Crystal structure of ethyl 2-amino-4-(4-meth-oxy-phen-yl)-4H-1-benzothieno[3,2-b]pyran-3-carboxyl-ate.

The mol-ecule of the title compound, C21H19NO4S, features a fused ring system whereby a five-membered ring is flanked by two six-membered rings. This is linked to an ethyl 3-carboxyl-ate group and to a meth-oxy-benzene group. The fused-ring system is quasi-planar, with the greatest deviation from the mean plane being 0.131 (1) Å for the methine C atom. The plane through the meth-oxy-benzene ring is nearly perpendicular to that through the fused-ring system, as indicated by the dihedral angle of 85.72 (6)°. An intra-molecular N-H⋯O hydrogen bond is noted. In the crystal, mol-ecules are linked by N-H⋯O hydrogen bonds, forming layers that stack along the a axis.

Related literature

For biological properties of substituted 2-amino-4-aryl-4H-pyran derivatives, see: Panda et al. (1997 ▸); Mungra et al. (2011 ▸). For the reactivity of (Z)-2-aryl­idenebenzo[b]thio­phen-3(2H)-ones (thio­aurones), see: Boughaleb et al. (2010 ▸; 2011 ▸); Bakhouch et al. (2014 ▸, 2015 ▸). For the preparation of the title compound, using condensation reactions, see: Daisley et al. (1982 ▸).

Experimental

Crystal data

C21H19NO4S

M = 381.43

Monoclinic,

a = 11.8355 (7) Å

b = 18.6222 (11) Å

c = 9.0110 (5) Å

β = 106.502 (2)°

V = 1904.25 (19) Å3

Z = 4

Mo Kα radiation

μ = 0.20 mm−1

T = 296 K

0.42 × 0.31 × 0.26 mm

Data collection

Bruker X8 APEX diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1995 ▸) T min = 0.673, T max = 0.746

38870 measured reflections

5347 independent reflections

4118 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.130

S = 1.06

5347 reflections

244 parameters

H-atom parameters constrained

Δρmax = 0.25 e Å−3

Δρmin = −0.27 e Å−3

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT (Bruker, 2009 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: PLATON (Spek, 2009 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015008154/tk5366sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015008154/tk5366Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015008154/tk5366Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015008154/tk5366fig1.tif

Plot of the mol­ecule of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small circles.

CCDC reference: 1061576

Additional supporting information: crystallographic information; 3D view; checkCIF report

C21H19NO4S	F(000) = 800
Mr = 381.43	Dx = 1.330 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5347 reflections
a = 11.8355 (7) Å	θ = 2.2–29.6°
b = 18.6222 (11) Å	µ = 0.20 mm−1
c = 9.0110 (5) Å	T = 296 K
β = 106.502 (2)°	Block, colourless
V = 1904.25 (19) Å3	0.42 × 0.31 × 0.26 mm
Z = 4

Bruker X8 APEX diffractometer	5347 independent reflections
Radiation source: fine-focus sealed tube	4118 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
φ and ω scans	θmax = 29.6°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1995)	h = −16→16
Tmin = 0.673, Tmax = 0.746	k = −25→25
38870 measured reflections	l = −8→12

