



Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989015008154/tk5366sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S2056989015008154/tk5366Isup2.hkl |
![]() | Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989015008154/tk5366Isup3.cml |
CCDC reference: 1061576
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean
(C-C)= 0.002 Å
- R factor = 0.044
- wR factor = 0.130
- Data-to-parameter ratio = 21.9
checkCIF/PLATON results
No syntax errors found No errors found in this datablock
In a 100 ml flask equipped with a condenser was dissolved 4 mmol of (Z)-2-(4-methoxybenzylidene)-1-benzo[b]thiophen-3(2H)-one and 5 mmol of ethyl cyanoacetate in 30 ml of ethanol. Then, 1 ml of piperidine was added, and the reaction mixture was refluxed for 6 h. Thin layer chromatography revealed the formation of a single product. The organic phase was evaporated under reduced pressure. The resulting residue was recrystallized from ethanol by slow evaporation (Yield: 28%; m.pt: 395 K).
H atoms were located in a difference map and treated as riding with C—H = 0.93–0.98 Å and N—H = 0.86 Å, and with Uiso(H) = 1.2–1.5 Ueq(C) and Uiso(H) = 1.2 Ueq(N). Two reflections, i.e. (1 0 0) and (1 1 0), were omitted from the final refinement owing to poor agreement.
Substituted 2-amino-4-aryl-4H-pyran derivatives are an important class of heterocyclic compounds, which frequently exhibit a wide range of biological properties viz. antiproliferative, antitubercular activities (Panda et al., 1997; Mungra et al., 2011). Thus, in view of the large spectrum of applications of these compounds and in continuation of ongoing research focused on the reactivity of the (Z)-2-arylidenebenzo[b]thiophen- 3(2H)-ones (thioaurones) (Boughaleb et al., 2010; 2011; Bakhouch et al., 2014; 2015), the title compound was investigated This was prepared by the the action of ethyl cyanoacetate on (Z)-2-(4- methoxybenzylidene)benzo[b]thiophen-3(2H)-one (Daisley et al., 1982). The subsequent tautomeric transformation gives rise to ethyl 2-amino-4-(4-methoxyphenyl)-4H-1-benzothieno[3,2-b]pyran-3- carboxylate.
The molecule of the title compound is formed by three fused rings linked to an ethyl-3-carboxylate group and to a methoxybenzene group as shown in Fig. 1. The three fused rings (S1C1 to C11 O1) are nearly coplanar, with the maximum deviation from the mean plane being -0.131 (1) Å at C10, and makes a dihedral angle of 85.72 (6)° with the plans through this attached methoxyphenyl group.
In the crystal, the molecules are linked by N—H···O hydrogen bonds as shown in Fig. 2 and Table 1.
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 the (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).
Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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).
![]() | Fig. 1. 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. |
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 |
C21H19NO4S | V = 1904.25 (19) Å3 |
Mr = 381.43 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.8355 (7) Å | µ = 0.20 mm−1 |
b = 18.6222 (11) Å | T = 296 K |
c = 9.0110 (5) Å | 0.42 × 0.31 × 0.26 mm |
β = 106.502 (2)° |
Bruker X8 APEX diffractometer | 5347 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1995) | 4118 reflections with I > 2σ(I) |
Tmin = 0.673, Tmax = 0.746 | Rint = 0.031 |
38870 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.25 e Å−3 |
5347 reflections | Δρmin = −0.27 e Å−3 |
244 parameters |
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 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+2, y+1/2, −z+3/2. |
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 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+2, y+1/2, −z+3/2. |
Substituted 2-amino-4-aryl-4H-pyran derivatives are an important class of heterocyclic compounds, which frequently exhibit a wide range of biological properties viz. antiproliferative, antitubercular activities (Panda et al., 1997; Mungra et al., 2011). Thus, in view of the large spectrum of applications of these compounds and in continuation of ongoing research focused on the reactivity of the (Z)-2-arylidenebenzo[b]thiophen- 3(2H)-ones (thioaurones) (Boughaleb et al., 2010; 2011; Bakhouch et al., 2014; 2015), the title compound was investigated This was prepared by the the action of ethyl cyanoacetate on (Z)-2-(4- methoxybenzylidene)benzo[b]thiophen-3(2H)-one (Daisley et al., 1982). The subsequent tautomeric transformation gives rise to ethyl 2-amino-4-(4-methoxyphenyl)-4H-1-benzothieno[3,2-b]pyran-3- carboxylate.
The molecule of the title compound is formed by three fused rings linked to an ethyl-3-carboxylate group and to a methoxybenzene group as shown in Fig. 1. The three fused rings (S1C1 to C11 O1) are nearly coplanar, with the maximum deviation from the mean plane being -0.131 (1) Å at C10, and makes a dihedral angle of 85.72 (6)° with the plans through this attached methoxyphenyl group.
In the crystal, the molecules are linked by N—H···O hydrogen bonds as shown in Fig. 2 and Table 1.