Ethyl 3-amino-4H-thieno[2,3-b]pyridine-2-carboxyl­ate

Zheng, R.; Zhang, W.; Yu, L.-T.; Yang, S.-Y.; Yang, L.

doi:10.1107/S1600536808039974

organic compounds

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Volume 65| Part 1| January 2009| Page o9

doi:10.1107/S1600536808039974

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Ethyl 3-amino-4H-thieno[2,3-b]pyridine-2-carboxylate

Ren-lin Zheng,^a Wen-qin Zhang,^a Luo-Ting Yu,^a Sheng-Yong Yang ^a and Li Yang ^a ^*

^aState Key Laboratory of Biotherapy and Cancer Center, West China Hospital, West China Medical School, Sichuan University, Chengdu 610041, People's Republic of China
^*Correspondence e-mail: yangli@scu.edu.cn

(Received 20 November 2008; accepted 27 November 2008; online 3 December 2008)

The molecule of the title compound, C₁₀H₁₀N₂O₂S, is essentially planar, except for the ethyl group, which is twisted away from the carboxyl plane by −90.5 (3)°. In the crystal structure, molecules are linked into a zigzag sheet propagating along the b axis by intermolecular N—H⋯O and N—H⋯N hydrogen bonds.

Related literature

For general background, see: Litvinov et al. (2005 ).

Experimental

Crystal data

C₁₀H₁₀N₂O₂S
M_r = 222.26
Monoclinic, P 2₁ /c
a = 6.657 (4) Å
b = 13.891 (4) Å
c = 10.902 (4) Å
β = 91.64 (4)°
V = 1007.8 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 292 (2) K
0.60 × 0.46 × 0.42 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: spherical (Dwiggins, 1975 ) T_min = 0.840, T_max = 0.884
1978 measured reflections
1864 independent reflections
1515 reflections with I > 2σ(I)
R_int = 0.008
3 standard reflections every 150 reflections intensity decay: 0.6%

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.118
S = 1.14
1864 reflections
145 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O2	0.84 (2)	2.26 (2)	2.848 (3)	127 (2)
N2—H1N2⋯O2ⁱ	0.84 (2)	2.38 (3)	3.067 (3)	139 (2)
N2—H2N2⋯N1ⁱⁱ	0.81 (3)	2.38 (3)	3.118 (3)	152 (3)
Symmetry codes: (i) -x, -y+1, -z+1; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: DIFRAC (Gabe & White, 1993 ); cell refinement: DIFRAC; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808039974/ci2735sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808039974/ci2735Isup2.hkl

checkCIF report

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 molecule (Fig.1) is essentially planar. The amino group and the carbonyl group are nearly coplanar with the heterocyclic ring system. The ethyl group is twisted perpendicular to the remaining part of the molecule [C8—O1—C9—C10 = -90.5 (3)°].

In the crystal structure, the molecules are linked into a zigzag sheet propagating along the b axis by intermolecular N—H···O and N—H···N hydrogen bonds (Fig. 2).

Related literature top

For general background, see: Litvinov et al. (2005).

Experimental top

A mixture of 2-chloro-3-cyanopyridine (3.3 g, 0.023 mol), ethyl 2-mercaptoacetate (3.62 g, 0.03 mol), sodium carbonate (2.65 g, 0.025 mol) and anhydrous ethanol (12.0 ml) was heated for 4.5 h under reflux. The reaction mixture was cooled to ambient temperature and added to water (150 ml). The resultant precipitate was stirred for 45 min and then filtered. The filter cake was washed with two portions of water (25 ml) and dried to yield the title compound as a yellow solid (5.032 g, 95.1% yield). Single crystals suitable for X-ray analysis were obtained by slow evaporation of a tetrahydrofuran solution.

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

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. A packing diagram of the title compound. Intermolecular hydrogen bonds are shown as dashed open lines.