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0559P)2 + 0.5166P] where P = (Fo2 + 2Fc2)/3
5347 reflections	(Δ/σ)max = 0.001
244 parameters	Δρmax = 0.25 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.54915 (13)	0.61283 (8)	0.9681 (2)	0.0525 (4)
C2	0.46963 (16)	0.61032 (10)	1.0560 (3)	0.0699 (5)
H2	0.4006	0.5837	1.0231	0.084*
C3	0.4953 (2)	0.64792 (11)	1.1919 (3)	0.0816 (6)
H3	0.4434	0.6463	1.2522	0.098*
C4	0.5973 (2)	0.68840 (11)	1.2411 (3)	0.0830 (7)
H4	0.6126	0.7137	1.3337	0.100*
C5	0.67644 (18)	0.69176 (9)	1.1550 (2)	0.0666 (5)
H5	0.7445	0.7193	1.1885	0.080*
C6	0.65300 (13)	0.65344 (7)	1.01733 (18)	0.0460 (3)
C7	0.72073 (12)	0.64514 (7)	0.90952 (16)	0.0412 (3)
C8	0.88161 (12)	0.67389 (7)	0.81926 (15)	0.0394 (3)
C9	0.84330 (12)	0.62861 (7)	0.69542 (15)	0.0405 (3)
C10	0.73518 (13)	0.58116 (7)	0.67067 (16)	0.0434 (3)
H10	0.6822	0.5911	0.5675	0.052*
C11	0.67418 (12)	0.60232 (7)	0.78831 (17)	0.0436 (3)
C12	0.76078 (13)	0.50065 (7)	0.68312 (15)	0.0416 (3)
C13	0.83473 (14)	0.47133 (8)	0.81661 (16)	0.0484 (3)
H13	0.8741	0.5016	0.8968	0.058*
C14	0.85118 (15)	0.39799 (8)	0.83308 (19)	0.0537 (4)
H14	0.9009	0.3792	0.9239	0.064*
C15	0.79345 (14)	0.35251 (8)	0.7142 (2)	0.0517 (4)
C16	0.72156 (16)	0.38052 (9)	0.5795 (2)	0.0587 (4)
H16	0.6839	0.3503	0.4983	0.070*
C17	0.70549 (15)	0.45444 (9)	0.56549 (18)	0.0547 (4)
H17	0.6561	0.4732	0.4743	0.066*
C18	0.7396 (2)	0.23146 (10)	0.6393 (4)	0.0980 (8)
H18A	0.7623	0.1832	0.6719	0.147*
H18B	0.7473	0.2389	0.5372	0.147*
H18C	0.6592	0.2392	0.6384	0.147*
C19	0.90696 (14)	0.62770 (7)	0.58012 (16)	0.0462 (3)
C20	0.9195 (2)	0.56999 (10)	0.3491 (2)	0.0703 (5)
H20A	1.0017	0.5579	0.3960	0.084*
H20B	0.9156	0.6133	0.2881	0.084*
C21	0.8570 (3)	0.50952 (12)	0.2497 (2)	0.0897 (7)
H21A	0.8935	0.5004	0.1691	0.135*
H21B	0.7758	0.5223	0.2045	0.135*
H21C	0.8614	0.4672	0.3118	0.135*
N2	0.97404 (11)	0.71791 (7)	0.84860 (15)	0.0496 (3)
H2A	0.9907	0.7445	0.9300	0.060*
H2B	1.0171	0.7197	0.7862	0.060*
O1	0.82701 (9)	0.68022 (6)	0.93374 (12)	0.0483 (2)
O2	0.99346 (11)	0.66385 (6)	0.58006 (13)	0.0556 (3)
O3	0.85945 (12)	0.58024 (6)	0.46707 (12)	0.0600 (3)
O4	0.81361 (12)	0.28053 (6)	0.74361 (18)	0.0727 (4)
S1	0.53964 (4)	0.56789 (3)	0.79591 (6)	0.06281 (15)

