3-Cyano-4-[2-(4-methoxy­phenyl)­ethenyl]-6-methyl-2H-1-benzo­pyran-2-one

Vijayalakshmi, L.; Parthasarathi, V.; Varu, B.; Shah, A.

doi:10.1107/S1600536801002653

3-Cyano-4-[2-(4-methoxyphenyl)ethenyl]-6-methyl-2H-1-benzopyran-2-one

L. Vijayalakshmi, V. Parthasarathi, B. Varu and A. Shah

Benzopyran derivatives are known to possess various biological activities. In the title compound, C₂₀H₁₅NO₃, the benzopyran ring is essentially planar and the dihedral angle between the benzopyran and phenyl rings is 56.5 (1)°. In the crystal, the carbonyl and methoxy O atoms are involved in weak C—H

O-type intermolecular interactions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801002653/ci6005sup1.cif Contains datablocks 1, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536801002653/ci6005Isup2.hkl Contains datablock I

CCDC reference: 159858

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.004 Å
R factor = 0.051
wR factor = 0.144
Data-to-parameter ratio = 8.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_371  Alert C Long   C(sp2)-C(sp1) Bond  C(3)   -   C(21)  =       1.42 Ang.

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           69.84
         From the CIF: _reflns_number_total               1804
         Count of symmetry unique reflns         1804
         Completeness (_total/calc)            100.00%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured         0
         Fraction of Friedel pairs measured     0.000
         Are heavy atom types Z>Si present           no
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

Comment top

Many derivatives of benzopyran are found to possess medicinal and biological activities like antithrombotic effect, vasodilating effect on coronary vessels, tonic influence on capillary blood vessels, reduction in blood pressure, antispastic and photosensitizing effect (Borowiak & Wolska, 1989). The structure determination of the title compound, (I), was taken up as part our study on benzopyrans.

The benzopyran ring is planar, with a maximum deviation of -0.024 (3) Å for C3. The dihedral angle between the phenyl and benzopyran rings is 56.5 (1)°. The alternate single and double bonds between O2 and C10 [O2═C2 1.213 (4), C2—C3 1.449 (5), C3═C4 1.372 (4) and C4—C10 1.443 (4) Å] indicate conjugation (Allen et al., 1987; Alcock & Hough, 1972). The coplanarity of the methoxy carbon with the phenyl ring [C16—C15—O19—C20 1.6 (5)°] is resulted in a close approach between C20 and C16 [2.807 (5) Å] and this caused the widening of C16—C15—O19 [125.3 (3)°] and narrowing of C14—C15—O19 [114.8 (3)°] from 120° (Sheldrick et al., 1980; Koetzle & Williams, 1976; Sakaki et al., 1976). Steric interactions cause the deviation of C4—C10—C5 [123.7 (3)°] and O1—C9—C8 [116.7 (3)°] angles from 120°, a common feature observed in the coumarin derivatives (Ramasubbu, 1982; Ramasubbu et al., 1982; Borowiak & Wolska, 1989). In the crystal, weak C—H···O-type intermolecular interactions involving O2 and O19 are observed (Jeffrey & Saenger, 1991).

Experimental top

A mixture of 3-cyano-4,6-dimethyl-2H-1-benzopyran-2-one (0.01 mol) and 4-methoxy benzaldehyde (0.01 mol) were dissolved in chloroform (75–80 ml) and a few drops of piperidine (8–10 drops) was added as a catalyst. The mixture was heated with stirring for 15–16 h. After evaporation, the solid residue was recrystallized from dimethylformamide to give white crystals [m.p. 484 K; yield 56%].

Computing details top

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: MolEN (Fair, 1990); data reduction: MolEN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP97 (Zsolnai, 1997); software used to prepare material for publication: SHELXL97 and PARST95 (Nardelli, 1995).

Figures top

Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids.

