Ethyl 2-amino-4-(3-nitro-phen-yl)-4H-1-benzothieno[3,2-b]pyran-3-carboxyl-ate.

The mol-ecule of the title compound, C20H16N2O5S, is built up by one fused five-membered and two fused six-membered rings linked to eth-oxy-carbonyl and 3-nitro-phenyl groups. The benzothieno-pyran ring system is nearly planar (r.m.s deviation = 0.0392 Å) and forms a dihedral angle of 86.90 (6)° with the aromatic ring of the nitro-benzene group. In the crystal, mol-ecules are linked by N-H⋯O hydrogen bonds and by π-π inter-actions between the phenyl ring and the six-membered heterocyle [inter-centroid distance = 3.5819 (8) Å], forming a three-dimensional network.

Related literature

For background to the organic synthesis of the title compound, see: House (1972 ▶); Kabashima et al. (2000 ▶); Jung (1991 ▶). For the preparation of heterocyclic compounds using condensation reactions, see: Boughaleb et al. (2011 ▶); Cabiddu et al. (2002 ▶); Pradhan & Asish (2005 ▶).

Experimental

Crystal data

C20H16N2O5S

M = 396.41

Triclinic,

a = 8.3670 (2) Å

b = 9.4319 (2) Å

c = 12.8948 (4) Å

α = 102.505 (1)°

β = 106.493 (1)°

γ = 94.840 (1)°

V = 940.96 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.21 mm−1

T = 296 K

0.42 × 0.31 × 0.26 mm

Data collection

Bruker X8 APEX diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.673, T max = 0.746

20668 measured reflections

4857 independent reflections

3954 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.137

S = 1.05

4857 reflections

253 parameters

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −0.25 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/S1600536814008538/rz5118sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814008538/rz5118Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814008538/rz5118Isup3.cml

CCDC reference: 997474

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

C20H16N2O5S	Z = 2
Mr = 396.41	F(000) = 412
Triclinic, P1	Dx = 1.399 Mg m−3
Hall symbol: -P 1	Melting point: 493 K
a = 8.3670 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.4319 (2) Å	Cell parameters from 4857 reflections
c = 12.8948 (4) Å	θ = 2.5–28.7°
α = 102.505 (1)°	µ = 0.21 mm−1
β = 106.493 (1)°	T = 296 K
γ = 94.840 (1)°	Block, colourless
V = 940.96 (4) Å3	0.42 × 0.31 × 0.26 mm

Bruker X8 APEX diffractometer	4857 independent reflections
Radiation source: fine-focus sealed tube	3954 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
φ and ω scans	θmax = 28.7°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
Tmin = 0.673, Tmax = 0.746	k = −12→12
20668 measured reflections	l = −17→17