	U11	U22	U33	U12	U13	U23
C1	0.0427 (7)	0.0455 (7)	0.0715 (10)	0.0012 (6)	0.0199 (7)	0.0062 (7)
C2	0.0508 (9)	0.0631 (10)	0.1059 (15)	−0.0028 (8)	0.0388 (10)	0.0102 (10)
C3	0.0858 (14)	0.0717 (12)	0.1146 (18)	−0.0017 (10)	0.0725 (14)	0.0004 (12)
C4	0.1067 (16)	0.0694 (12)	0.1008 (16)	−0.0151 (11)	0.0746 (14)	−0.0204 (11)
C5	0.0791 (12)	0.0565 (9)	0.0813 (12)	−0.0179 (8)	0.0506 (10)	−0.0193 (9)
C6	0.0471 (7)	0.0364 (6)	0.0608 (9)	−0.0011 (5)	0.0253 (6)	0.0012 (6)
C7	0.0417 (6)	0.0352 (6)	0.0491 (7)	−0.0029 (5)	0.0169 (6)	−0.0019 (5)
C8	0.0445 (6)	0.0358 (6)	0.0414 (7)	0.0006 (5)	0.0181 (5)	0.0004 (5)
C9	0.0516 (7)	0.0336 (6)	0.0379 (7)	0.0003 (5)	0.0150 (6)	0.0020 (5)
C10	0.0501 (7)	0.0408 (6)	0.0350 (6)	−0.0021 (5)	0.0053 (5)	−0.0008 (5)
C11	0.0412 (6)	0.0392 (6)	0.0483 (8)	−0.0011 (5)	0.0093 (6)	0.0010 (5)
C12	0.0507 (7)	0.0392 (6)	0.0347 (6)	−0.0062 (5)	0.0120 (5)	−0.0052 (5)
C13	0.0635 (9)	0.0413 (7)	0.0368 (7)	−0.0032 (6)	0.0086 (6)	−0.0061 (5)
C14	0.0648 (9)	0.0446 (8)	0.0515 (9)	0.0040 (7)	0.0162 (7)	0.0033 (6)
C15	0.0564 (8)	0.0375 (7)	0.0727 (10)	−0.0054 (6)	0.0370 (8)	−0.0095 (6)
C16	0.0681 (10)	0.0511 (8)	0.0597 (10)	−0.0175 (7)	0.0230 (8)	−0.0239 (7)
C17	0.0639 (9)	0.0534 (8)	0.0417 (8)	−0.0105 (7)	0.0068 (7)	−0.0106 (6)
C18	0.0876 (14)	0.0439 (9)	0.175 (3)	−0.0152 (9)	0.0570 (16)	−0.0330 (13)
C19	0.0666 (9)	0.0370 (6)	0.0378 (7)	0.0055 (6)	0.0192 (6)	0.0035 (5)
C20	0.1086 (16)	0.0698 (11)	0.0429 (9)	0.0043 (10)	0.0384 (10)	−0.0031 (7)
C21	0.146 (2)	0.0812 (14)	0.0477 (10)	−0.0027 (14)	0.0360 (12)	−0.0168 (9)
N2	0.0545 (7)	0.0493 (6)	0.0527 (7)	−0.0134 (5)	0.0276 (6)	−0.0125 (5)
O1	0.0499 (5)	0.0532 (6)	0.0486 (6)	−0.0163 (4)	0.0248 (4)	−0.0154 (4)
O2	0.0742 (7)	0.0480 (6)	0.0545 (6)	−0.0039 (5)	0.0345 (6)	0.0020 (5)
O3	0.0858 (8)	0.0595 (6)	0.0406 (6)	−0.0071 (6)	0.0277 (6)	−0.0085 (5)
O4	0.0800 (8)	0.0368 (5)	0.1128 (11)	−0.0022 (5)	0.0458 (8)	−0.0092 (6)
S1	0.0452 (2)	0.0688 (3)	0.0704 (3)	−0.01563 (18)	0.00995 (19)	−0.0072 (2)