3-cyano-4-[2-(4-methoxyphenyl)ethenyl]-6-methyl-2H-1-benzopyran-2-one top

Crystal data top

C₂₀H₁₅NO₃	D_x = 1.298 Mg m⁻³
M_r = 317.33	Cu Kα radiation, λ = 1.54175 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 25 reflections
a = 7.8683 (12) Å	θ = 2–25°
b = 7.913 (2) Å	µ = 0.71 mm⁻¹
c = 26.0869 (11) Å	T = 293 K
V = 1624.1 (5) Å³	Needle, white
Z = 4	0.20 × 0.12 × 0.10 mm
F(000) = 664

Data collection top

Enraf-Nonius CAD-4 diffractometer	1626 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.000
Graphite monochromator	θ_max = 69.8°, θ_min = 3.4°
ω–2θ scans	h = 0→9
Absorption correction: ψ scan (North et al., 1968)	k = 0→9
T_min = 0.875, T_max = 0.930	l = 0→31
1805 measured reflections	3 standard reflections every 60 reflections
1804 independent reflections	intensity decay: 0.1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.051	H-atom parameters constrained
wR(F²) = 0.144	w = 1/[σ²(F_o²) + (0.0837P)² + 0.2613P] where P = (F_o² + 2F_c²)/3
S = 1.17	(Δ/σ)_max = 0.009
1804 reflections	Δρ_max = 0.26 e Å⁻³
222 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0079 (11)

Crystal data top

C₂₀H₁₅NO₃	V = 1624.1 (5) Å³
M_r = 317.33	Z = 4
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 7.8683 (12) Å	µ = 0.71 mm⁻¹
b = 7.913 (2) Å	T = 293 K
c = 26.0869 (11) Å	0.20 × 0.12 × 0.10 mm

