Ethyl 2-amino-4-phenyl-4H-1-benzo-thieno[3,2-b]pyran-3-carboxyl-ate.

The title heterocyclic compound, C(20)H(17)NO(3)S, was synthesized by condensation of ethyl cyano-acetate with (Z)-2-benzyl-idenebenzo[b]thio-phen-3(2H)-one in the presence of a basic catalyst in ethanol. The phenyl and ester groups make dihedral angles of 77.67 (6) and 8.52 (6)°, respectively, with the benzothienopyran ring system [maximum r.m.s. deviation = 0.1177 (13) Å]. In the crystal, centrosymmetric dimers are formed through pairs of N-H⋯O hydrogen bonds between the amine and ester groups. Inter-molecular C-H⋯N hydrogen bonds and C-H⋯π inter-actions involving the thio-phene ring are also observed.

Related literature

For general background to Michael addition reactions, see: Perlmutter (1992 ▶); Czarnocki et al. (2005 ▶); Rossiter & Swingle (1992 ▶).

Experimental

Crystal data

C20H17NO3S

M = 351.41

Monoclinic,

a = 8.6612 (3) Å

b = 5.9156 (2) Å

c = 32.3008 (10) Å

β = 94.962 (2)°

V = 1648.77 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.22 mm−1

T = 296 K

0.25 × 0.14 × 0.12 mm

Data collection

Bruker APEXII CCD detector diffractometer

21683 measured reflections

3608 independent reflections

3189 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.086

S = 1.04

3608 reflections

233 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.30 e Å−3

Δρmin = −0.22 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811027152/bh2365sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811027152/bh2365Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811027152/bh2365Isup3.cml

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

C20H17NO3S	F(000) = 736
Mr = 351.41	Dx = 1.416 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 232 reflections
a = 8.6612 (3) Å	θ = 2.6–25.3°
b = 5.9156 (2) Å	µ = 0.22 mm−1
c = 32.3008 (10) Å	T = 296 K
β = 94.962 (2)°	Prism, colourless
V = 1648.77 (9) Å3	0.25 × 0.14 × 0.12 mm
Z = 4

Bruker APEXII CCD detector diffractometer	3189 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
graphite	θmax = 27.0°, θmin = 2.4°
ω and φ scans	h = −11→11
21683 measured reflections	k = −7→7
3608 independent reflections	l = −41→37

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0386P)2 + 0.7884P] where P = (Fo2 + 2Fc2)/3
3608 reflections	(Δ/σ)max = 0.001
233 parameters	Δρmax = 0.30 e Å−3
2 restraints	Δρmin = −0.22 e Å−3
0 constraints

	x	y	z	Uiso*/Ueq
S1	0.18188 (4)	1.17172 (6)	0.191397 (10)	0.02581 (10)
O3	0.03012 (11)	0.62652 (16)	0.13342 (3)	0.0244 (2)
C9	0.15146 (15)	0.8299 (2)	0.08005 (4)	0.0209 (3)
C7	0.07313 (15)	0.8007 (2)	0.16060 (4)	0.0209 (3)
C12	0.39539 (14)	1.0315 (2)	0.11368 (4)	0.0191 (3)
C10	0.21849 (14)	1.0162 (2)	0.10886 (4)	0.0193 (3)
H10	0.1785	1.1610	0.0978	0.023*
C11	0.15652 (15)	0.9814 (2)	0.15042 (4)	0.0206 (3)
C6	0.02270 (15)	0.8029 (2)	0.20170 (4)	0.0219 (3)
C18	0.16810 (15)	0.8490 (2)	0.03571 (4)	0.0233 (3)
C8	0.06481 (15)	0.6545 (2)	0.09321 (4)	0.0212 (3)
C1	0.07339 (15)	1.0023 (2)	0.22215 (4)	0.0233 (3)
C2	0.03563 (16)	1.0502 (3)	0.26251 (4)	0.0280 (3)
H2	0.0692	1.1827	0.2759	0.034*
C5	−0.06701 (16)	0.6470 (3)	0.22184 (4)	0.0263 (3)
H5	−0.1011	0.5140	0.2087	0.032*
C4	−0.10381 (16)	0.6953 (3)	0.26180 (4)	0.0300 (3)
H4	−0.1633	0.5936	0.2756	0.036*
C13	0.48520 (16)	0.8567 (2)	0.13167 (4)	0.0246 (3)
H13	0.4379	0.7236	0.1392	0.030*
C17	0.46835 (16)	1.2279 (2)	0.10227 (4)	0.0240 (3)
H17	0.4097	1.3453	0.0899	0.029*
C19	0.26683 (17)	1.0704 (3)	−0.01709 (4)	0.0287 (3)
H19A	0.1676	1.0940	−0.0328	0.034*
H19B	0.3159	0.9389	−0.0282	0.034*
C3	−0.05272 (17)	0.8949 (3)	0.28169 (4)	0.0303 (3)
H3	−0.0790	0.9234	0.3085	0.036*
C16	0.62864 (17)	1.2511 (3)	0.10919 (5)	0.0294 (3)
H16	0.6764	1.3835	0.1015	0.035*
C14	0.64516 (16)	0.8792 (3)	0.13841 (4)	0.0292 (3)
H14	0.7043	0.7608	0.1503	0.035*
C15	0.71678 (16)	1.0774 (3)	0.12754 (4)	0.0305 (3)
H15	0.8236	1.0935	0.1326	0.037*
C20	0.36800 (19)	1.2749 (3)	−0.01999 (5)	0.0361 (4)
H20A	0.3148	1.4059	−0.0110	0.054*
H20B	0.3914	1.2954	−0.0483	0.054*
H20C	0.4625	1.2542	−0.0026	0.054*
O1	0.24544 (11)	1.03714 (17)	0.02657 (3)	0.0257 (2)
O2	0.11868 (12)	0.71560 (19)	0.00872 (3)	0.0319 (2)
N1	0.00146 (15)	0.4847 (2)	0.06999 (4)	0.0279 (3)
H1A	−0.062 (2)	0.392 (3)	0.0809 (5)	0.034*
H1B	0.009 (2)	0.484 (3)	0.0443 (6)	0.034*