Ethyl 3-amino-4H-thieno[2,3-b]pyridine-2-carboxylate top

Crystal data top

C₁₀H₁₀N₂O₂S	F(000) = 464
M_r = 222.26	D_x = 1.465 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 22 reflections
a = 6.657 (4) Å	θ = 4.3–5.7°
b = 13.891 (4) Å	µ = 0.30 mm⁻¹
c = 10.902 (4) Å	T = 292 K
β = 91.64 (4)°	Block, colourless
V = 1007.8 (8) Å³	0.60 × 0.46 × 0.42 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1515 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.008
Graphite monochromator	θ_max = 25.5°, θ_min = 2.4°
ω/2θ scans	h = −8→8
Absorption correction: for a sphere (Dwiggins, 1975)	k = 0→16
T_min = 0.840, T_max = 0.884	l = −6→13
1978 measured reflections	3 standard reflections every 150 reflections
1864 independent reflections	intensity decay: 0.6%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: mixed
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ²(F_o²) + (0.0562P)² + 0.4962P] where P = (F_o² + 2F_c²)/3
1864 reflections	(Δ/σ)_max = 0.001
145 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₁₀H₁₀N₂O₂S	V = 1007.8 (8) Å³
M_r = 222.26	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.657 (4) Å	µ = 0.30 mm⁻¹
b = 13.891 (4) Å	T = 292 K
c = 10.902 (4) Å	0.60 × 0.46 × 0.42 mm
β = 91.64 (4)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1515 reflections with I > 2σ(I)
Absorption correction: for a sphere (Dwiggins, 1975)	R_int = 0.008
T_min = 0.840, T_max = 0.884	3 standard reflections every 150 reflections
1978 measured reflections	intensity decay: 0.6%
1864 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	Δρ_max = 0.26 e Å⁻³
1864 reflections	Δρ_min = −0.38 e Å⁻³
145 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.20405 (9)	0.73591 (5)	0.16994 (5)	0.0405 (2)
O1	−0.1351 (2)	0.60921 (12)	0.17935 (15)	0.0442 (4)
O2	−0.0551 (3)	0.52930 (13)	0.35384 (16)	0.0487 (5)
N1	0.5470 (3)	0.83735 (15)	0.20206 (18)	0.0416 (5)
N2	0.3157 (4)	0.58481 (17)	0.46991 (19)	0.0429 (5)
H1N2	0.215 (4)	0.5502 (18)	0.481 (2)	0.032 (7)*
H2N2	0.407 (4)	0.593 (2)	0.519 (3)	0.049 (8)*
C1	0.7139 (4)	0.8539 (2)	0.2686 (2)	0.0461 (6)
H1	0.8010	0.9013	0.2419	0.055*
C2	0.7661 (4)	0.8045 (2)	0.3756 (2)	0.0468 (6)
H2	0.8851	0.8192	0.4184	0.056*
C3	0.6422 (4)	0.73450 (18)	0.4178 (2)	0.0394 (6)
H3	0.6751	0.7009	0.4894	0.047*
C4	0.4659 (3)	0.71448 (16)	0.35153 (19)	0.0326 (5)
C5	0.3088 (3)	0.64550 (16)	0.3736 (2)	0.0333 (5)
C6	0.1607 (3)	0.64942 (17)	0.2830 (2)	0.0348 (5)
C7	0.4275 (3)	0.76841 (17)	0.2448 (2)	0.0344 (5)
C8	−0.0161 (4)	0.59041 (17)	0.2784 (2)	0.0363 (5)
C9	−0.3115 (4)	0.5493 (2)	0.1610 (2)	0.0457 (6)
H9A	−0.4178	0.5864	0.1209	0.055*
H9B	−0.3587	0.5280	0.2398	0.055*
C10	−0.2633 (4)	0.4637 (2)	0.0840 (3)	0.0527 (7)
H10A	−0.2104	0.4849	0.0076	0.079*
H10B	−0.3832	0.4268	0.0684	0.079*
H10C	−0.1653	0.4245	0.1267	0.079*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0453 (4)	0.0474 (4)	0.0286 (3)	−0.0085 (3)	−0.0057 (2)	0.0056 (2)
O1	0.0454 (10)	0.0502 (10)	0.0366 (9)	−0.0120 (8)	−0.0092 (7)	0.0033 (8)
O2	0.0504 (11)	0.0543 (11)	0.0411 (10)	−0.0142 (8)	−0.0030 (8)	0.0107 (8)
N1	0.0478 (12)	0.0464 (12)	0.0307 (10)	−0.0095 (9)	0.0028 (9)	0.0007 (9)
N2	0.0456 (13)	0.0488 (13)	0.0338 (11)	−0.0089 (11)	−0.0060 (10)	0.0094 (9)
C1	0.0465 (14)	0.0514 (16)	0.0404 (14)	−0.0145 (12)	0.0050 (11)	−0.0037 (12)
C2	0.0390 (14)	0.0640 (17)	0.0372 (13)	−0.0085 (12)	−0.0022 (10)	−0.0084 (12)
C3	0.0399 (13)	0.0513 (14)	0.0268 (11)	−0.0002 (11)	−0.0007 (9)	−0.0036 (10)
C4	0.0371 (12)	0.0358 (12)	0.0250 (11)	−0.0001 (9)	0.0024 (9)	−0.0048 (9)
C5	0.0380 (12)	0.0364 (12)	0.0258 (11)	0.0013 (9)	0.0024 (9)	−0.0026 (9)
C6	0.0396 (13)	0.0372 (12)	0.0277 (11)	−0.0029 (10)	−0.0002 (9)	0.0008 (9)
C7	0.0404 (13)	0.0387 (12)	0.0242 (10)	−0.0020 (10)	0.0024 (9)	−0.0039 (9)
C8	0.0396 (13)	0.0390 (13)	0.0303 (12)	−0.0014 (10)	−0.0012 (10)	−0.0023 (10)
C9	0.0386 (14)	0.0545 (16)	0.0435 (14)	−0.0059 (11)	−0.0068 (11)	−0.0061 (12)
C10	0.0517 (16)	0.0523 (16)	0.0540 (16)	−0.0050 (13)	0.0001 (13)	−0.0078 (13)

