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Acta Cryst. (2009). E65, o257    [ doi:10.1107/S1600536809000269 ]

Ethyl 3-(4-methylbenzenesulfonamido)thieno[2,3-b]pyridine-2-carboxylate

W. Zhang, R. Zheng, H. Song, S.-Y. Yang and L.-T. Yu

Abstract top

The thieno[2,3-b]pyridine ring system of the title compound, C17H16N2O4S2, is essentially planar, the amino and carbonyl groups being nearly coplanar with the heterocyclic ring system. There are two N-H...O hydrogen-bonding interactions involving the same N-H donor set and two different acceptors, one in an intramolecular bond helping to fix the molecular geometry and the other defining a dimeric structure around the symmetry centre at (0, {\script{1\over 2}}, {\script{1\over 2}}).

Comment top

Thieno[2,3-b]pyridine derivatives are of great importance owing to their wide biological properties (Litvinov et al.,2005). The title compound is one of the key intermediates in our synthetic investigations of antitumor drugs. We report here its crystal structure.

The thieno[2,3-b]pyridine ring system of the title compound C17H16N2O4S2, (Fig.1) is essentially planar, with the amino and the carbonyl groups being nearly coplanar with the heterocyclic ring system.

There are two main N-H···O H-bonding interactions (Table 1), involving the same N1-H1N donor set and two different acceptors, O4 (in an intramolecular bond fixing the molecular geometry) and O2 i, i: -x, -y+1, -z+1, defining a dimeric structure around the symmetry centre at (0,0.5,0.5) (Fig.2)

Related literature top

For general background, see: Litvinov et al. (2005). For related literature, see: Dwiggins (1975).

Experimental top

A solution of ethyl 3-amino-4H-thieno[2,3-b]pyridine -2-carboxylate(2 g, 9 mmol), p-toluenesulfonyl chloride (5.2 g, 27 mmol) and pyridine (3.7 ml, 45 mmol) in dichloromethane (100 ml) was stirred until the reaction was complete. The reaction mixture was washed twice with a saturated aqueous solution of CuSO4 and once with water. The organic layer was dried and concentrated in vacuum and the resulting residue was purified by crystallization from dichloromethane to yield a white solid (3.1 g, 91%). Crystals suitable for X-ray analysis were obtained by slow evaporation from a solution of dichloromethane and petroleum (1:2).

Refinement top

The crystal used for data collection was ground into a spheroidal shape in order to facilitate the absorption correction. This was made through an interpolation procedure with local modifications to the one reported by Dwiggins, 1975. muR values in the range 0-2.5 were taken from the International Tables for X-ray Crystallography (1992, Vol. C, p. 523), while those for muR in the range 2.6-10.0. were taken from International Tables for X-ray Crystallography (1959, Vol II, p. 302)

H atoms of the amino group were located in a difference map and refined freely. The remaining H atoms were positioned geometrically (C—H = 0.93–0.97 Å) and refined using a riding model, with Uĩso~(H) = 1.2–1.5U~eq~(C).

Computing details top

Data collection: DIFRAC (Gabe & White, 1993); cell refinement: DIFRAC (Gabe & White, 1993); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.
[Figure 2] Fig. 2. View of the dimeric structure in the title compound. Hydrogen bonds are shown as hollow bonds (intermolecular ones as dashed lines, intramolecular ones in full lining). Symmetry code: (i) -x, -y+1, -z+1.
Ethyl 3-(4-methylbenzenesulfonamido)thieno[2,3-b]pyridine-2-carboxylate top
Crystal data top
C17H16N2O4S2F(000) = 1568
Mr = 376.46Dx = 1.457 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 24 reflections
a = 14.809 (4) Åθ = 4.5–7.7°
b = 11.892 (3) ŵ = 0.34 mm−1
c = 19.494 (5) ÅT = 293 K
V = 3433.1 (15) Å3Block, colourless
Z = 80.46 × 0.44 × 0.42 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		2032 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.005
graphiteθmax = 25.6°, θmin = 2.1°
ω/2θ scansh = −17→10
Absorption correction: for a sphere
(interpolation; International Tables for X-ray Crystallography, 1959, Vol II, p. 302; 1992, Vol. C, p. 523); Table 5.3.6 B for muR in the range 2.6-10.0. The interpolation procedure of C.W.Dwiggins Jr (Acta Cryst.(1975) A31,146-148) is used with some modification.		k = −2→14
Tmin = 0.861, Tmax = 0.872l = −13→23
3590 measured reflections3 standard reflections every 200 reflections
3075 independent reflections intensity decay: 3.0%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.055H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.186 w = 1/[σ2(Fo2) + (0.0996P)2 + 1.4444P]
where P = (Fo2 + 2Fc2)/3
S = 1.13(Δ/σ)max < 0.001
3075 reflectionsΔρmax = 0.36 e Å−3
233 parametersΔρmin = −0.74 e Å−3
1 restraintExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0175 (17)
Crystal data top
C17H16N2O4S2V = 3433.1 (15) Å3
Mr = 376.46Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 14.809 (4) ŵ = 0.34 mm−1
b = 11.892 (3) ÅT = 293 K
c = 19.494 (5) Å0.46 × 0.44 × 0.42 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		2032 reflections with I > 2σ(I)
Absorption correction: for a sphere
(interpolation; International Tables for X-ray Crystallography, 1959, Vol II, p. 302; 1992, Vol. C, p. 523); Table 5.3.6 B for muR in the range 2.6-10.0. The interpolation procedure of C.W.Dwiggins Jr (Acta Cryst.(1975) A31,146-148) is used with some modification.		Rint = 0.005
Tmin = 0.861, Tmax = 0.872θmax = 25.6°
3590 measured reflections3 standard reflections every 200 reflections
3075 independent reflections intensity decay: 3.0%
Refinement top
R[F2 > 2σ(F2)] = 0.055H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.186Δρmax = 0.36 e Å−3
S = 1.13Δρmin = −0.74 e Å−3
3075 reflectionsAbsolute structure: ?
233 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Special details top