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) = 0.137	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0782P)2 + 0.1615P] where P = (Fo2 + 2Fc2)/3
4857 reflections	(Δ/σ)max = 0.001
253 parameters	Δρmax = 0.37 e Å−3
0 restraints	Δρmin = −0.25 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	1.03581 (19)	0.74569 (16)	0.51586 (12)	0.0444 (3)
C2	1.1714 (2)	0.7184 (2)	0.59752 (14)	0.0572 (4)
H2	1.1539	0.6646	0.6469	0.069*
C3	1.3318 (2)	0.7739 (2)	0.60256 (14)	0.0596 (4)
H3	1.4239	0.7566	0.6561	0.072*
C4	1.3590 (2)	0.8552 (2)	0.52938 (14)	0.0553 (4)
H4	1.4689	0.8908	0.5347	0.066*
C5	1.22638 (19)	0.88383 (17)	0.44927 (13)	0.0472 (3)
H5	1.2455	0.9388	0.4010	0.057*
C6	1.06239 (17)	0.82841 (14)	0.44214 (11)	0.0388 (3)
C7	0.90329 (17)	0.83869 (14)	0.36665 (11)	0.0366 (3)
C8	0.76677 (17)	0.76734 (14)	0.37893 (11)	0.0373 (3)
C9	0.59063 (16)	0.75463 (14)	0.30354 (11)	0.0356 (3)
H9	0.5205	0.7943	0.3487	0.043*
C10	0.59569 (16)	0.84817 (14)	0.22130 (11)	0.0361 (3)
C11	0.74244 (17)	0.91953 (14)	0.21693 (11)	0.0371 (3)
C12	0.43789 (18)	0.86851 (15)	0.14814 (12)	0.0418 (3)
C13	0.1380 (2)	0.8102 (3)	0.0990 (2)	0.0859 (7)
H13A	0.1389	0.8011	0.0228	0.103*
H13B	0.1031	0.9034	0.1248	0.103*
C14	0.0200 (2)	0.6887 (2)	0.1031 (2)	0.0785 (6)
H14A	−0.0914	0.6910	0.0564	0.118*
H14B	0.0192	0.6988	0.1787	0.118*
H14C	0.0549	0.5969	0.0770	0.118*
C15	0.51766 (16)	0.59335 (14)	0.24462 (11)	0.0363 (3)
C16	0.5980 (2)	0.50862 (16)	0.17907 (13)	0.0486 (3)
H16	0.6969	0.5507	0.1710	0.058*
C17	0.5336 (2)	0.36266 (18)	0.12555 (16)	0.0598 (4)
H17	0.5895	0.3077	0.0820	0.072*
C18	0.3863 (2)	0.29794 (17)	0.13649 (15)	0.0592 (5)
H18	0.3414	0.2000	0.1008	0.071*
C19	0.30905 (19)	0.38353 (17)	0.20176 (14)	0.0516 (4)
C20	0.37110 (17)	0.52953 (16)	0.25679 (12)	0.0439 (3)
H20	0.3155	0.5835	0.3010	0.053*
N1	0.75846 (17)	0.99963 (14)	0.14576 (11)	0.0500 (3)
H1A	0.8569	1.0394	0.1494	0.060*
H1B	0.6704	1.0114	0.0963	0.060*
N2	0.1493 (2)	0.3189 (2)	0.21188 (16)	0.0745 (5)
O1	0.89774 (12)	0.91629 (11)	0.28705 (8)	0.0435 (2)
O2	0.41926 (14)	0.93260 (13)	0.07393 (10)	0.0551 (3)
O3	0.30471 (13)	0.80479 (15)	0.16981 (11)	0.0597 (3)
O4	0.0661 (2)	0.3993 (2)	0.2526 (2)	0.1098 (7)
O5	0.1064 (2)	0.1868 (2)	0.17700 (19)	0.1165 (7)
S1	0.82193 (5)	0.68473 (5)	0.48947 (3)	0.05225 (14)