C1—C2	1.393 (2)	C13—C14	1.382 (2)
C1—C6	1.404 (2)	C13—H13	0.9300
C1—S1	1.7381 (18)	C14—C15	1.384 (2)
C2—C3	1.367 (3)	C14—H14	0.9300
C2—H2	0.9300	C15—C16	1.372 (3)
C3—C4	1.385 (3)	C15—O4	1.3742 (18)
C3—H3	0.9300	C16—C17	1.390 (2)
C4—C5	1.377 (2)	C16—H16	0.9300
C4—H4	0.9300	C17—H17	0.9300
C5—C6	1.389 (2)	C18—O4	1.420 (3)
C5—H5	0.9300	C18—H18A	0.9600
C6—C7	1.4327 (19)	C18—H18B	0.9600
C7—C11	1.3381 (19)	C18—H18C	0.9600
C7—O1	1.3786 (16)	C19—O2	1.2255 (19)
C8—N2	1.3319 (17)	C19—O3	1.3451 (18)
C8—O1	1.3691 (15)	C20—O3	1.450 (2)
C8—C9	1.3691 (18)	C20—C21	1.497 (3)
C9—C19	1.4464 (19)	C20—H20A	0.9700
C9—C10	1.5185 (19)	C20—H20B	0.9700
C10—C11	1.495 (2)	C21—H21A	0.9600
C10—C12	1.5273 (19)	C21—H21B	0.9600
C10—H10	0.9800	C21—H21C	0.9600
C11—S1	1.7360 (14)	N2—H2A	0.8600
C12—C17	1.3778 (19)	N2—H2B	0.8600
C12—C13	1.383 (2)
C2—C1—C6	120.72 (17)	C12—C13—H13	119.4
C2—C1—S1	127.51 (14)	C13—C14—C15	119.88 (15)
C6—C1—S1	111.75 (12)	C13—C14—H14	120.1
C3—C2—C1	118.55 (17)	C15—C14—H14	120.1
C3—C2—H2	120.7	C16—C15—O4	124.87 (15)
C1—C2—H2	120.7	C16—C15—C14	119.85 (14)
C2—C3—C4	121.17 (17)	O4—C15—C14	115.28 (16)
C2—C3—H3	119.4	C15—C16—C17	119.43 (14)
C4—C3—H3	119.4	C15—C16—H16	120.3
C5—C4—C3	120.97 (19)	C17—C16—H16	120.3
C5—C4—H4	119.5	C12—C17—C16	121.70 (15)
C3—C4—H4	119.5	C12—C17—H17	119.1
C4—C5—C6	118.99 (18)	C16—C17—H17	119.1
C4—C5—H5	120.5	O4—C18—H18A	109.5
C6—C5—H5	120.5	O4—C18—H18B	109.5
C5—C6—C1	119.60 (14)	H18A—C18—H18B	109.5
C5—C6—C7	130.75 (14)	O4—C18—H18C	109.5
C1—C6—C7	109.63 (13)	H18A—C18—H18C	109.5
C11—C7—O1	123.86 (12)	H18B—C18—H18C	109.5
C11—C7—C6	115.96 (13)	O2—C19—O3	122.02 (13)
O1—C7—C6	120.17 (12)	O2—C19—C9	126.84 (13)
N2—C8—O1	109.53 (11)	O3—C19—C9	111.15 (13)
N2—C8—C9	127.16 (12)	O3—C20—C21	105.98 (17)
O1—C8—C9	123.31 (12)	O3—C20—H20A	110.5
C8—C9—C19	118.24 (12)	C21—C20—H20A	110.5
C8—C9—C10	123.25 (12)	O3—C20—H20B	110.5
C19—C9—C10	118.48 (12)	C21—C20—H20B	110.5
C11—C10—C9	107.39 (11)	H20A—C20—H20B	108.7
C11—C10—C12	109.41 (11)	C20—C21—H21A	109.5
C9—C10—C12	114.78 (12)	C20—C21—H21B	109.5
C11—C10—H10	108.4	H21A—C21—H21B	109.5
C9—C10—H10	108.4	C20—C21—H21C	109.5
C12—C10—H10	108.4	H21A—C21—H21C	109.5
C7—C11—C10	124.48 (13)	H21B—C21—H21C	109.5
C7—C11—S1	110.95 (11)	C8—N2—H2A	120.0
C10—C11—S1	124.31 (10)	C8—N2—H2B	120.0
C17—C12—C13	117.87 (13)	H2A—N2—H2B	120.0
C17—C12—C10	121.04 (13)	C8—O1—C7	116.40 (10)
C13—C12—C10	120.98 (12)	C19—O3—C20	117.08 (14)
C14—C13—C12	121.25 (13)	C15—O4—C18	117.34 (17)
C14—C13—H13	119.4	C11—S1—C1	91.71 (7)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O2	0.86	2.08	2.6903 (16)	128
N2—H2A···O2i	0.86	2.17	2.9964 (16)	161
N2—H2B···O4ii	0.86	2.38	3.0908 (17)	140

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N2H2BO2	0.86	2.08	2.6903(16)	128
N2H2AO2i	0.86	2.17	2.9964(16)	161
N2H2BO4ii	0.86	2.38	3.0908(17)	140

Symmetry codes: (i) ; (ii) .