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 (Å2) top
xyzUiso*/Ueq
S10.09964 (6)0.61780 (8)0.44511 (5)0.0446 (3)
S2−0.09888 (7)0.97224 (9)0.42142 (5)0.0519 (3)
O10.14122 (18)0.6604 (2)0.38494 (13)0.0557 (7)
O20.09322 (18)0.4988 (2)0.45432 (15)0.0578 (8)
O3−0.12382 (18)0.9327 (2)0.56425 (12)0.0497 (7)
O4−0.0664 (2)0.7593 (3)0.57213 (13)0.0617 (8)
N1−0.0053 (2)0.6628 (3)0.44558 (15)0.0422 (7)
H1N−0.033 (3)0.642 (3)0.4875 (12)0.067 (13)*
N2−0.0759 (3)0.9677 (3)0.28514 (19)0.0651 (10)
C10.2655 (4)0.8311 (6)0.6960 (4)0.129 (3)
H1A0.21730.87230.71720.194*
H1B0.31260.88210.68280.194*
H1C0.28900.77690.72780.194*
C20.2296 (3)0.7703 (6)0.6323 (3)0.0842 (18)
C30.2462 (3)0.8165 (5)0.5677 (3)0.0783 (15)
H30.28270.87980.56350.094*
C40.2083 (3)0.7678 (3)0.5100 (2)0.0578 (11)
H40.21970.79750.46680.069*
C50.1529 (2)0.6741 (3)0.51725 (19)0.0469 (9)
C60.1372 (3)0.6279 (4)0.5808 (2)0.0622 (11)
H60.10060.56460.58500.075*
C70.1755 (3)0.6751 (5)0.6376 (2)0.0826 (16)
H70.16520.64330.68050.099*
C8−0.0288 (2)0.7731 (3)0.42354 (17)0.0399 (8)
C9−0.0649 (2)0.8527 (3)0.46538 (18)0.0417 (8)
C10−0.0648 (2)0.9136 (4)0.34493 (19)0.0495 (10)
C11−0.0285 (2)0.8071 (3)0.35295 (17)0.0434 (9)
C12−0.0836 (2)0.8412 (4)0.53894 (18)0.0446 (9)
C13−0.1472 (3)0.9290 (3)0.63719 (18)0.0524 (10)
H13A−0.09310.92080.66480.063*
H13B−0.18670.86570.64640.063*
C14−0.1939 (3)1.0370 (4)0.6541 (2)0.0623 (11)
H14A−0.15381.09880.64560.093*
H14B−0.21121.03670.70160.093*
H14C−0.24681.04460.62600.093*
C15−0.0523 (3)0.9075 (5)0.2299 (2)0.0724 (14)
H15−0.06060.94030.18700.087*
C16−0.0170 (3)0.8024 (5)0.2319 (2)0.0662 (13)
H16−0.00150.76700.19100.079*
C17−0.0036 (2)0.7466 (4)0.29326 (19)0.0511 (10)
H170.02020.67430.29520.061*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0471 (6)0.0449 (6)0.0417 (6)0.0037 (4)0.0058 (4)−0.0009 (4)
S20.0528 (6)0.0546 (7)0.0483 (6)0.0089 (5)−0.0010 (4)0.0069 (5)
O10.0528 (15)0.0707 (19)0.0435 (16)0.0033 (14)0.0104 (12)0.0073 (13)
O20.0690 (19)0.0428 (17)0.0617 (19)0.0040 (13)0.0060 (13)−0.0015 (13)
O30.0542 (15)0.0584 (17)0.0365 (14)0.0043 (13)0.0087 (11)−0.0027 (12)
O40.084 (2)0.066 (2)0.0350 (15)0.0072 (16)0.0038 (14)0.0072 (14)
N10.0420 (16)0.0428 (17)0.0418 (17)−0.0035 (13)0.0015 (13)0.0029 (13)
N20.072 (2)0.075 (3)0.048 (2)0.0039 (19)−0.0066 (17)0.0199 (19)
C10.093 (4)0.175 (7)0.120 (5)0.051 (4)−0.052 (4)−0.086 (5)
C20.047 (3)0.123 (5)0.083 (4)0.031 (3)−0.024 (2)−0.047 (3)
