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

The title compound, C20H16ClNO3S, is built up from three fused rings, one five- and two six-membered rings, linked to a 3-eth-oxy-carbonyl group and to a 4-chloro-phenyl ring. The hydropyran ring has a flattened envelope conformation, with the C atom substituted by the 4-chloro-phenyl ring as the flap (displaced by 0.077 (2) Å from the plane through the other atoms). The fused three-ring system is quasi-planar (r.m.s. deviation = 0.057 Å), with the largest deviation from the mean plane being 0.106 (1) Å for the C atom substituted by the 4-chloro-phenyl ring. The 4-chloro-phenyl ring is approximately perpendicular to the mean plane of the fused ring system, as indicated by the dihedral angle of 77.32 (6)° between their mean planes. There is an intra-molecular N-H⋯O hydrogen bond forming an S(6) ring motif. In the crystal, mol-ecules are linked by pairs of N-H⋯O hydrogen bonds, forming inversion dimers with an R 2 (2)(12) ring motif. There are also short inter-molecular Cl⋯O inter-actions present [3.1226 (12) Å] between neighbouring mol-ecules.

Related literature

For the reactivity of the thio­aurones [(Z)-2-aryl­idene­benzo[b]thio­phen-3(2H)-ones], see: Boughaleb et al. (2010 ▸, 2011 ▸); Bakhouch et al. (2014 ▸, 2015 ▸); Cabiddu et al. (2002 ▸); Pradhan et al. (2005 ▸). For the preparation of the title compound using condensation reactions, see: Daisley et al. (1982 ▸).

Experimental

Crystal data

C20H16ClNO3S

M = 385.85

Triclinic,

a = 8.3606 (4) Å

b = 10.9186 (6) Å

c = 11.0971 (6) Å

α = 104.592 (2)°

β = 106.849 (2)°

γ = 102.174 (2)°

V = 893.09 (8) Å3

Z = 2

Mo Kα radiation

μ = 0.35 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

22918 measured reflections

3892 independent reflections

3422 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.097

S = 1.04

3892 reflections

235 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.24 e Å−3

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT (Bruker, 2009 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2009 ▸); software used to prepare material for publication: SHELXL2013, PLATON and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015014085/su5182sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015014085/su5182Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015014085/su5182Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015014085/su5182fig1.tif

A view of the mol­ecule structure of the title compound, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. The intra­molecular N-H⋯O hydrogen bond is shown as a dashed line (see Table 1).

Click here for additional data file.

a . DOI: 10.1107/S2056989015014085/su5182fig2.tif

A view along the a axis of the crystal packing for the title compound. The hydrogen bonds are shown as dashed lines (see Table 1), and C-bound H atoms have been omitted for clarity.

CCDC reference: 1415291

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

C20H16ClNO3S	Z = 2
Mr = 385.85	F(000) = 400
Triclinic, P1	Dx = 1.435 Mg m−3
a = 8.3606 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.9186 (6) Å	Cell parameters from 3892 reflections
c = 11.0971 (6) Å	θ = 2.3–27.0°
α = 104.592 (2)°	µ = 0.35 mm−1
β = 106.849 (2)°	T = 296 K
γ = 102.174 (2)°	Block, colourless
V = 893.09 (8) Å3	0.42 × 0.31 × 0.26 mm

Bruker X8 APEX diffractometer	3892 independent reflections
Radiation source: fine-focus sealed tube	3422 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
φ and ω scans	θmax = 27.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
Tmin = 0.673, Tmax = 0.746	k = −13→13
22918 measured reflections	l = −14→14

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033	H-atom parameters constrained
wR(F2) = 0.097	w = 1/[σ2(Fo2) + (0.0548P)2 + 0.2464P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
3892 reflections	Δρmax = 0.30 e Å−3
235 parameters	Δρmin = −0.24 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.

