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The crystal structure of the title compound, C16H11NO4S, is stabilized by intermolecular hydrogen bonds of the types O—H...O, O—H...N and C—H...O. The thieno­[2,3-b]­pyridine moiety is planar.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803005464/na6210sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803005464/na6210Isup2.hkl
Contains datablock I

CCDC reference: 209944

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.055
  • wR factor = 0.167
  • Data-to-parameter ratio = 12.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 69.29 From the CIF: _reflns_number_total 2535 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 2716 Completeness (_total/calc) 93.34% Alert C: < 95% complete
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

Thieno[2,3-b]pyridine derivatives form a class of fused heterocyclic compounds whith interesting bio- and pharmacological properties. The activity of some dihydrothieno[2,3-b]pyridine derivatives has been throroughly investigated as calcium antagonists in the treatment of cardiovascular diseases (Dessy et al., 1993). Also, the enantioselective synthesis of thieno[2,3-b]pyridines as a 5-lipoxygenase (5-LO) inhibitor has been reported (Rohloff et al., 1994). In previous work, we described the crystal structure of two different dihydrothieno[2,3-b]pyridines (Duque et al., 1998, 2000) and recently we reported the crystal structure of 2,5-diethoxycarbonyl-6-methyl-4-phenylthieno[2,3-b]pyridine (Novoa de Armas et al., 2003a) and its substituted 4-(4-bromophenyl) analog (Novoa de Armas et al., 2003b). Saponification of the two ester groups yields the title compound, (I), as a crystalline solid. In (I), the thieno[2,3-b]pyridine moiety is planar and the dihedral angle between the least-squares plane of the thieno[2,3-b]pyridine moiety and the 4-phenyl ring is 46.3 (2)°. The carboxyl group C21/O22/O23 is nearly coplanar with the hieno[2,3-b]pyridine moiety [C3—C2—C21—O22 = 3.2 (7)°], while the other carboxyl group, C51/O52/O53, is not [C4—C5—C51—O52 = 71.2 (6)°]. The mean Csp2—Csp2 bond length within the 4-phenyl ring is 1.383 (4) Å. The crystal structure is stabilized by hydrogen bonds of the types O—H···O, O—H···N and C—H.·O. The diference between the ester 2,5-diethoxycarbonyl-6-methyl-4-phenylthieno[2,3-b]pyridine and title acid (I) is the presence of the intermolecular O–H···O -hydrogen bonds in the latter.

Experimental top

Diethyl 4-phenyl-thieno 2,3 − b pyridine-2,5-dicarboxylate (2 mmol) was mixed with 20 ml of 10% aqueous sodium hydroxide and the mixture was refluxed vigorously until all the solid ester had dissolved (about 1 h). The saponification mixture was then cooled and the aqueous solution was separated from any oil present. Afterwards, the solution was acidified to Congo red paper with 10% sulfuric acid. Compound (I) was collected by filtration and washed thoroughly with water, then dried (yield 86%; m.p. 638 K). IR (KBr, cm−1): 3384 (OH), 1724 (CO), 1685 (CO), 1600 (CC); 1H NMR (DMSO-δ6, p.p.m.): 7.58–7.51 (m, 5H, Ph), 7.49 (s, 1H, CH), 3.44 (br s, 2H, OH), 2.66 (s, 3H, CH3); 13C NMR (DMSO-δ6, p.p.m.): 168.6 (CO), 162.2 (CO), 161.1 (C6), 154.2 (C4), 143.0 (C1'), 134.9 (C2), 133.8 (C7a), 128.9 (C4'), 128.6 (C3a), 128.4 (C3' and C5'), 128.3 (C2' and C6'), 127.1 (C3), 126.4 (C5), 22.7 (CH3); MS, m/Z (intensity %): 313 (M+, 100), 296 (30), 295 (50), 222 (12), 78 (19), 63 (38). Crystals suitable for X-ray analysis were obtained by slow evaporation from methanol.

Refinement top

H atoms were calculated geometrically and included in the refinement, but were constrained to ride on their parent atoms, with Uiso(H) values fixed at 1.3Ueq of their parent atoms.

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Bergerhoff, 1996); software used to prepare material for publication: PLATON (Spek, 2003), PARST (Nardelli, 1995) and PARSTCIF (Nardelli, 1991).