	U11	U22	U33	U12	U13	U23
S1	0.02830 (19)	0.02802 (19)	0.02170 (17)	−0.00438 (14)	0.00562 (13)	−0.00647 (14)
O3	0.0311 (5)	0.0234 (5)	0.0187 (5)	−0.0041 (4)	0.0023 (4)	−0.0009 (4)
C9	0.0206 (6)	0.0245 (7)	0.0173 (6)	0.0016 (5)	−0.0005 (5)	−0.0016 (5)
C7	0.0192 (6)	0.0240 (7)	0.0191 (6)	0.0016 (5)	−0.0001 (5)	−0.0022 (5)
C12	0.0204 (6)	0.0240 (6)	0.0130 (5)	0.0008 (5)	0.0021 (5)	−0.0034 (5)
C10	0.0193 (6)	0.0209 (6)	0.0176 (6)	0.0024 (5)	0.0005 (5)	−0.0004 (5)
C11	0.0187 (6)	0.0243 (7)	0.0187 (6)	0.0019 (5)	0.0009 (5)	−0.0026 (5)
C6	0.0179 (6)	0.0284 (7)	0.0194 (6)	0.0054 (5)	0.0003 (5)	0.0005 (5)
C18	0.0218 (6)	0.0272 (7)	0.0206 (6)	0.0023 (5)	0.0000 (5)	−0.0018 (5)
C8	0.0211 (6)	0.0233 (7)	0.0185 (6)	0.0040 (5)	−0.0016 (5)	−0.0009 (5)
C1	0.0192 (6)	0.0297 (7)	0.0210 (6)	0.0042 (5)	0.0015 (5)	0.0004 (6)
C2	0.0274 (7)	0.0355 (8)	0.0209 (6)	0.0068 (6)	0.0016 (5)	−0.0035 (6)
C5	0.0233 (7)	0.0315 (7)	0.0241 (7)	0.0005 (6)	0.0011 (5)	0.0038 (6)
C4	0.0240 (7)	0.0422 (9)	0.0243 (7)	0.0034 (6)	0.0043 (5)	0.0094 (6)
C13	0.0254 (7)	0.0256 (7)	0.0227 (6)	0.0008 (5)	0.0007 (5)	0.0017 (6)
C17	0.0252 (7)	0.0249 (7)	0.0222 (6)	0.0017 (5)	0.0034 (5)	0.0021 (6)
C19	0.0335 (8)	0.0369 (8)	0.0161 (6)	0.0048 (6)	0.0034 (5)	0.0020 (6)
C3	0.0263 (7)	0.0460 (9)	0.0191 (6)	0.0104 (6)	0.0047 (5)	0.0023 (6)
C16	0.0266 (7)	0.0333 (8)	0.0292 (7)	−0.0055 (6)	0.0073 (6)	0.0016 (6)
C14	0.0246 (7)	0.0341 (8)	0.0282 (7)	0.0072 (6)	−0.0015 (6)	0.0021 (6)
C15	0.0192 (7)	0.0442 (9)	0.0283 (7)	−0.0003 (6)	0.0026 (5)	−0.0021 (7)
C20	0.0381 (9)	0.0423 (9)	0.0289 (8)	0.0019 (7)	0.0082 (6)	0.0084 (7)
O1	0.0322 (5)	0.0294 (5)	0.0157 (4)	−0.0024 (4)	0.0027 (4)	0.0003 (4)
O2	0.0390 (6)	0.0359 (6)	0.0206 (5)	−0.0061 (5)	0.0010 (4)	−0.0076 (4)
N1	0.0353 (7)	0.0262 (6)	0.0219 (6)	−0.0057 (5)	0.0001 (5)	−0.0029 (5)