	U11	U22	U33	U12	U13	U23
C1	0.0450 (7)	0.0467 (7)	0.0397 (7)	0.0057 (6)	0.0084 (6)	0.0138 (6)
C2	0.0577 (10)	0.0676 (10)	0.0468 (8)	0.0126 (8)	0.0067 (7)	0.0273 (7)
C3	0.0479 (9)	0.0773 (11)	0.0482 (9)	0.0150 (8)	0.0012 (7)	0.0211 (8)
C4	0.0391 (8)	0.0712 (10)	0.0487 (9)	0.0056 (7)	0.0063 (6)	0.0119 (7)
C5	0.0410 (7)	0.0539 (8)	0.0423 (7)	0.0017 (6)	0.0072 (6)	0.0130 (6)
C6	0.0404 (7)	0.0371 (6)	0.0342 (6)	0.0037 (5)	0.0068 (5)	0.0064 (5)
C7	0.0392 (7)	0.0346 (6)	0.0343 (6)	0.0025 (5)	0.0082 (5)	0.0107 (5)
C8	0.0394 (7)	0.0373 (6)	0.0343 (6)	0.0030 (5)	0.0083 (5)	0.0126 (5)
C9	0.0349 (6)	0.0380 (6)	0.0360 (6)	0.0032 (5)	0.0121 (5)	0.0129 (5)
C10	0.0377 (7)	0.0355 (6)	0.0373 (6)	0.0054 (5)	0.0113 (5)	0.0139 (5)
C11	0.0380 (6)	0.0356 (6)	0.0386 (7)	0.0054 (5)	0.0106 (5)	0.0131 (5)
C12	0.0388 (7)	0.0452 (7)	0.0477 (8)	0.0116 (5)	0.0156 (6)	0.0197 (6)
C13	0.0361 (9)	0.1282 (19)	0.1168 (18)	0.0216 (10)	0.0176 (10)	0.0839 (16)
C14	0.0483 (10)	0.0803 (13)	0.0881 (15)	0.0057 (9)	0.0018 (10)	0.0096 (11)
C15	0.0341 (6)	0.0387 (6)	0.0365 (6)	0.0011 (5)	0.0075 (5)	0.0166 (5)
C16	0.0476 (8)	0.0441 (7)	0.0552 (9)	0.0014 (6)	0.0198 (7)	0.0119 (6)
C17	0.0684 (11)	0.0455 (8)	0.0610 (10)	0.0067 (7)	0.0188 (9)	0.0067 (7)
C18	0.0655 (10)	0.0412 (7)	0.0560 (9)	−0.0078 (7)	−0.0024 (8)	0.0160 (7)
C19	0.0409 (7)	0.0545 (8)	0.0533 (8)	−0.0106 (6)	−0.0014 (6)	0.0292 (7)
C20	0.0358 (7)	0.0509 (7)	0.0467 (8)	−0.0001 (6)	0.0094 (6)	0.0228 (6)
N1	0.0416 (6)	0.0573 (7)	0.0569 (8)	0.0010 (5)	0.0113 (6)	0.0342 (6)
N2	0.0517 (9)	0.0814 (11)	0.0832 (11)	−0.0221 (8)	0.0030 (8)	0.0424 (9)
O1	0.0356 (5)	0.0502 (5)	0.0465 (5)	−0.0001 (4)	0.0085 (4)	0.0239 (4)
O2	0.0458 (6)	0.0699 (7)	0.0608 (7)	0.0148 (5)	0.0145 (5)	0.0404 (6)
O3	0.0343 (5)	0.0866 (8)	0.0737 (8)	0.0155 (5)	0.0171 (5)	0.0496 (7)
O4	0.0650 (10)	0.1204 (15)	0.1621 (19)	−0.0096 (10)	0.0533 (12)	0.0581 (14)
O5	0.0925 (12)	0.0841 (11)	0.1571 (18)	−0.0447 (9)	0.0255 (12)	0.0378 (11)
S1	0.0472 (2)	0.0633 (3)	0.0485 (2)	−0.00050 (17)	0.00801 (16)	0.03121 (18)