Data collection top

Enraf-Nonius CAD-4 diffractometer	1626 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.000
T_min = 0.875, T_max = 0.930	3 standard reflections every 60 reflections
1805 measured reflections	intensity decay: 0.1%
1804 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.144	H-atom parameters constrained
S = 1.17	Δρ_max = 0.26 e Å⁻³
1804 reflections	Δρ_min = −0.20 e Å⁻³
222 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.5438 (3)	0.1758 (3)	0.12170 (9)	0.0672 (7)
O2	0.3666 (3)	0.0550 (4)	0.17594 (13)	0.0942 (10)
C2	0.5083 (4)	0.1108 (4)	0.16893 (15)	0.0649 (9)
C3	0.6427 (4)	0.1127 (4)	0.20688 (12)	0.0536 (7)
C4	0.8000 (4)	0.1806 (4)	0.19728 (11)	0.0475 (6)
C5	0.9887 (4)	0.3146 (4)	0.13108 (12)	0.0529 (7)
H5	1.0766	0.3215	0.1548	0.067 (4)*
C6	1.0157 (5)	0.3723 (4)	0.08248 (12)	0.0604 (8)
C7	0.8824 (5)	0.3648 (5)	0.04749 (13)	0.0697 (10)
H7	0.8988	0.4041	0.0143	0.067 (4)*
C8	0.7263 (5)	0.3001 (5)	0.06136 (13)	0.0681 (9)
H8	0.6377	0.2967	0.0378	0.067 (4)*
C9	0.7032 (4)	0.2410 (4)	0.11011 (13)	0.0557 (8)
C10	0.8323 (4)	0.2450 (4)	0.14645 (11)	0.0482 (7)
C11	0.9320 (3)	0.1890 (4)	0.23647 (11)	0.0499 (7)
H11	1.0412	0.1533	0.2282	0.067 (4)*
C12	0.9023 (4)	0.2455 (4)	0.28332 (11)	0.0496 (7)
H12	0.7910	0.2776	0.2904	0.067 (4)*
C13	0.9767 (4)	0.3503 (4)	0.36948 (11)	0.0515 (7)
H13	0.8686	0.3973	0.3713	0.067 (4)*
C14	1.0833 (4)	0.3690 (4)	0.41012 (12)	0.0567 (8)
H14	1.0475	0.4263	0.4393	0.067 (4)*
C15	1.2475 (4)	0.3010 (4)	0.40758 (11)	0.0530 (7)
C16	1.2980 (4)	0.2143 (4)	0.36462 (11)	0.0537 (7)
H16	1.4065	0.1679	0.3631	0.067 (4)*
C17	1.1884 (4)	0.1956 (4)	0.32378 (11)	0.0518 (7)
H17	1.2242	0.1372	0.2948	0.067 (4)*
C18	1.0237 (4)	0.2633 (4)	0.32530 (11)	0.0473 (6)
O19	1.3445 (3)	0.3271 (4)	0.45007 (8)	0.0732 (7)
C20	1.5138 (5)	0.2619 (7)	0.44906 (15)	0.0834 (12)
H201	1.5107	0.1434	0.4413	0.123 (8)*
H202	1.5660	0.2786	0.4819	0.123 (8)*
H203	1.5783	0.3200	0.4233	0.123 (8)*
C21	0.5997 (4)	0.0334 (5)	0.25419 (15)	0.0645 (9)
N21	0.5661 (5)	−0.0349 (5)	0.29175 (15)	0.0883 (10)
C22	1.1854 (5)	0.4455 (6)	0.06776 (15)	0.0783 (11)
H221	1.2285	0.5125	0.0955	0.123 (8)*
H222	1.1724	0.5151	0.0379	0.123 (8)*
H223	1.2635	0.3555	0.0605	0.123 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0383 (11)	0.0745 (14)	0.0888 (16)	−0.0068 (11)	−0.0153 (10)	−0.0109 (13)
O2	0.0425 (13)	0.098 (2)	0.142 (2)	−0.0279 (15)	−0.0157 (15)	0.0056 (19)
C2	0.0411 (16)	0.0581 (18)	0.096 (2)	−0.0096 (15)	−0.0065 (17)	−0.0073 (17)
C3	0.0366 (14)	0.0476 (15)	0.0765 (19)	−0.0042 (13)	−0.0016 (14)	−0.0058 (14)
C4	0.0348 (13)	0.0418 (13)	0.0658 (16)	−0.0007 (12)	−0.0022 (12)	−0.0061 (12)
C5	0.0412 (14)	0.0519 (15)	0.0654 (16)	−0.0036 (14)	−0.0017 (14)	−0.0053 (13)
C6	0.0595 (19)	0.0605 (17)	0.0611 (17)	−0.0042 (17)	0.0021 (15)	−0.0052 (15)
C7	0.080 (2)	0.074 (2)	0.0556 (17)	−0.001 (2)	−0.0048 (17)	−0.0017 (16)
C8	0.061 (2)	0.076 (2)	0.068 (2)	0.0018 (19)	−0.0197 (16)	−0.0107 (17)
C9	0.0421 (15)	0.0526 (16)	0.0723 (18)	−0.0002 (14)	−0.0083 (14)	−0.0116 (14)
C10	0.0380 (14)	0.0471 (14)	0.0595 (15)	0.0001 (13)	−0.0050 (12)	−0.0111 (12)
C11	0.0313 (12)	0.0528 (15)	0.0657 (16)	−0.0014 (12)	−0.0017 (12)	0.0004 (14)
C12	0.0361 (13)	0.0492 (14)	0.0634 (16)	0.0004 (13)	0.0001 (12)	0.0022 (12)
C13	0.0431 (14)	0.0548 (15)	0.0566 (15)	0.0070 (13)	0.0054 (13)	0.0035 (13)
C14	0.0567 (18)	0.0570 (17)	0.0563 (15)	0.0134 (16)	0.0064 (15)	−0.0019 (14)
C15	0.0520 (16)	0.0559 (16)	0.0510 (14)	0.0032 (15)	−0.0057 (13)	0.0057 (13)
C16	0.0413 (14)	0.0578 (16)	0.0618 (17)	0.0082 (14)	0.0003 (13)	0.0047 (13)
C17	0.0413 (14)	0.0567 (16)	0.0576 (15)	0.0069 (14)	0.0025 (13)	−0.0060 (13)
C18	0.0383 (13)	0.0454 (13)	0.0581 (15)	0.0005 (12)	0.0014 (12)	0.0040 (12)
O19	0.0648 (15)	0.0912 (17)	0.0638 (13)	0.0191 (15)	−0.0148 (11)	−0.0054 (12)
C20	0.058 (2)	0.107 (3)	0.085 (2)	0.013 (2)	−0.0243 (19)	0.000 (2)
C21	0.0432 (16)	0.0580 (17)	0.092 (2)	−0.0076 (16)	0.0087 (17)	−0.0055 (18)
N21	0.073 (2)	0.081 (2)	0.111 (2)	−0.018 (2)	0.025 (2)	0.009 (2)
C22	0.067 (2)	0.094 (3)	0.074 (2)	−0.018 (2)	0.0129 (19)	0.002 (2)