Figures top
[Figure 1] Fig. 1. Plot showing the atomic numbering scheme for the title compound. Displacement ellipsoids are drawn at 50% probability level for non-H atoms.
6-Methyl-4-phenylthieno[2,3-b]pyridine-2,5-dicarboxylic acid top
Crystal data top
C16H11NO4SF(000) = 648
Mr = 313.32Dx = 1.433 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54180 Å
a = 13.3208 (5) ÅCell parameters from 39 reflections
b = 12.5015 (4) Åθ = 6.8–27.9°
c = 8.9448 (4) ŵ = 2.15 mm1
β = 102.859 (3)°T = 293 K
V = 1452.22 (8) Å3Plate, colourless
Z = 40.40 × 0.20 × 0.02 mm
Data collection top
Siemens P4 four-circle
diffractometer
Rint = 0.042
ω/2θ scansθmax = 69.3°
Absorption correction: ψ scan
(North et al., 1968)
h = 1616
Tmin = 0.627, Tmax = 0.958k = 151
3514 measured reflectionsl = 110
2535 independent reflections3 standard reflections every 100 reflections
1565 reflections with F2 > 2σ(F2) intensity decay: 2%
Refinement top
Refinement on F2H-atom parameters constrained
Least-squares matrix: full w = 1/[σ2(Fo2) + (0.0433P)2 + 2.354P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.055(Δ/σ)max = 0.001
wR(F2) = 0.167Δρmax = 0.33 e Å3
S = 1.11Δρmin = 0.27 e Å3
2535 reflectionsExtinction correction: SHELXL97', Fc*=kFc[1+0.001xFc2λ3/sin((2θ)]-1/4
203 parametersExtinction coefficient: 0.0050 (5)
Crystal data top
C16H11NO4SV = 1452.22 (8) Å3
Mr = 313.32Z = 4
Monoclinic, P21/cCu Kα radiation
a = 13.3208 (5) ŵ = 2.15 mm1
b = 12.5015 (4) ÅT = 293 K
c = 8.9448 (4) Å0.40 × 0.20 × 0.02 mm
β = 102.859 (3)°
Data collection top
Siemens P4 four-circle
diffractometer
1565 reflections with F2 > 2σ(F2)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.042
Tmin = 0.627, Tmax = 0.9583 standard reflections every 100 reflections
3514 measured reflections intensity decay: 2%
2535 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.055203 parameters
wR(F2) = 0.167H-atom parameters constrained
S = 1.11Δρmax = 0.33 e Å3
2535 reflectionsΔρmin = 0.27 e Å3
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.77152 (8)0.39908 (8)0.81170 (14)0.0550 (4)
O220.5391 (2)0.3737 (2)1.0132 (4)0.0670 (11)
O230.6114 (3)0.5134 (2)0.9184 (4)0.0713 (13)
O520.8690 (3)0.1027 (2)0.6492 (4)0.0698 (11)
O531.0069 (2)0.0639 (2)0.8349 (4)0.0605 (10)
N70.8995 (2)0.2564 (3)0.7276 (4)0.0480 (10)
C20.6799 (3)0.3444 (3)0.8994 (5)0.0493 (14)
C30.6837 (3)0.2361 (3)0.9109 (5)0.0496 (14)
C3A0.7635 (3)0.1912 (3)0.8481 (5)0.0443 (11)
C40.7950 (3)0.0838 (3)0.8343 (5)0.0439 (11)
C50.8791 (3)0.0681 (3)0.7688 (5)0.0462 (14)
C60.9296 (3)0.1548 (3)0.7158 (5)0.0476 (14)
C7A0.8185 (3)0.2722 (3)0.7911 (5)0.0463 (14)
C210.6039 (3)0.4118 (3)0.9495 (6)0.0566 (14)
C410.7395 (3)0.0060 (3)0.8916 (5)0.0494 (14)
C420.6322 (3)0.0097 (4)0.8550 (6)0.0593 (16)
C430.5816 (4)0.0920 (4)0.9095 (7)0.0756 (19)
C440.6354 (4)0.1712 (4)0.9981 (7)0.086 (2)
C450.7411 (4)0.1696 (4)1.0328 (7)0.0765 (19)
C460.7938 (3)0.0872 (3)0.9807 (5)0.0575 (14)
C510.9162 (3)0.0427 (3)0.7446 (5)0.0475 (14)
C611.0175 (3)0.1398 (3)0.6389 (5)0.0579 (14)
H30.639140.195720.954820.0619*
H230.564540.546580.943100.0891*
H420.594810.043320.793860.0742*
H430.509970.093790.885710.0941*
H440.600420.226161.034930.1080*
H450.777540.224131.091670.0953*
H460.865370.086171.005250.0720*
H531.028290.121140.809760.0759*
H61A0.994070.102050.544140.0724*
H61B1.070920.099390.704720.0724*
H61C1.043980.208440.618600.0724*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0555 (6)0.0377 (5)0.0779 (8)0.0027 (4)0.0280 (5)0.0001 (5)
O220.0646 (19)0.0526 (18)0.094 (2)0.0079 (15)0.0395 (18)0.0041 (17)
O230.068 (2)0.0442 (17)0.113 (3)0.0119 (14)0.044 (2)0.0013 (17)
O520.068 (2)0.0525 (18)0.087 (2)0.0031 (15)0.0129 (18)0.0229 (17)
