Crystal structure of 2-amino-3-cyano-4-(4-meth-oxy-phen-yl)-4H-1-benzo-thieno[3,2-b]pyran.

The three fused five- and six-membered rings in the title compound, C19H14N2O2S, are virtually coplanar, with the maximum deviation from the mean plane being 0.060 (1) Å. This benzothieno[3,2-b]pyran ring system is nearly perpendic-ular to the plane of the 4-meth-oxy-phenyl ring, forming a dihedral angle of 83.65 (5)°. In the crystal, mol-ecules are linked by pairs of N-H⋯N hydrogen bonds into inversion dimers. The dimeric units are further connected by an N-H⋯O hydrogen bond into a tape running along the b axis. The tapes are linked together by C-H⋯N and π-π inter-actions [centroid-centroid distance = 3.7743 (8) Å], forming a three-dimensional network.

Related literature

For biological properties of 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. (2015 ▸). For a related structure, see: Bakhouch et al. (2014 ▸).

Experimental

Crystal data

C19H14N2O2S

M = 334.38

Triclinic,

a = 6.0469 (3) Å

b = 10.8135 (5) Å

c = 13.3260 (6) Å

α = 109.943 (2)°

β = 93.226 (2)°

γ = 95.439 (2)°

V = 811.76 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.21 mm−1

T = 296 K

0.40 × 0.37 × 0.24 mm

Data collection

Bruker X8 APEX diffractometer

33610 measured reflections

4563 independent reflections

3683 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.123

S = 1.02

4563 reflections

217 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.26 e Å−3

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT (Bruker, 2009 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2015a ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b ▸); 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/S2056989015023464/is5436sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015023464/is5436Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015023464/is5436Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015023464/is5436fig1.tif

The mol­ecular structure 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.

Click here for additional data file.

. DOI: 10.1107/S2056989015023464/is5436fig2.tif

A packing diagram of the title compound showing mol­ecules linked by hydrogen bonds (dashed blue lines) and a π–π inter­action (dashed green line).

CCDC reference: 1440832

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

C19H14N2O2S	F(000) = 348
Mr = 334.38	Dx = 1.368 Mg m−3
Triclinic, P1	Melting point: 515 K
a = 6.0469 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.8135 (5) Å	Cell parameters from 4563 reflections
c = 13.3260 (6) Å	θ = 2.1–29.6°
α = 109.943 (2)°	µ = 0.21 mm−1
β = 93.226 (2)°	T = 296 K
γ = 95.439 (2)°	Block, colourless
V = 811.76 (7) Å3	0.40 × 0.37 × 0.24 mm
Z = 2

Bruker X8 APEX diffractometer	3683 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.030
Graphite monochromator	θmax = 29.6°, θmin = 2.1°
φ and ω scans	h = −8→8
33610 measured reflections	k = −15→15
4563 independent reflections	l = −18→18

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039	H-atom parameters constrained
wR(F2) = 0.123	w = 1/[σ2(Fo2) + (0.0643P)2 + 0.197P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
4563 reflections	Δρmax = 0.30 e Å−3
217 parameters	Δρmin = −0.26 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	0.9654 (2)	0.25649 (14)	0.46217 (11)	0.0435 (3)
C2	1.1515 (3)	0.27892 (17)	0.53633 (13)	0.0560 (4)
H2	1.1870	0.3600	0.5917	0.067*
C3	1.2798 (3)	0.17813 (19)	0.52500 (15)	0.0630 (5)
H3	1.4041	0.1914	0.5735	0.076*
C4	1.2285 (3)	0.05642 (19)	0.44279 (15)	0.0592 (4)
H4	1.3203	−0.0096	0.4365	0.071*
C5	1.0432 (2)	0.03195 (16)	0.37019 (12)	0.0481 (3)
H5	1.0082	−0.0501	0.3159	0.058*
C6	0.9100 (2)	0.13312 (13)	0.38033 (10)	0.0387 (3)
C7	0.7137 (2)	0.13537 (12)	0.31555 (10)	0.0361 (3)
C8	0.6294 (2)	0.25117 (12)	0.34268 (10)	0.0368 (3)
C9	0.4291 (2)	0.27703 (12)	0.28465 (10)	0.0354 (2)
H9	0.3147	0.3014	0.3347	0.042*
C10	0.3425 (2)	0.14569 (12)	0.19663 (10)	0.0351 (2)
C11	0.4390 (2)	0.03198 (12)	0.17479 (10)	0.0376 (3)
C12	0.1396 (2)	0.14023 (12)	0.13670 (10)	0.0389 (3)
C13	0.4803 (2)	0.38855 (11)	0.24049 (9)	0.0347 (2)
C14	0.3445 (2)	0.48861 (13)	0.25600 (11)	0.0425 (3)
H14	0.2199	0.4878	0.2937	0.051*
C15	0.3923 (3)	0.58966 (14)	0.21602 (13)	0.0483 (3)
H15	0.3001	0.6563	0.2272	0.058*
C16	0.5767 (2)	0.59197 (13)	0.15942 (11)	0.0435 (3)
C17	0.7125 (3)	0.49179 (15)	0.14233 (13)	0.0496 (3)
H17	0.8362	0.4919	0.1040	0.060*
C18	0.6619 (2)	0.39158 (14)	0.18300 (12)	0.0463 (3)
H18	0.7531	0.3244	0.1712	0.056*
C19	0.8083 (4)	0.7080 (2)	0.0723 (2)	0.0811 (6)
H19A	0.8128	0.7853	0.0522	0.122*
H19B	0.9378	0.7155	0.1201	0.122*
H19C	0.8065	0.6307	0.0094	0.122*
N1	0.3666 (2)	−0.08499 (12)	0.09804 (11)	0.0568 (4)
H1A	0.2477	−0.0932	0.0567	0.068*
H1B	0.4392	−0.1518	0.0902	0.068*
N2	−0.0263 (2)	0.13768 (13)	0.08954 (11)	0.0548 (3)
O1	0.62572 (16)	0.02236 (9)	0.23233 (8)	0.0432 (2)
O2	0.6139 (2)	0.69683 (11)	0.12427 (11)	0.0626 (3)
S1	0.78335 (7)	0.36908 (4)	0.45395 (3)	0.04948 (12)

