Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803005464/na6210sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803005464/na6210Isup2.hkl |
CCDC reference: 209944
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 (C═O), 1685 (C═O), 1600 (C═C); 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.
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.
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).
Fig. 1. Plot showing the atomic numbering scheme for the title compound. Displacement ellipsoids are drawn at 50% probability level for non-H atoms. |
C16H11NO4S | F(000) = 648 |
Mr = 313.32 | Dx = 1.433 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54180 Å |
a = 13.3208 (5) Å | Cell parameters from 39 reflections |
b = 12.5015 (4) Å | θ = 6.8–27.9° |
c = 8.9448 (4) Å | µ = 2.15 mm−1 |
β = 102.859 (3)° | T = 293 K |
V = 1452.22 (8) Å3 | Plate, colourless |
Z = 4 | 0.40 × 0.20 × 0.02 mm |
Siemens P4 four-circle diffractometer | Rint = 0.042 |
ω/2θ scans | θmax = 69.3° |
Absorption correction: ψ scan (North et al., 1968) | h = −16→16 |
Tmin = 0.627, Tmax = 0.958 | k = −15→1 |
3514 measured reflections | l = −1→10 |
2535 independent reflections | 3 standard reflections every 100 reflections |
1565 reflections with F2 > 2σ(F2) | intensity decay: 2% |
Refinement on F2 | H-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) = 0.167 | Δρmax = 0.33 e Å−3 |
S = 1.11 | Δρmin = −0.27 e Å−3 |
2535 reflections | Extinction correction: SHELXL97', Fc*=kFc[1+0.001xFc2λ3/sin((2θ)]-1/4 |
203 parameters | Extinction coefficient: 0.0050 (5) |
C16H11NO4S | V = 1452.22 (8) Å3 |
Mr = 313.32 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 13.3208 (5) Å | µ = 2.15 mm−1 |
b = 12.5015 (4) Å | T = 293 K |
c = 8.9448 (4) Å | 0.40 × 0.20 × 0.02 mm |
β = 102.859 (3)° |
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 = 0.958 | 3 standard reflections every 100 reflections |
3514 measured reflections | intensity decay: 2% |
2535 independent reflections |
R[F2 > 2σ(F2)] = 0.055 | 203 parameters |
wR(F2) = 0.167 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.33 e Å−3 |
2535 reflections | Δρmin = −0.27 e Å−3 |
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 |
x | y | z | Uiso*/Ueq | ||
S1 | 0.77152 (8) | 0.39908 (8) | 0.81170 (14) | 0.0550 (4) | |
O22 | 0.5391 (2) | 0.3737 (2) | 1.0132 (4) | 0.0670 (11) | |
O23 | 0.6114 (3) | 0.5134 (2) | 0.9184 (4) | 0.0713 (13) | |
O52 | 0.8690 (3) | −0.1027 (2) | 0.6492 (4) | 0.0698 (11) | |