O530.0515 (16)0.0433 (16)0.087 (2)0.0069 (13)0.0160 (16)0.0126 (15)
N70.0452 (17)0.0392 (17)0.064 (2)0.0002 (14)0.0217 (16)0.0027 (16)
C20.046 (2)0.043 (2)0.062 (3)0.0025 (17)0.0188 (19)0.0012 (19)
C30.047 (2)0.044 (2)0.061 (3)0.0025 (17)0.019 (2)0.0032 (19)
C3A0.046 (2)0.0377 (19)0.052 (2)0.0003 (16)0.0170 (18)0.0012 (17)
C40.0434 (19)0.0388 (19)0.052 (2)0.0029 (16)0.0157 (18)0.0024 (17)
C50.052 (2)0.0351 (19)0.055 (3)0.0015 (16)0.0196 (19)0.0052 (17)
C60.043 (2)0.048 (2)0.055 (3)0.0032 (17)0.0178 (18)0.0034 (19)
C7A0.047 (2)0.038 (2)0.055 (3)0.0008 (16)0.0135 (19)0.0029 (17)
C210.051 (2)0.048 (2)0.074 (3)0.0057 (19)0.021 (2)0.004 (2)
C410.057 (2)0.038 (2)0.057 (3)0.0020 (17)0.021 (2)0.0040 (18)
C420.050 (2)0.059 (3)0.072 (3)0.003 (2)0.020 (2)0.007 (2)
C430.058 (3)0.072 (3)0.098 (4)0.016 (2)0.020 (3)0.011 (3)
C440.085 (4)0.063 (3)0.117 (5)0.022 (3)0.035 (4)0.017 (3)
C450.082 (3)0.047 (3)0.103 (4)0.002 (2)0.026 (3)0.024 (3)
C460.057 (2)0.045 (2)0.071 (3)0.0003 (19)0.015 (2)0.008 (2)
C510.044 (2)0.038 (2)0.065 (3)0.0027 (17)0.022 (2)0.0049 (19)
C610.056 (2)0.049 (2)0.075 (3)0.0006 (19)0.028 (2)0.006 (2)
Geometric parameters (Å, º) top
S1—C21.732 (4)C5—C61.412 (6)
S1—C7A1.730 (4)C6—C611.496 (6)
O22—C211.231 (5)C41—C461.390 (6)
O23—C211.309 (5)C41—C421.394 (6)
O52—C511.203 (5)C42—C431.377 (7)
O53—C511.322 (5)C43—C441.367 (8)
O23—H230.8197C44—C451.373 (8)
O53—H530.8200C45—C461.384 (7)
N7—C61.343 (5)C3—H30.9302
N7—C7A1.341 (5)C42—H420.9302
C2—C31.358 (5)C43—H430.9305
C2—C211.462 (6)C44—H440.9306
C3—C3A1.424 (6)C45—H450.9294
C3A—C7A1.410 (6)C46—H460.9296
C3A—C41.420 (5)C61—H61A0.9596
C4—C51.389 (6)C61—H61B0.9601
C4—C411.496 (6)C61—H61C0.9603
C5—C511.502 (5)
C2—S1—C7A89.7 (2)C42—C41—C46119.1 (4)
C21—O23—H23109.58C41—C42—C43119.9 (5)
C51—O53—H53109.48C42—C43—C44120.8 (5)
C6—N7—C7A117.1 (3)C43—C44—C45120.0 (5)
S1—C2—C21121.2 (3)C44—C45—C46120.4 (5)
S1—C2—C3114.2 (3)C41—C46—C45119.9 (4)
C3—C2—C21124.6 (4)O53—C51—C5112.5 (3)
C2—C3—C3A112.4 (4)O52—C51—O53124.8 (4)
C4—C3A—C7A117.4 (4)O52—C51—C5122.7 (4)
C3—C3A—C7A110.7 (3)C2—C3—H3123.82
C3—C3A—C4131.9 (4)C3A—C3—H3123.74
C3A—C4—C5116.9 (4)C41—C42—H42120.08
C3A—C4—C41120.1 (4)C43—C42—H42120.02
C5—C4—C41123.0 (3)C42—C43—H43119.65
C4—C5—C6121.5 (4)C44—C43—H43119.58
C6—C5—C51117.6 (4)C43—C44—H44120.05
C4—C5—C51120.9 (3)C45—C44—H44119.99
N7—C6—C61115.6 (3)C44—C45—H45119.83
N7—C6—C5121.8 (4)C46—C45—H45119.76
C5—C6—C61122.6 (3)C41—C46—H46120.05
S1—C7A—C3A113.0 (3)C45—C46—H46120.07
S1—C7A—N7121.6 (3)C6—C61—H61A109.50
N7—C7A—C3A125.4 (4)C6—C61—H61B109.46
O23—C21—C2113.8 (4)C6—C61—H61C109.45
O22—C21—C2121.6 (3)H61A—C61—H61B109.50
O22—C21—O23124.6 (4)H61A—C61—H61C109.47
C4—C41—C42120.2 (4)H61B—C61—H61C109.44
C4—C41—C46120.7 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O23—H23···O22i0.821.812.633 (5)176
O53—H53···N7ii0.821.882.688 (4)170
C45—H45···O52iii0.932.483.362 (6)158
Symmetry codes: (i) x+1, y+1, z+2; (ii) x+2, y1/2, z+3/2; (iii) x, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC16H11NO4S
Mr313.32
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)13.3208 (5), 12.5015 (4), 8.9448 (4)
β (°) 102.859 (3)
V3)1452.22 (8)
Z4
Radiation typeCu Kα
µ (mm1)2.15
Crystal size (mm)0.40 × 0.20 × 0.02
Data collection
DiffractometerSiemens P4 four-circle
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.627, 0.958
No. of measured, independent and
observed [F2 > 2σ(F2)] reflections
3514, 2535, 1565
Rint0.042
(sin θ/λ)max1)0.607
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.167, 1.11
No. of reflections2535
No. of parameters203
No. of restraints?
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.33, 0.27