	x	y	z	Uiso*/Ueq
C1	0.35626 (19)	0.05325 (15)	0.88366 (15)	0.0351 (3)
C2	0.2174 (2)	0.01998 (18)	0.92720 (18)	0.0471 (4)
H2	0.2128	0.0769	1.0033	0.057*
C3	0.0882 (2)	−0.0988 (2)	0.85487 (19)	0.0542 (4)
H3	−0.0054	−0.1223	0.8824	0.065*
C4	0.0936 (2)	−0.1852 (2)	0.74085 (19)	0.0539 (4)
H4	0.0034	−0.2648	0.6931	0.065*
C5	0.2317 (2)	−0.15375 (17)	0.69832 (16)	0.0432 (4)
H5	0.2359	−0.2120	0.6229	0.052*
C6	0.36455 (18)	−0.03341 (14)	0.77004 (14)	0.0325 (3)
C7	0.51995 (18)	0.02422 (13)	0.74848 (13)	0.0296 (3)
C8	0.62124 (18)	0.14449 (13)	0.83590 (13)	0.0294 (3)
C9	0.78415 (17)	0.22422 (13)	0.82693 (13)	0.0281 (3)
H9	0.8804	0.2515	0.9131	0.034*
C10	0.82868 (17)	0.13392 (13)	0.72085 (13)	0.0298 (3)
C11	0.71717 (18)	0.01172 (13)	0.63660 (13)	0.0298 (3)
C12	0.75379 (16)	0.34879 (13)	0.79785 (13)	0.0274 (3)
C13	0.7782 (2)	0.46098 (14)	0.90231 (14)	0.0354 (3)
H13	0.8217	0.4617	0.9898	0.042*
C14	0.7389 (2)	0.57212 (14)	0.87879 (15)	0.0385 (3)
H14	0.7540	0.6462	0.9494	0.046*
C15	0.67728 (18)	0.57080 (13)	0.74900 (15)	0.0346 (3)
C16	0.6569 (2)	0.46233 (15)	0.64347 (15)	0.0396 (3)
H16	0.6191	0.4637	0.5564	0.047*
C17	0.69348 (19)	0.35146 (14)	0.66880 (14)	0.0349 (3)
H17	0.6772	0.2774	0.5977	0.042*
C18	0.99172 (18)	0.18273 (14)	0.70204 (14)	0.0338 (3)
C19	1.2395 (2)	0.37234 (19)	0.76685 (18)	0.0508 (4)
H19A	1.2933	0.3086	0.7312	0.061*
H19B	1.3263	0.4365	0.8501	0.061*
C20	1.1832 (4)	0.4415 (3)	0.6705 (3)	0.1006 (10)
H20A	1.2833	0.4864	0.6551	0.151*
H20B	1.1310	0.5052	0.7063	0.151*
H20C	1.0989	0.3777	0.5877	0.151*
N1	0.74061 (17)	−0.07170 (12)	0.53678 (13)	0.0404 (3)
H1A	0.8348	−0.0502	0.5199	0.048*
H1B	0.6615	−0.1469	0.4894	0.048*
O1	0.55816 (13)	−0.04447 (10)	0.64299 (10)	0.0341 (2)
O2	1.09024 (13)	0.30414 (11)	0.79199 (11)	0.0412 (3)
O3	1.03951 (15)	0.12634 (12)	0.61632 (12)	0.0503 (3)
S1	0.53387 (5)	0.19821 (4)	0.95704 (4)	0.03808 (12)
Cl1	0.62208 (6)	0.70800 (4)	0.71743 (4)	0.05029 (13)