O53 | 1.0069 (2) | −0.0639 (2) | 0.8349 (4) | 0.0605 (10) | |
N7 | 0.8995 (2) | 0.2564 (3) | 0.7276 (4) | 0.0480 (10) | |
C2 | 0.6799 (3) | 0.3444 (3) | 0.8994 (5) | 0.0493 (14) | |
C3 | 0.6837 (3) | 0.2361 (3) | 0.9109 (5) | 0.0496 (14) | |
C3A | 0.7635 (3) | 0.1912 (3) | 0.8481 (5) | 0.0443 (11) | |
C4 | 0.7950 (3) | 0.0838 (3) | 0.8343 (5) | 0.0439 (11) | |
C5 | 0.8791 (3) | 0.0681 (3) | 0.7688 (5) | 0.0462 (14) | |
C6 | 0.9296 (3) | 0.1548 (3) | 0.7158 (5) | 0.0476 (14) | |
C7A | 0.8185 (3) | 0.2722 (3) | 0.7911 (5) | 0.0463 (14) | |
C21 | 0.6039 (3) | 0.4118 (3) | 0.9495 (6) | 0.0566 (14) | |
C41 | 0.7395 (3) | −0.0060 (3) | 0.8916 (5) | 0.0494 (14) | |
C42 | 0.6322 (3) | −0.0097 (4) | 0.8550 (6) | 0.0593 (16) | |
C43 | 0.5816 (4) | −0.0920 (4) | 0.9095 (7) | 0.0756 (19) | |
C44 | 0.6354 (4) | −0.1712 (4) | 0.9981 (7) | 0.086 (2) | |
C45 | 0.7411 (4) | −0.1696 (4) | 1.0328 (7) | 0.0765 (19) | |
C46 | 0.7938 (3) | −0.0872 (3) | 0.9807 (5) | 0.0575 (14) | |
C51 | 0.9162 (3) | −0.0427 (3) | 0.7446 (5) | 0.0475 (14) | |
C61 | 1.0175 (3) | 0.1398 (3) | 0.6389 (5) | 0.0579 (14) | |
H3 | 0.63914 | 0.19572 | 0.95482 | 0.0619* | |
H23 | 0.56454 | 0.54658 | 0.94310 | 0.0891* | |
H42 | 0.59481 | 0.04332 | 0.79386 | 0.0742* | |
H43 | 0.50997 | −0.09379 | 0.88571 | 0.0941* | |
H44 | 0.60042 | −0.22616 | 1.03493 | 0.1080* | |
H45 | 0.77754 | −0.22413 | 1.09167 | 0.0953* | |
H46 | 0.86537 | −0.08617 | 1.00525 | 0.0720* | |
H53 | 1.02829 | −0.12114 | 0.80976 | 0.0759* | |
H61A | 0.99407 | 0.10205 | 0.54414 | 0.0724* | |
H61B | 1.07092 | 0.09939 | 0.70472 | 0.0724* | |
H61C | 1.04398 | 0.20844 | 0.61860 | 0.0724* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0555 (6) | 0.0377 (5) | 0.0779 (8) | 0.0027 (4) | 0.0280 (5) | −0.0001 (5) |
O22 | 0.0646 (19) | 0.0526 (18) | 0.094 (2) | 0.0079 (15) | 0.0395 (18) | −0.0041 (17) |
O23 | 0.068 (2) | 0.0442 (17) | 0.113 (3) | 0.0119 (14) | 0.044 (2) | 0.0013 (17) |
O52 | 0.068 (2) | 0.0525 (18) | 0.087 (2) | −0.0031 (15) | 0.0129 (18) | −0.0229 (17) |
O53 | 0.0515 (16) | 0.0433 (16) | 0.087 (2) | 0.0069 (13) | 0.0160 (16) | −0.0126 (15) |
N7 | 0.0452 (17) | 0.0392 (17) | 0.064 (2) | −0.0002 (14) | 0.0217 (16) | −0.0027 (16) |
C2 | 0.046 (2) | 0.043 (2) | 0.062 (3) | 0.0025 (17) | 0.0188 (19) | −0.0012 (19) |
C3 | 0.047 (2) | 0.044 (2) | 0.061 (3) | 0.0025 (17) | 0.019 (2) | 0.0032 (19) |
C3A | 0.046 (2) | 0.0377 (19) | 0.052 (2) | −0.0003 (16) | 0.0170 (18) | 0.0012 (17) |
C4 | 0.0434 (19) | 0.0388 (19) | 0.052 (2) | 0.0029 (16) | 0.0157 (18) | −0.0024 (17) |