C30.053 (3)0.084 (4)0.098 (4)0.010 (2)−0.017 (3)−0.028 (3)
C40.050 (2)0.049 (2)0.074 (3)0.0013 (18)−0.005 (2)−0.002 (2)
C50.043 (2)0.050 (2)0.048 (2)0.0082 (17)0.0021 (16)0.0002 (17)
C60.053 (2)0.079 (3)0.055 (3)−0.001 (2)−0.0040 (19)0.007 (2)
C70.058 (3)0.140 (5)0.050 (3)0.026 (3)−0.010 (2)−0.012 (3)
C80.0349 (17)0.053 (2)0.0318 (18)−0.0077 (15)−0.0022 (14)0.0041 (15)
C90.0363 (17)0.055 (2)0.0337 (18)0.0026 (16)−0.0032 (14)0.0031 (16)
C100.0427 (19)0.065 (3)0.041 (2)−0.0023 (18)−0.0064 (16)0.0121 (18)
C110.0354 (17)0.063 (2)0.0315 (19)−0.0086 (16)−0.0014 (14)0.0019 (17)
C120.0399 (19)0.063 (2)0.0313 (19)−0.0064 (17)−0.0003 (14)0.0004 (18)
C130.059 (2)0.063 (3)0.034 (2)−0.003 (2)0.0059 (17)−0.0042 (18)
C140.068 (3)0.068 (3)0.051 (3)−0.007 (2)0.012 (2)−0.011 (2)
C150.071 (3)0.106 (4)0.040 (3)−0.005 (3)−0.009 (2)0.023 (3)
C160.060 (3)0.108 (4)0.030 (2)−0.024 (3)−0.0005 (17)0.003 (2)
C170.050 (2)0.061 (3)0.042 (2)−0.0113 (18)0.0022 (16)−0.0028 (17)
Geometric parameters (Å, °) top
S1—O11.418 (3)C4—H40.9300
S1—O21.430 (3)C5—C61.375 (6)
S1—N11.643 (3)C6—C71.366 (6)
S1—C51.746 (4)C6—H60.9300
S2—C101.722 (4)C7—H70.9300
S2—C91.734 (4)C8—C91.359 (5)
O3—C121.335 (5)C8—C111.434 (5)
O3—C131.464 (4)C9—C121.467 (5)
O4—C121.197 (5)C10—C111.384 (6)
N1—C81.423 (5)C11—C171.417 (5)
N1—H1N0.95 (3)C13—C141.496 (6)
N2—C151.340 (6)C13—H13A0.9700
N2—C101.342 (5)C13—H13B0.9700
C1—C21.532 (7)C14—H14A0.9600
C1—H1A0.9600C14—H14B0.9600
C1—H1B0.9600C14—H14C0.9600
C1—H1C0.9600C15—C161.355 (7)
C2—C71.390 (8)C15—H150.9300
C2—C31.395 (8)C16—C171.383 (6)
C3—C41.385 (6)C16—H160.9300
C3—H30.9300C17—H170.9300
C4—C51.390 (5)
O1—S1—O2119.11 (18)C9—C8—N1123.8 (3)
O1—S1—N1107.37 (16)C9—C8—C11112.4 (3)
O2—S1—N1105.00 (16)N1—C8—C11123.3 (3)
O1—S1—C5109.43 (18)C8—C9—C12126.6 (3)
O2—S1—C5107.97 (18)C8—C9—S2112.9 (3)
N1—S1—C5107.34 (16)C12—C9—S2120.3 (3)
C10—S2—C990.63 (18)N2—C10—C11125.8 (4)
C12—O3—C13116.1 (3)N2—C10—S2121.5 (4)
C8—N1—S1122.0 (2)C11—C10—S2112.7 (3)
C8—N1—H1N114 (3)C10—C11—C17118.2 (3)
S1—N1—H1N109 (3)C10—C11—C8111.4 (3)
C15—N2—C10114.2 (4)C17—C11—C8130.2 (4)
C2—C1—H1A109.5O4—C12—O3124.0 (3)
C2—C1—H1B109.5O4—C12—C9124.4 (4)
H1A—C1—H1B109.5O3—C12—C9111.7 (3)
C2—C1—H1C109.5O3—C13—C14107.3 (3)
H1A—C1—H1C109.5O3—C13—H13A110.3
H1B—C1—H1C109.5C14—C13—H13A110.3
C7—C2—C3119.4 (5)O3—C13—H13B110.3
C7—C2—C1121.5 (7)C14—C13—H13B110.3
C3—C2—C1118.9 (6)H13A—C13—H13B108.5
C4—C3—C2119.7 (5)C13—C14—H14A109.5
C4—C3—H3120.1C13—C14—H14B109.5