Geometric parameters (Å, º) top

S1—C7	1.736 (3)	C2—H2	0.93
S1—C6	1.752 (2)	C3—C4	1.389 (3)
O1—C8	1.347 (3)	C3—H3	0.93
O1—C9	1.448 (3)	C4—C7	1.401 (3)
O2—C8	1.215 (3)	C4—C5	1.444 (3)
N1—C1	1.330 (3)	C5—C6	1.376 (3)
N1—C7	1.337 (3)	C6—C8	1.434 (3)
N2—C5	1.346 (3)	C9—C10	1.495 (4)
N2—H1N2	0.84 (2)	C9—H9A	0.97
N2—H2N2	0.81 (3)	C9—H9B	0.97
C1—C2	1.389 (4)	C10—H10A	0.96
C1—H1	0.93	C10—H10B	0.96
C2—C3	1.364 (4)	C10—H10C	0.96

C7—S1—C6	90.20 (11)	C5—C6—C8	125.0 (2)
C8—O1—C9	117.08 (19)	C5—C6—S1	113.77 (17)
C1—N1—C7	115.4 (2)	C8—C6—S1	121.27 (17)
C5—N2—H1N2	117.9 (17)	N1—C7—C4	125.2 (2)
C5—N2—H2N2	116 (2)	N1—C7—S1	122.16 (18)
H1N2—N2—H2N2	125 (3)	C4—C7—S1	112.63 (17)
N1—C1—C2	123.9 (2)	O2—C8—O1	123.1 (2)
N1—C1—H1	118.0	O2—C8—C6	124.5 (2)
C2—C1—H1	118.0	O1—C8—C6	112.4 (2)
C3—C2—C1	119.8 (2)	O1—C9—C10	110.4 (2)
C3—C2—H2	120.1	O1—C9—H9A	109.6
C1—C2—H2	120.1	C10—C9—H9A	109.6
C2—C3—C4	118.5 (2)	O1—C9—H9B	109.6
C2—C3—H3	120.7	C10—C9—H9B	109.6
C4—C3—H3	120.7	H9A—C9—H9B	108.1
C3—C4—C7	117.1 (2)	C9—C10—H10A	109.5
C3—C4—C5	130.7 (2)	C9—C10—H10B	109.5
C7—C4—C5	112.2 (2)	H10A—C10—H10B	109.5
N2—C5—C6	126.3 (2)	C9—C10—H10C	109.5
N2—C5—C4	122.5 (2)	H10A—C10—H10C	109.5
C6—C5—C4	111.2 (2)	H10B—C10—H10C	109.5