	U11	U22	U33	U12	U13	U23
C1	0.0365 (7)	0.0397 (7)	0.0395 (7)	0.0175 (6)	0.0224 (6)	0.0158 (6)
C2	0.0454 (9)	0.0575 (10)	0.0523 (9)	0.0213 (8)	0.0346 (8)	0.0170 (8)
C3	0.0390 (9)	0.0698 (12)	0.0624 (11)	0.0136 (8)	0.0341 (8)	0.0206 (9)
C4	0.0365 (8)	0.0595 (11)	0.0591 (11)	0.0042 (8)	0.0223 (8)	0.0119 (9)
C5	0.0378 (8)	0.0492 (9)	0.0420 (8)	0.0101 (7)	0.0203 (7)	0.0099 (7)
C6	0.0316 (7)	0.0393 (7)	0.0351 (7)	0.0159 (6)	0.0179 (6)	0.0158 (6)
C7	0.0324 (7)	0.0354 (7)	0.0311 (6)	0.0175 (5)	0.0190 (5)	0.0131 (5)
C8	0.0348 (7)	0.0329 (7)	0.0307 (6)	0.0173 (5)	0.0202 (5)	0.0121 (5)
C9	0.0306 (6)	0.0313 (6)	0.0270 (6)	0.0136 (5)	0.0150 (5)	0.0087 (5)
C10	0.0312 (7)	0.0333 (7)	0.0335 (7)	0.0163 (5)	0.0192 (5)	0.0116 (5)
C11	0.0336 (7)	0.0330 (7)	0.0331 (6)	0.0172 (5)	0.0198 (5)	0.0133 (5)
C12	0.0250 (6)	0.0296 (6)	0.0292 (6)	0.0092 (5)	0.0134 (5)	0.0076 (5)
C13	0.0428 (8)	0.0348 (7)	0.0273 (6)	0.0137 (6)	0.0131 (6)	0.0063 (5)
C14	0.0444 (8)	0.0291 (7)	0.0364 (7)	0.0118 (6)	0.0135 (6)	0.0023 (6)
C15	0.0305 (7)	0.0283 (7)	0.0430 (8)	0.0097 (5)	0.0104 (6)	0.0113 (6)
C16	0.0444 (8)	0.0427 (8)	0.0309 (7)	0.0170 (7)	0.0100 (6)	0.0123 (6)
C17	0.0405 (8)	0.0347 (7)	0.0280 (6)	0.0148 (6)	0.0122 (6)	0.0053 (5)
C18	0.0327 (7)	0.0387 (7)	0.0360 (7)	0.0155 (6)	0.0183 (6)	0.0115 (6)
C19	0.0330 (8)	0.0570 (10)	0.0541 (10)	0.0021 (7)	0.0224 (7)	0.0070 (8)
C20	0.0660 (15)	0.115 (2)	0.130 (2)	0.0027 (15)	0.0361 (16)	0.078 (2)
N1	0.0442 (7)	0.0356 (6)	0.0458 (7)	0.0121 (5)	0.0308 (6)	0.0040 (5)
O1	0.0347 (5)	0.0343 (5)	0.0358 (5)	0.0099 (4)	0.0222 (4)	0.0054 (4)
O2	0.0327 (5)	0.0451 (6)	0.0417 (6)	0.0059 (4)	0.0211 (5)	0.0039 (5)
O3	0.0465 (6)	0.0504 (7)	0.0569 (7)	0.0128 (5)	0.0373 (6)	0.0029 (5)
S1	0.0447 (2)	0.0385 (2)	0.0392 (2)	0.01531 (16)	0.02879 (17)	0.00859 (15)
Cl1	0.0518 (2)	0.0325 (2)	0.0608 (3)	0.01558 (17)	0.00947 (19)	0.01663 (18)