C2—C3—H3120.1H14A—C14—H14B109.5
C3—C4—C5119.5 (5)C13—C14—H14C109.5
C3—C4—H4120.3H14A—C14—H14C109.5
C5—C4—H4120.3H14B—C14—H14C109.5
C6—C5—C4120.8 (4)N2—C15—C16124.8 (4)
C6—C5—S1119.7 (3)N2—C15—H15117.6
C4—C5—S1119.5 (3)C16—C15—H15117.6
C7—C6—C5119.7 (5)C15—C16—C17121.6 (4)
C7—C6—H6120.1C15—C16—H16119.2
C5—C6—H6120.1C17—C16—H16119.2
C6—C7—C2120.9 (5)C16—C17—C11115.4 (4)
C6—C7—H7119.6C16—C17—H17122.3
C2—C7—H7119.6C11—C17—H17122.3
O1—S1—N1—C8−38.8 (3)C10—S2—C9—C12−174.1 (3)
O2—S1—N1—C8−166.5 (3)C15—N2—C10—C113.0 (6)
C5—S1—N1—C878.8 (3)C15—N2—C10—S2−175.2 (3)
C7—C2—C3—C40.5 (7)C9—S2—C10—N2178.1 (4)
C1—C2—C3—C4−174.8 (4)C9—S2—C10—C11−0.3 (3)
C2—C3—C4—C50.9 (7)N2—C10—C11—C17−2.6 (6)
C3—C4—C5—C6−1.5 (6)S2—C10—C11—C17175.8 (3)
C3—C4—C5—S1176.2 (3)N2—C10—C11—C8−178.3 (4)
O1—S1—C5—C6−166.5 (3)S2—C10—C11—C80.0 (4)
O2—S1—C5—C6−35.5 (4)C9—C8—C11—C100.4 (4)
N1—S1—C5—C677.3 (4)N1—C8—C11—C10172.4 (3)
O1—S1—C5—C415.8 (4)C9—C8—C11—C17−174.7 (3)
O2—S1—C5—C4146.9 (3)N1—C8—C11—C17−2.7 (6)
N1—S1—C5—C4−100.4 (3)C13—O3—C12—O4−0.1 (5)
C4—C5—C6—C70.7 (7)C13—O3—C12—C9178.8 (3)
S1—C5—C6—C7−176.9 (3)C8—C9—C12—O42.4 (6)
C5—C6—C7—C20.6 (7)S2—C9—C12—O4176.2 (3)
C3—C2—C7—C6−1.2 (7)C8—C9—C12—O3−176.5 (3)
C1—C2—C7—C6173.9 (4)S2—C9—C12—O3−2.7 (4)
S1—N1—C8—C9−115.8 (4)C12—O3—C13—C14−178.0 (3)
S1—N1—C8—C1173.0 (4)C10—N2—C15—C16−2.2 (7)
N1—C8—C9—C121.5 (6)N2—C15—C16—C171.0 (7)
C11—C8—C9—C12173.5 (3)C15—C16—C17—C11−0.4 (6)
N1—C8—C9—S2−172.6 (3)C10—C11—C17—C161.1 (5)
C11—C8—C9—S2−0.6 (4)C8—C11—C17—C16175.9 (4)
C10—S2—C9—C80.5 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O40.95 (3)2.22 (3)2.867 (4)125 (3)
N1—H1N···O2i0.95 (3)2.21 (3)3.033 (4)145 (3)
Symmetry codes: (i) −x, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O40.95 (3)2.22 (3)2.867 (4)125 (3)
N1—H1N···O2i0.95 (3)2.21 (3)3.033 (4)145 (3)
Symmetry codes: (i) −x, −y+1, −z+1.
Acknowledgements top

The project was sponsored by the Scientific Research Foundation for Returned Overseas Chinese Scholars (No. 20071108–18–14), State Education Ministry.

references
References top

Dwiggins, C. W. (1975). Acta Cryst. A31, 146–148.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst. 22, 384–387.

Gabe, E. J. & White, P. S. (1993). DIFRAC. American Crystallographic Association Meeting, Pittsburgh, Abstract PA 104.

Litvinov, V. P., Dotsenko, V. V. & Krivokolysko, S. G. (2005). Russ. Chem. Bull. 54, 864–904.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.