C7—N1—C1—C2	0.0 (4)	C1—N1—C7—C4	0.0 (4)
N1—C1—C2—C3	−0.1 (4)	C1—N1—C7—S1	−179.49 (18)
C1—C2—C3—C4	0.1 (4)	C3—C4—C7—N1	0.0 (4)
C2—C3—C4—C7	0.0 (3)	C5—C4—C7—N1	179.9 (2)
C2—C3—C4—C5	−180.0 (2)	C3—C4—C7—S1	179.53 (17)
C3—C4—C5—N2	−1.1 (4)	C5—C4—C7—S1	−0.5 (2)
C7—C4—C5—N2	178.9 (2)	C6—S1—C7—N1	179.8 (2)
C3—C4—C5—C6	−179.5 (2)	C6—S1—C7—C4	0.22 (18)
C7—C4—C5—C6	0.6 (3)	C9—O1—C8—O2	−3.2 (3)
N2—C5—C6—C8	1.9 (4)	C9—O1—C8—C6	176.0 (2)
C4—C5—C6—C8	−179.8 (2)	C5—C6—C8—O2	−0.6 (4)
N2—C5—C6—S1	−178.65 (19)	S1—C6—C8—O2	−179.94 (19)
C4—C5—C6—S1	−0.4 (3)	C5—C6—C8—O1	−179.8 (2)
C7—S1—C6—C5	0.12 (19)	S1—C6—C8—O1	0.9 (3)
C7—S1—C6—C8	179.6 (2)	C8—O1—C9—C10	−90.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O2	0.84 (2)	2.26 (2)	2.848 (3)	127 (2)
N2—H1N2···O2ⁱ	0.84 (2)	2.38 (3)	3.067 (3)	139 (2)
N2—H2N2···N1ⁱⁱ	0.81 (3)	2.38 (3)	3.118 (3)	152 (3)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀N₂O₂S
M_r	222.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	292
a, b, c (Å)	6.657 (4), 13.891 (4), 10.902 (4)
β (°)	91.64 (4)
V (Å³)	1007.8 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.60 × 0.46 × 0.42

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	For a sphere (Dwiggins, 1975)
T_min, T_max	0.840, 0.884
No. of measured, independent and observed [I > 2σ(I)] reflections	1978, 1864, 1515
R_int	0.008
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.118, 1.14
No. of reflections	1864
No. of parameters	145
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.38

Computer programs: DIFRAC (Gabe & White, 1993), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O2	0.84 (2)	2.26 (2)	2.848 (3)	127 (2)
N2—H1N2···O2ⁱ	0.84 (2)	2.38 (3)	3.067 (3)	139 (2)
N2—H2N2···N1ⁱⁱ	0.81 (3)	2.38 (3)	3.118 (3)	152 (3)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, −y+3/2, z+1/2.

References

Dwiggins, C. W. (1975). Acta Cryst. A31, 146–148. CrossRef IUCr Journals Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst. 22, 384–387. CrossRef CAS Web of Science IUCr Journals Google Scholar
Gabe, E. J. & White, P. S. (1993). DIFRAC. American Crystallographic Association Meeting, Pittsburgh, Abstract PA 104. Google Scholar
Litvinov, V. P., Dotsenko, V. V. & Krivokolysko, S. G. (2005). Russ. Chem. Bull. 54, 864–904. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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doi:10.1107/S1600536808039974

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