C5 | 0.052 (2) | 0.0351 (19) | 0.055 (3) | 0.0015 (16) | 0.0196 (19) | −0.0052 (17) |
C6 | 0.043 (2) | 0.048 (2) | 0.055 (3) | −0.0032 (17) | 0.0178 (18) | −0.0034 (19) |
C7A | 0.047 (2) | 0.038 (2) | 0.055 (3) | 0.0008 (16) | 0.0135 (19) | −0.0029 (17) |
C21 | 0.051 (2) | 0.048 (2) | 0.074 (3) | 0.0057 (19) | 0.021 (2) | −0.004 (2) |
C41 | 0.057 (2) | 0.038 (2) | 0.057 (3) | −0.0020 (17) | 0.021 (2) | −0.0040 (18) |
C42 | 0.050 (2) | 0.059 (3) | 0.072 (3) | −0.003 (2) | 0.020 (2) | 0.007 (2) |
C43 | 0.058 (3) | 0.072 (3) | 0.098 (4) | −0.016 (2) | 0.020 (3) | 0.011 (3) |
C44 | 0.085 (4) | 0.063 (3) | 0.117 (5) | −0.022 (3) | 0.035 (4) | 0.017 (3) |
C45 | 0.082 (3) | 0.047 (3) | 0.103 (4) | −0.002 (2) | 0.026 (3) | 0.024 (3) |
C46 | 0.057 (2) | 0.045 (2) | 0.071 (3) | 0.0003 (19) | 0.015 (2) | 0.008 (2) |
C51 | 0.044 (2) | 0.038 (2) | 0.065 (3) | −0.0027 (17) | 0.022 (2) | −0.0049 (19) |
C61 | 0.056 (2) | 0.049 (2) | 0.075 (3) | 0.0006 (19) | 0.028 (2) | −0.006 (2) |
S1—C2 | 1.732 (4) | C5—C6 | 1.412 (6) |
S1—C7A | 1.730 (4) | C6—C61 | 1.496 (6) |
O22—C21 | 1.231 (5) | C41—C46 | 1.390 (6) |
O23—C21 | 1.309 (5) | C41—C42 | 1.394 (6) |
O52—C51 | 1.203 (5) | C42—C43 | 1.377 (7) |
O53—C51 | 1.322 (5) | C43—C44 | 1.367 (8) |
O23—H23 | 0.8197 | C44—C45 | 1.373 (8) |
O53—H53 | 0.8200 | C45—C46 | 1.384 (7) |
N7—C6 | 1.343 (5) | C3—H3 | 0.9302 |
N7—C7A | 1.341 (5) | C42—H42 | 0.9302 |
C2—C3 | 1.358 (5) | C43—H43 | 0.9305 |
C2—C21 | 1.462 (6) | C44—H44 | 0.9306 |
C3—C3A | 1.424 (6) | C45—H45 | 0.9294 |
C3A—C7A | 1.410 (6) | C46—H46 | 0.9296 |
C3A—C4 | 1.420 (5) | C61—H61A | 0.9596 |
C4—C5 | 1.389 (6) | C61—H61B | 0.9601 |
C4—C41 | 1.496 (6) | C61—H61C | 0.9603 |
C5—C51 | 1.502 (5) | ||
C2—S1—C7A | 89.7 (2) | C42—C41—C46 | 119.1 (4) |
C21—O23—H23 | 109.58 | C41—C42—C43 | 119.9 (5) |
C51—O53—H53 | 109.48 | C42—C43—C44 | 120.8 (5) |
C6—N7—C7A | 117.1 (3) | C43—C44—C45 | 120.0 (5) |
S1—C2—C21 | 121.2 (3) | C44—C45—C46 | 120.4 (5) |
S1—C2—C3 | 114.2 (3) | C41—C46—C45 | 119.9 (4) |
C3—C2—C21 | 124.6 (4) | O53—C51—C5 | 112.5 (3) |
C2—C3—C3A | 112.4 (4) | O52—C51—O53 | 124.8 (4) |
C4—C3A—C7A | 117.4 (4) | O52—C51—C5 | 122.7 (4) |
C3—C3A—C7A | 110.7 (3) | C2—C3—H3 | 123.82 |
C3—C3A—C4 | 131.9 (4) | C3A—C3—H3 | 123.74 |
C3A—C4—C5 | 116.9 (4) | C41—C42—H42 | 120.08 |
C3A—C4—C41 | 120.1 (4) | C43—C42—H42 | 120.02 |
C5—C4—C41 | 123.0 (3) | C42—C43—H43 | 119.65 |
C4—C5—C6 | 121.5 (4) | C44—C43—H43 | 119.58 |
C6—C5—C51 | 117.6 (4) | C43—C44—H44 | 120.05 |