	U11	U22	U33	U12	U13	U23
C1	0.0426 (7)	0.0494 (7)	0.0399 (6)	−0.0059 (5)	−0.0089 (5)	0.0224 (6)
C2	0.0547 (9)	0.0610 (9)	0.0499 (8)	−0.0129 (7)	−0.0208 (7)	0.0254 (7)
C3	0.0489 (9)	0.0776 (11)	0.0678 (10)	−0.0069 (8)	−0.0239 (8)	0.0405 (9)
C4	0.0463 (8)	0.0718 (11)	0.0686 (10)	0.0073 (7)	−0.0116 (7)	0.0387 (9)
C5	0.0443 (7)	0.0536 (8)	0.0508 (8)	0.0039 (6)	−0.0070 (6)	0.0263 (6)
C6	0.0351 (6)	0.0469 (7)	0.0384 (6)	−0.0032 (5)	−0.0055 (5)	0.0238 (5)
C7	0.0352 (6)	0.0383 (6)	0.0349 (6)	−0.0018 (5)	−0.0060 (5)	0.0159 (5)
C8	0.0381 (6)	0.0372 (6)	0.0333 (5)	−0.0011 (5)	−0.0055 (5)	0.0129 (5)
C9	0.0353 (6)	0.0352 (6)	0.0342 (6)	0.0051 (4)	−0.0008 (4)	0.0106 (5)
C10	0.0335 (6)	0.0351 (6)	0.0358 (6)	0.0025 (4)	−0.0042 (4)	0.0127 (5)
C11	0.0367 (6)	0.0351 (6)	0.0403 (6)	0.0013 (5)	−0.0084 (5)	0.0148 (5)
C12	0.0393 (6)	0.0357 (6)	0.0385 (6)	0.0094 (5)	−0.0026 (5)	0.0087 (5)
C13	0.0365 (6)	0.0308 (5)	0.0341 (6)	0.0070 (4)	−0.0023 (4)	0.0080 (4)
C14	0.0394 (6)	0.0439 (7)	0.0437 (7)	0.0148 (5)	0.0046 (5)	0.0121 (5)
C15	0.0497 (8)	0.0405 (7)	0.0572 (8)	0.0210 (6)	0.0018 (6)	0.0166 (6)
C16	0.0502 (7)	0.0343 (6)	0.0475 (7)	0.0082 (5)	−0.0039 (6)	0.0165 (5)
C17	0.0496 (8)	0.0461 (7)	0.0617 (9)	0.0162 (6)	0.0167 (7)	0.0252 (7)
C18	0.0472 (7)	0.0388 (6)	0.0604 (8)	0.0204 (6)	0.0147 (6)	0.0215 (6)
C19	0.0820 (14)	0.0726 (12)	0.1117 (17)	0.0095 (10)	0.0202 (13)	0.0596 (13)
N1	0.0588 (8)	0.0342 (6)	0.0648 (8)	0.0082 (5)	−0.0296 (6)	0.0061 (5)
N2	0.0480 (7)	0.0517 (7)	0.0530 (7)	0.0193 (5)	−0.0130 (5)	0.0027 (6)
O1	0.0421 (5)	0.0351 (4)	0.0482 (5)	0.0055 (4)	−0.0155 (4)	0.0119 (4)
O2	0.0705 (8)	0.0488 (6)	0.0832 (8)	0.0155 (5)	0.0089 (6)	0.0395 (6)
S1	0.0563 (2)	0.04306 (19)	0.04101 (19)	−0.00067 (15)	−0.01393 (15)	0.00898 (14)

