	121.1
N2—C3—C4	124.5 (2)	C11—C12—H12	121.1
N2—C3—C2	119.2 (2)	C13'—C12—H12	121.1
C4—C3—C2	116.25 (18)	C13—C12—H12	121.1
C7—C4—C3	117.46 (18)	C9—C14—C13'	118.9 (2)
C7—C4—C5	110.70 (19)	C9—C14—C13	118.9 (2)
C3—C4—C5	131.71 (19)	C13'—C14—C13	0.00 (7)
C6—C5—C4	113.0 (2)	C9—C14—H14	120.6
C6—C5—H5	123.5	C13'—C14—H14	120.6
C4—C5—H5	123.5	C13—C14—H14	120.6
C5—C6—S1	113.36 (17)	F1—C11—C12	113.5 (3)
C5—C6—H6	123.3	F1—C11—C10	123.8 (3)
S1—C6—H6	123.3	C12—C11—C10	122.6 (2)
N1—C7—C4	127.12 (19)	C12—C13—C14	122.1 (2)
N1—C7—S1	120.36 (16)	C12—C13—H13	118.9
C4—C7—S1	112.43 (15)	C14—C13—H13	118.9
O2—C8—O1	122.0 (2)	C12—C11'—C10	122.6 (2)
O2—C8—C2	123.44 (19)	C12—C11'—H11	118.7
O1—C8—C2	114.57 (19)	C10—C11'—H11	118.7
C14—C9—C10	120.1 (2)	F1'—C13'—C12	109.9 (3)
C14—C9—N2	121.3 (2)	F1'—C13'—C14	127.8 (3)
C10—C9—N2	118.2 (2)	C12—C13'—C14	122.1 (2)
C11'—C10—C11	0.0 (2)
C7—N1—C1—C2	−0.3 (3)	C10—C9—C14—C13'	−0.5 (3)
N1—C1—C2—C3	−1.9 (3)	N2—C9—C14—C13'	172.4 (2)
N1—C1—C2—C8	−178.91 (19)	C10—C9—C14—C13	−0.5 (3)
C9—N2—C3—C4	9.1 (4)	N2—C9—C14—C13	172.4 (2)
C9—N2—C3—C2	−173.2 (2)	C11'—C12—C11—F1	0 (97)
C1—C2—C3—N2	−174.7 (2)	C13'—C12—C11—F1	−176.8 (2)
C8—C2—C3—N2	2.2 (3)	C13—C12—C11—F1	−176.8 (2)
C1—C2—C3—C4	3.1 (3)	C11'—C12—C11—C10	0 (100)
C8—C2—C3—C4	−179.95 (19)	C13'—C12—C11—C10	−0.4 (4)
N2—C3—C4—C7	175.4 (2)	C13—C12—C11—C10	−0.4 (4)
C2—C3—C4—C7	−2.3 (3)	C11'—C10—C11—F1	0 (100)
N2—C3—C4—C5	0.0 (4)	C9—C10—C11—F1	176.5 (3)
C2—C3—C4—C5	−177.7 (2)	C11'—C10—C11—C12	0 (75)
C7—C4—C5—C6	0.2 (3)	C9—C10—C11—C12	0.4 (4)
C3—C4—C5—C6	175.9 (2)	C11'—C12—C13—C14	−0.1 (4)
C4—C5—C6—S1	−0.3 (3)	C11—C12—C13—C14	−0.1 (4)
C7—S1—C6—C5	0.20 (18)	C13'—C12—C13—C14	0 (100)
C1—N1—C7—C4	1.2 (3)	C9—C14—C13—C12	0.6 (4)
C1—N1—C7—S1	177.51 (16)	C13'—C14—C13—C12	0 (100)
C3—C4—C7—N1	0.2 (3)	C11—C12—C11'—C10	0 (100)
C5—C4—C7—N1	176.5 (2)	C13'—C12—C11'—C10	−0.4 (4)
C3—C4—C7—S1	−176.41 (16)	C13—C12—C11'—C10	−0.4 (4)
C5—C4—C7—S1	−0.1 (2)	C11—C10—C11'—C12	0 (75)
C6—S1—C7—N1	−176.90 (18)	C9—C10—C11'—C12	0.4 (4)
C6—S1—C7—C4	−0.07 (17)	C11'—C12—C13'—F1'	174.9 (3)
C1—C2—C8—O2	166.8 (2)	C11—C12—C13'—F1'	174.9 (3)
C3—C2—C8—O2	−10.2 (3)	C13—C12—C13'—F1'	0 (59)
C1—C2—C8—O1	−13.5 (3)	C11'—C12—C13'—C14	−0.1 (4)
C3—C2—C8—O1	169.52 (19)	C11—C12—C13'—C14	−0.1 (4)
C3—N2—C9—C14	65.4 (4)	C13—C12—C13'—C14	0 (100)
C3—N2—C9—C10	−121.5 (3)	C9—C14—C13'—F1'	−173.6 (3)
C14—C9—C10—C11'	0.0 (3)	C13—C14—C13'—F1'	0 (79)
N2—C9—C10—C11'	−173.1 (2)	C9—C14—C13'—C12	0.6 (4)
C14—C9—C10—C11	0.0 (3)	C13—C14—C13'—C12	0 (100)
N2—C9—C10—C11	−173.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···N1i	0.86 (2)	1.84 (2)	2.681 (2)	167 (3)
N2—H2n···O2	0.88 (2)	1.85 (2)	2.635 (2)	147 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1o⋯N1i	0.86 (2)	1.84 (2)	2.681 (2)	167 (3)
N2—H2n⋯O2	0.88 (2)	1.85 (2)	2.635 (2)	147 (2)

Symmetry code: (i) .