C1—C2	1.396 (2)	C12—O3	1.3482 (17)
C1—C6	1.405 (2)	C13—O3	1.446 (2)
C1—S1	1.7449 (16)	C13—C14	1.469 (3)
C2—C3	1.377 (3)	C13—H13A	0.9700
C2—H2	0.9300	C13—H13B	0.9700
C3—C4	1.392 (3)	C14—H14A	0.9600
C3—H3	0.9300	C14—H14B	0.9600
C4—C5	1.376 (2)	C14—H14C	0.9600
C4—H4	0.9300	C15—C20	1.3843 (18)
C5—C6	1.397 (2)	C15—C16	1.388 (2)
C5—H5	0.9300	C16—C17	1.383 (2)
C6—C7	1.4338 (18)	C16—H16	0.9300
C7—C8	1.3423 (18)	C17—C18	1.386 (3)
C7—O1	1.3768 (15)	C17—H17	0.9300
C8—C9	1.4959 (18)	C18—C19	1.371 (3)
C8—S1	1.7378 (14)	C18—H18	0.9300
C9—C10	1.5261 (17)	C19—C20	1.384 (2)
C9—C15	1.5308 (17)	C19—N2	1.473 (2)
C9—H9	0.9800	C20—H20	0.9300
C10—C11	1.3712 (18)	N1—H1A	0.8600
C10—C12	1.4436 (19)	N1—H1B	0.8600
C11—N1	1.3356 (17)	N2—O4	1.208 (3)
C11—O1	1.3633 (16)	N2—O5	1.214 (2)
C12—O2	1.2195 (17)
C2—C1—C6	120.99 (15)	O3—C13—C14	108.58 (16)
C2—C1—S1	127.04 (13)	O3—C13—H13A	110.0
C6—C1—S1	111.96 (11)	C14—C13—H13A	110.0
C3—C2—C1	117.84 (16)	O3—C13—H13B	110.0
C3—C2—H2	121.1	C14—C13—H13B	110.0
C1—C2—H2	121.1	H13A—C13—H13B	108.4
C2—C3—C4	121.46 (15)	C13—C14—H14A	109.5
C2—C3—H3	119.3	C13—C14—H14B	109.5
C4—C3—H3	119.3	H14A—C14—H14B	109.5
C5—C4—C3	121.21 (16)	C13—C14—H14C	109.5
C5—C4—H4	119.4	H14A—C14—H14C	109.5
C3—C4—H4	119.4	H14B—C14—H14C	109.5
C4—C5—C6	118.47 (15)	C20—C15—C16	119.01 (13)
C4—C5—H5	120.8	C20—C15—C9	120.39 (12)
C6—C5—H5	120.8	C16—C15—C9	120.59 (11)
C5—C6—C1	120.03 (13)	C17—C16—C15	121.20 (15)
C5—C6—C7	130.31 (13)	C17—C16—H16	119.4
C1—C6—C7	109.65 (12)	C15—C16—H16	119.4
C8—C7—O1	124.23 (12)	C16—C17—C18	120.27 (17)
C8—C7—C6	115.68 (12)	C16—C17—H17	119.9
O1—C7—C6	120.09 (11)	C18—C17—H17	119.9
C7—C8—C9	124.19 (12)	C19—C18—C17	117.59 (14)
C7—C8—S1	111.37 (10)	C19—C18—H18	121.2
C9—C8—S1	124.38 (10)	C17—C18—H18	121.2
C8—C9—C10	107.83 (10)	C18—C19—C20	123.38 (14)
C8—C9—C15	110.43 (11)	C18—C19—N2	118.73 (15)
C10—C9—C15	112.40 (10)	C20—C19—N2	117.87 (17)
C8—C9—H9	108.7	C19—C20—C15	118.54 (15)
C10—C9—H9	108.7	C19—C20—H20	120.7
C15—C9—H9	108.7	C15—C20—H20	120.7
C11—C10—C12	118.22 (12)	C11—N1—H1A	120.0
C11—C10—C9	123.25 (12)	C11—N1—H1B	120.0
C12—C10—C9	118.45 (11)	H1A—N1—H1B	120.0
N1—C11—O1	109.61 (11)	O4—N2—O5	123.09 (19)
N1—C11—C10	127.07 (13)	O4—N2—C19	118.92 (16)
O1—C11—C10	123.32 (12)	O5—N2—C19	118.0 (2)
O2—C12—O3	121.52 (13)	C11—O1—C7	116.95 (10)
O2—C12—C10	126.91 (13)	C12—O3—C13	117.57 (13)
O3—C12—C10	111.56 (12)	C8—S1—C1	91.31 (7)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O2	0.86	2.09	2.6950 (17)	127
N1—H1B···O2i	0.86	2.30	3.0327 (17)	143
N1—H1A···O5ii	0.86	2.30	3.1489 (19)	169

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O2	0.86	2.09	2.6950 (17)	127
N1—H1B⋯O2i	0.86	2.30	3.0327 (17)	143
N1—H1A⋯O5ii	0.86	2.30	3.1489 (19)	169

Symmetry codes: (i) ; (ii) .