C4—C5—C51 | 120.9 (3) | C45—C44—H44 | 119.99 |
N7—C6—C61 | 115.6 (3) | C44—C45—H45 | 119.83 |
N7—C6—C5 | 121.8 (4) | C46—C45—H45 | 119.76 |
C5—C6—C61 | 122.6 (3) | C41—C46—H46 | 120.05 |
S1—C7A—C3A | 113.0 (3) | C45—C46—H46 | 120.07 |
S1—C7A—N7 | 121.6 (3) | C6—C61—H61A | 109.50 |
N7—C7A—C3A | 125.4 (4) | C6—C61—H61B | 109.46 |
O23—C21—C2 | 113.8 (4) | C6—C61—H61C | 109.45 |
O22—C21—C2 | 121.6 (3) | H61A—C61—H61B | 109.50 |
O22—C21—O23 | 124.6 (4) | H61A—C61—H61C | 109.47 |
C4—C41—C42 | 120.2 (4) | H61B—C61—H61C | 109.44 |
C4—C41—C46 | 120.7 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O23—H23···O22i | 0.82 | 1.81 | 2.633 (5) | 176 |
O53—H53···N7ii | 0.82 | 1.88 | 2.688 (4) | 170 |
C45—H45···O52iii | 0.93 | 2.48 | 3.362 (6) | 158 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+2, y−1/2, −z+3/2; (iii) x, −y−1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C16H11NO4S |
Mr | 313.32 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 13.3208 (5), 12.5015 (4), 8.9448 (4) |
β (°) | 102.859 (3) |
V (Å3) | 1452.22 (8) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 2.15 |
Crystal size (mm) | 0.40 × 0.20 × 0.02 |
Data collection | |
Diffractometer | Siemens P4 four-circle diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.627, 0.958 |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 3514, 2535, 1565 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.607 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.167, 1.11 |
No. of reflections | 2535 |
No. of parameters | 203 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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).
S1—C2 | 1.732 (4) | O52—C51 | 1.203 (5) |
S1—C7A | 1.730 (4) | O53—C51 | 1.322 (5) |
O22—C21 | 1.231 (5) | N7—C6 | 1.343 (5) |
O23—C21 | 1.309 (5) | N7—C7A | 1.341 (5) |
C2—S1—C7A | 89.7 (2) | N7—C7A—C3A | 125.4 (4) |
C6—N7—C7A | 117.1 (3) | O23—C21—C2 | 113.8 (4) |
S1—C2—C21 | 121.2 (3) | O22—C21—C2 | 121.6 (3) |
S1—C2—C3 | 114.2 (3) | O22—C21—O23 | 124.6 (4) |
N7—C6—C61 | 115.6 (3) | O53—C51—C5 | 112.5 (3) |
N7—C6—C5 | 121.8 (4) | O52—C51—O53 | 124.8 (4) |
S1—C7A—C3A | 113.0 (3) | O52—C51—C5 | 122.7 (4) |
S1—C7A—N7 | 121.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O23—H23···O22i | 0.82 | 1.81 | 2.633 (5) | 176 |
O53—H53···N7ii | 0.82 | 1.88 | 2.688 (4) | 170 |
C45—H45···O52iii | 0.93 | 2.48 | 3.362 (6) | 158 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+2, y−1/2, −z+3/2; (iii) x, −y−1/2, z+1/2. |
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.