C1—C2	1.4007 (19)	C11—N1	1.3416 (16)
C1—C6	1.4011 (19)	C11—O1	1.3612 (14)
C1—S1	1.7427 (15)	C12—N2	1.1462 (17)
C2—C3	1.369 (3)	C13—C18	1.3779 (19)
C2—H2	0.9300	C13—C14	1.3867 (17)
C3—C4	1.389 (3)	C14—C15	1.384 (2)
C3—H3	0.9300	C14—H14	0.9300
C4—C5	1.382 (2)	C15—C16	1.384 (2)
C4—H4	0.9300	C15—H15	0.9300
C5—C6	1.394 (2)	C16—O2	1.3717 (16)
C5—H5	0.9300	C16—C17	1.3858 (19)
C6—C7	1.4349 (16)	C17—C18	1.385 (2)
C7—C8	1.3385 (18)	C17—H17	0.9300
C7—O1	1.3755 (14)	C18—H18	0.9300
C8—C9	1.4997 (17)	C19—O2	1.414 (2)
C8—S1	1.7382 (12)	C19—H19A	0.9600
C9—C10	1.5233 (16)	C19—H19B	0.9600
C9—C13	1.5265 (17)	C19—H19C	0.9600
C9—H9	0.9800	N1—H1A	0.8600
C10—C11	1.3594 (17)	N1—H1B	0.8600
C10—C12	1.4110 (16)
C2—C1—C6	120.66 (14)	N1—C11—O1	110.43 (11)
C2—C1—S1	127.61 (13)	C10—C11—O1	122.91 (11)
C6—C1—S1	111.71 (10)	N2—C12—C10	178.75 (15)
C3—C2—C1	118.14 (15)	C18—C13—C14	118.18 (12)
C3—C2—H2	120.9	C18—C13—C9	120.75 (11)
C1—C2—H2	120.9	C14—C13—C9	121.07 (12)
C2—C3—C4	121.54 (14)	C15—C14—C13	120.76 (13)
C2—C3—H3	119.2	C15—C14—H14	119.6
C4—C3—H3	119.2	C13—C14—H14	119.6
C5—C4—C3	121.02 (16)	C16—C15—C14	120.31 (12)
C5—C4—H4	119.5	C16—C15—H15	119.8
C3—C4—H4	119.5	C14—C15—H15	119.8
C4—C5—C6	118.42 (15)	O2—C16—C15	116.47 (12)
C4—C5—H5	120.8	O2—C16—C17	124.00 (14)
C6—C5—H5	120.8	C15—C16—C17	119.52 (13)
C5—C6—C1	120.21 (12)	C18—C17—C16	119.31 (13)
C5—C6—C7	129.87 (13)	C18—C17—H17	120.3
C1—C6—C7	109.91 (12)	C16—C17—H17	120.3
C8—C7—O1	124.87 (11)	C13—C18—C17	121.91 (12)
C8—C7—C6	115.62 (11)	C13—C18—H18	119.0
O1—C7—C6	119.51 (11)	C17—C18—H18	119.0
C7—C8—C9	124.73 (11)	O2—C19—H19A	109.5
C7—C8—S1	111.22 (9)	O2—C19—H19B	109.5
C9—C8—S1	124.05 (9)	H19A—C19—H19B	109.5
C8—C9—C10	105.99 (10)	O2—C19—H19C	109.5
C8—C9—C13	113.02 (10)	H19A—C19—H19C	109.5
C10—C9—C13	112.31 (10)	H19B—C19—H19C	109.5
C8—C9—H9	108.5	C11—N1—H1A	120.0
C10—C9—H9	108.5	C11—N1—H1B	120.0
C13—C9—H9	108.5	H1A—N1—H1B	120.0
C11—C10—C12	117.49 (11)	C11—O1—C7	116.13 (10)
C11—C10—C9	125.31 (11)	C16—O2—C19	118.42 (13)
C12—C10—C9	117.12 (10)	C8—S1—C1	91.51 (6)
N1—C11—C10	126.65 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2i	0.86	2.18	3.0060 (17)	160
N1—H1B···O2ii	0.86	2.19	3.0158 (16)	162
C18—H18···N2iii	0.93	2.49	3.3997 (17)	165

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N2i	0.86	2.18	3.0060 (17)	160
N1—H1B⋯O2ii	0.86	2.19	3.0158 (16)	162
C18—H18⋯N2iii	0.93	2.49	3.3997 (17)	165

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