Geometric parameters (Å, º) top

O1—C2	1.364 (4)	C12—H12	0.9300
O1—C9	1.389 (4)	C13—C14	1.360 (4)
O2—C2	1.213 (4)	C13—C18	1.392 (4)
C2—C3	1.449 (5)	C13—H13	0.9300
C3—C4	1.372 (4)	C14—C15	1.401 (4)
C3—C21	1.426 (5)	C14—H14	0.9300
C4—C10	1.443 (4)	C15—O19	1.362 (4)
C4—C11	1.459 (4)	C15—C16	1.373 (4)
C5—C6	1.364 (4)	C16—C17	1.378 (4)
C5—C10	1.407 (4)	C16—H16	0.9300
C5—H5	0.9300	C17—C18	1.403 (4)
C6—C7	1.392 (5)	C17—H17	0.9300
C6—C22	1.505 (5)	O19—C20	1.428 (5)
C7—C8	1.379 (6)	C20—H201	0.9600
C7—H7	0.9300	C20—H202	0.9600
C8—C9	1.367 (5)	C20—H203	0.9600
C8—H8	0.9300	C21—N21	1.150 (5)
C9—C10	1.390 (4)	C22—H221	0.9600
C11—C12	1.322 (4)	C22—H222	0.9600
C11—H11	0.9300	C22—H223	0.9600
C12—C18	1.460 (4)

C2—O1—C9	121.4 (2)	C18—C12—H12	116.2
O2—C2—O1	117.5 (3)	C14—C13—C18	122.4 (3)
O2—C2—C3	124.9 (4)	C14—C13—H13	118.8
O1—C2—C3	117.6 (3)	C18—C13—H13	118.8
C4—C3—C21	123.0 (3)	C13—C14—C15	119.3 (3)
C4—C3—C2	122.5 (3)	C13—C14—H14	120.3
C21—C3—C2	114.4 (3)	C15—C14—H14	120.3
C3—C4—C10	117.7 (3)	O19—C15—C16	125.3 (3)
C3—C4—C11	122.2 (3)	O19—C15—C14	114.8 (3)
C10—C4—C11	120.1 (2)	C16—C15—C14	119.8 (3)
C6—C5—C10	122.2 (3)	C15—C16—C17	120.2 (3)
C6—C5—H5	118.9	C15—C16—H16	119.9
C10—C5—H5	118.9	C17—C16—H16	119.9
C5—C6—C7	118.6 (3)	C16—C17—C18	121.0 (3)
C5—C6—C22	120.3 (3)	C16—C17—H17	119.5
C7—C6—C22	121.2 (3)	C18—C17—H17	119.5
C8—C7—C6	121.0 (3)	C13—C18—C17	117.2 (3)
C8—C7—H7	119.5	C13—C18—C12	119.7 (3)
C6—C7—H7	119.5	C17—C18—C12	123.1 (3)
C9—C8—C7	119.3 (3)	C15—O19—C20	116.9 (3)
C9—C8—H8	120.3	O19—C20—H201	109.5
C7—C8—H8	120.3	O19—C20—H202	109.5
C8—C9—O1	116.7 (3)	H201—C20—H202	109.5
C8—C9—C10	121.9 (3)	O19—C20—H203	109.5
O1—C9—C10	121.3 (3)	H201—C20—H203	109.5
C9—C10—C5	117.0 (3)	H202—C20—H203	109.5
C9—C10—C4	119.3 (3)	N21—C21—C3	178.1 (4)
C5—C10—C4	123.7 (3)	C6—C22—H221	109.5
C12—C11—C4	122.5 (3)	C6—C22—H222	109.5
C12—C11—H11	118.7	H221—C22—H222	109.5
C4—C11—H11	118.7	C6—C22—H223	109.5
C11—C12—C18	127.6 (3)	H221—C22—H223	109.5
C11—C12—H12	116.2	H222—C22—H223	109.5