S1—C11	1.7371 (13)	C5—H5	0.9300
S1—C1	1.7422 (14)	C4—C3	1.398 (2)
O3—C8	1.3681 (16)	C4—H4	0.9300
O3—C7	1.3839 (16)	C13—C14	1.390 (2)
C9—C8	1.3694 (19)	C13—H13	0.9300
C9—C18	1.4561 (18)	C17—C16	1.394 (2)
C9—C10	1.5247 (18)	C17—H17	0.9300
C7—C11	1.3465 (19)	C19—O1	1.4516 (15)
C7—C6	1.4330 (18)	C19—C20	1.501 (2)
C12—C17	1.3879 (19)	C19—H19A	0.9700
C12—C13	1.3905 (19)	C19—H19B	0.9700
C12—C10	1.5293 (17)	C3—H3	0.9300
C10—C11	1.5022 (17)	C16—C15	1.383 (2)
C10—H10	0.9800	C16—H16	0.9300
C6—C5	1.402 (2)	C14—C15	1.386 (2)
C6—C1	1.404 (2)	C14—H14	0.9300
C18—O2	1.2253 (17)	C15—H15	0.9300
C18—O1	1.3448 (17)	C20—H20A	0.9600
C8—N1	1.3421 (18)	C20—H20B	0.9600
C1—C2	1.4000 (18)	C20—H20C	0.9600
C2—C3	1.377 (2)	N1—H1A	0.871 (19)
C2—H2	0.9300	N1—H1B	0.838 (18)
C5—C4	1.386 (2)
C11—S1—C1	91.31 (7)	C5—C4—C3	120.89 (14)
C8—O3—C7	116.29 (10)	C5—C4—H4	119.6
C8—C9—C18	117.89 (12)	C3—C4—H4	119.6
C8—C9—C10	123.22 (11)	C14—C13—C12	120.55 (13)
C18—C9—C10	118.65 (12)	C14—C13—H13	119.7
C11—C7—O3	123.83 (12)	C12—C13—H13	119.7
C11—C7—C6	115.61 (12)	C12—C17—C16	120.65 (13)
O3—C7—C6	120.49 (12)	C12—C17—H17	119.7
C17—C12—C13	118.85 (12)	C16—C17—H17	119.7
C17—C12—C10	119.85 (12)	O1—C19—C20	107.10 (12)
C13—C12—C10	121.19 (12)	O1—C19—H19A	110.3
C11—C10—C9	107.45 (11)	C20—C19—H19A	110.3
C11—C10—C12	110.46 (10)	O1—C19—H19B	110.3
C9—C10—C12	115.47 (10)	C20—C19—H19B	110.3
C11—C10—H10	107.7	H19A—C19—H19B	108.5
C9—C10—H10	107.7	C2—C3—C4	121.53 (13)
C12—C10—H10	107.7	C2—C3—H3	119.2
C7—C11—C10	124.58 (12)	C4—C3—H3	119.2
C7—C11—S1	111.31 (10)	C15—C16—C17	120.08 (14)
C10—C11—S1	124.10 (10)	C15—C16—H16	120.0
C5—C6—C1	119.86 (12)	C17—C16—H16	120.0
C5—C6—C7	130.52 (13)	C15—C14—C13	120.20 (13)
C1—C6—C7	109.59 (12)	C15—C14—H14	119.9
O2—C18—O1	121.79 (12)	C13—C14—H14	119.9
O2—C18—C9	126.25 (13)	C16—C15—C14	119.65 (13)
O1—C18—C9	111.95 (11)	C16—C15—H15	120.2
N1—C8—O3	109.09 (12)	C14—C15—H15	120.2
N1—C8—C9	127.01 (13)	C19—C20—H20A	109.5
O3—C8—C9	123.90 (12)	C19—C20—H20B	109.5
C2—C1—C6	121.28 (13)	H20A—C20—H20B	109.5
C2—C1—S1	126.56 (12)	C19—C20—H20C	109.5
C6—C1—S1	112.16 (10)	H20A—C20—H20C	109.5
C3—C2—C1	117.90 (14)	H20B—C20—H20C	109.5
C3—C2—H2	121.1	C18—O1—C19	115.69 (11)
C1—C2—H2	121.1	C8—N1—H1A	119.0 (11)
C4—C5—C6	118.54 (14)	C8—N1—H1B	119.6 (13)
C4—C5—H5	120.7	H1A—N1—H1B	120.2 (17)
C6—C5—H5	120.7

Cg1 is the centroid of the thiophene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O2i	0.838 (19)	2.285 (19)	2.9143 (16)	132.1 (15)
C10—H10···N1ii	0.98	2.57	3.5189 (17)	164.
C15—H15···Cg1iii	0.93	2.95	3.7493 (15)	145

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the thio­phene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O2i	0.838 (19)	2.285 (19)	2.9143 (16)	132.1 (15)
C10—H10⋯N1ii	0.98	2.57	3.5189 (17)	164
C15—H15⋯Cg1iii	0.93	2.95	3.7493 (15)	145

Symmetry codes: (i) ; (ii) ; (iii) .