Computer programs: XSCANS (Siemens, 1996), XSCANS, SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), DIAMOND (Bergerhoff, 1996), PLATON (Spek, 2003), PARST (Nardelli, 1995) and PARSTCIF (Nardelli, 1991).

Selected geometric parameters (Å, º) top
S1—C21.732 (4)O52—C511.203 (5)
S1—C7A1.730 (4)O53—C511.322 (5)
O22—C211.231 (5)N7—C61.343 (5)
O23—C211.309 (5)N7—C7A1.341 (5)
C2—S1—C7A89.7 (2)N7—C7A—C3A125.4 (4)
C6—N7—C7A117.1 (3)O23—C21—C2113.8 (4)
S1—C2—C21121.2 (3)O22—C21—C2121.6 (3)
S1—C2—C3114.2 (3)O22—C21—O23124.6 (4)
N7—C6—C61115.6 (3)O53—C51—C5112.5 (3)
N7—C6—C5121.8 (4)O52—C51—O53124.8 (4)
S1—C7A—C3A113.0 (3)O52—C51—C5122.7 (4)
S1—C7A—N7121.6 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O23—H23···O22i0.821.812.633 (5)176
O53—H53···N7ii0.821.882.688 (4)170
C45—H45···O52iii0.932.483.362 (6)158
Symmetry codes: (i) x+1, y+1, z+2; (ii) x+2, y1/2, z+3/2; (iii) x, y1/2, z+1/2.
 

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