C9—O1—C2—O2	−179.4 (3)	C6—C5—C10—C9	−1.6 (4)
C9—O1—C2—C3	0.2 (5)	C6—C5—C10—C4	179.1 (3)
O2—C2—C3—C4	−178.6 (3)	C3—C4—C10—C9	2.0 (4)
O1—C2—C3—C4	1.7 (5)	C11—C4—C10—C9	−177.9 (3)
O2—C2—C3—C21	3.3 (5)	C3—C4—C10—C5	−178.6 (3)
O1—C2—C3—C21	−176.3 (3)	C11—C4—C10—C5	1.5 (4)
C21—C3—C4—C10	175.0 (3)	C3—C4—C11—C12	−47.6 (4)
C2—C3—C4—C10	−2.8 (4)	C10—C4—C11—C12	132.3 (3)
C21—C3—C4—C11	−5.1 (5)	C4—C11—C12—C18	−178.6 (3)
C2—C3—C4—C11	177.1 (3)	C18—C13—C14—C15	1.0 (5)
C10—C5—C6—C7	1.4 (5)	C13—C14—C15—O19	179.7 (3)
C10—C5—C6—C22	−179.9 (3)	C13—C14—C15—C16	−1.0 (5)
C5—C6—C7—C8	−0.2 (6)	O19—C15—C16—C17	179.9 (3)
C22—C6—C7—C8	−179.0 (3)	C14—C15—C16—C17	0.8 (5)
C6—C7—C8—C9	−0.6 (6)	C15—C16—C17—C18	−0.4 (5)
C7—C8—C9—O1	−179.3 (3)	C14—C13—C18—C17	−0.6 (4)
C7—C8—C9—C10	0.4 (5)	C14—C13—C18—C12	179.0 (3)
C2—O1—C9—C8	178.8 (3)	C16—C17—C18—C13	0.3 (4)
C2—O1—C9—C10	−0.9 (5)	C16—C17—C18—C12	−179.3 (3)
C8—C9—C10—C5	0.7 (5)	C11—C12—C18—C13	169.6 (3)
O1—C9—C10—C5	−179.6 (2)	C11—C12—C18—C17	−10.7 (5)
C8—C9—C10—C4	−180.0 (3)	C16—C15—O19—C20	1.6 (5)
O1—C9—C10—C4	−0.2 (4)	C14—C15—O19—C20	−179.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O2ⁱ	0.93	2.67	3.406 (4)	137
C13—H13···O2ⁱ	0.93	2.55	3.365 (4)	147
C22—H222···O19ⁱⁱ	0.96	2.61	3.566 (4)	173

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+5/2, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₅NO₃
M_r	317.33
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	7.8683 (12), 7.913 (2), 26.0869 (11)
V (Å³)	1624.1 (5)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.71
Crystal size (mm)	0.20 × 0.12 × 0.10

Data collection
Diffractometer	Enraf-Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.875, 0.930
No. of measured, independent and observed [I > 2σ(I)] reflections	1805, 1804, 1626
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.144, 1.17
No. of reflections	1804
No. of parameters	222
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.20

Computer programs: CAD-4 Software (Enraf-Nonius, 1989), MolEN (Fair, 1990), MolEN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ZORTEP97 (Zsolnai, 1997), SHELXL97 and PARST95 (Nardelli, 1995).