C1—C2	1.396 (2)	C12—C17	1.3837 (19)
C1—C6	1.4025 (19)	C12—C13	1.3885 (18)
C1—S1	1.7412 (16)	C13—C14	1.388 (2)
C2—C3	1.369 (3)	C13—H13	0.9300
C2—H2	0.9300	C14—C15	1.377 (2)
C3—C4	1.394 (3)	C14—H14	0.9300
C3—H3	0.9300	C15—C16	1.380 (2)
C4—C5	1.379 (2)	C15—Cl1	1.7441 (14)
C4—H4	0.9300	C16—C17	1.384 (2)
C5—C6	1.393 (2)	C16—H16	0.9300
C5—H5	0.9300	C17—H17	0.9300
C6—C7	1.4327 (18)	C18—O3	1.2134 (17)
C7—C8	1.340 (2)	C18—O2	1.3521 (18)
C7—O1	1.3821 (15)	C19—O2	1.4507 (18)
C8—C9	1.4983 (18)	C19—C20	1.484 (3)
C8—S1	1.7428 (13)	C19—H19A	0.9700
C9—C10	1.5235 (16)	C19—H19B	0.9700
C9—C12	1.5289 (17)	C20—H20A	0.9600
C9—H9	0.9800	C20—H20B	0.9600
C10—C11	1.366 (2)	C20—H20C	0.9600
C10—C18	1.4492 (19)	N1—H1A	0.8600
C11—N1	1.3371 (17)	N1—H1B	0.8600
C11—O1	1.3717 (16)
C2—C1—C6	120.93 (15)	C13—C12—C9	119.77 (12)
C2—C1—S1	126.81 (13)	C14—C13—C12	121.31 (13)
C6—C1—S1	112.26 (10)	C14—C13—H13	119.3
C3—C2—C1	118.18 (15)	C12—C13—H13	119.3
C3—C2—H2	120.9	C15—C14—C13	118.84 (13)
C1—C2—H2	120.9	C15—C14—H14	120.6
C2—C3—C4	121.53 (15)	C13—C14—H14	120.6
C2—C3—H3	119.2	C14—C15—C16	121.13 (13)
C4—C3—H3	119.2	C14—C15—Cl1	119.42 (11)
C5—C4—C3	120.57 (17)	C16—C15—Cl1	119.45 (11)
C5—C4—H4	119.7	C15—C16—C17	119.13 (13)
C3—C4—H4	119.7	C15—C16—H16	120.4
C4—C5—C6	118.99 (15)	C17—C16—H16	120.4
C4—C5—H5	120.5	C12—C17—C16	121.25 (13)
C6—C5—H5	120.5	C12—C17—H17	119.4
C5—C6—C1	119.78 (13)	C16—C17—H17	119.4
C5—C6—C7	130.77 (13)	O3—C18—O2	121.50 (13)
C1—C6—C7	109.45 (13)	O3—C18—C10	126.35 (14)
C8—C7—O1	124.03 (12)	O2—C18—C10	112.14 (11)
C8—C7—C6	115.98 (12)	O2—C19—C20	110.42 (16)
O1—C7—C6	119.99 (12)	O2—C19—H19A	109.6
C7—C8—C9	124.22 (11)	C20—C19—H19A	109.6
C7—C8—S1	111.10 (10)	O2—C19—H19B	109.6
C9—C8—S1	124.64 (10)	C20—C19—H19B	109.6
C8—C9—C10	107.59 (11)	H19A—C19—H19B	108.1
C8—C9—C12	109.14 (10)	C19—C20—H20A	109.5
C10—C9—C12	113.90 (10)	C19—C20—H20B	109.5
C8—C9—H9	108.7	H20A—C20—H20B	109.5
C10—C9—H9	108.7	C19—C20—H20C	109.5
C12—C9—H9	108.7	H20A—C20—H20C	109.5
C11—C10—C18	118.03 (12)	H20B—C20—H20C	109.5
C11—C10—C9	123.05 (11)	C11—N1—H1A	120.0
C18—C10—C9	118.79 (12)	C11—N1—H1B	120.0
N1—C11—C10	127.48 (13)	H1A—N1—H1B	120.0
N1—C11—O1	108.97 (12)	C11—O1—C7	116.36 (11)
C10—C11—O1	123.55 (11)	C18—O2—C19	116.32 (11)
C17—C12—C13	118.29 (12)	C1—S1—C8	91.21 (7)
C17—C12—C9	121.86 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3	0.86	2.07	2.6796 (18)	127
N1—H1A···O3i	0.86	2.18	2.8956 (15)	141

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1H1AO3	0.86	2.07	2.6796(18)	127
N1H1AO3i	0.86	2.18	2.8956(15)	141

Symmetry code: (i) .