3-Cyano-4-[2-(4-methyl­thio­phenyl)­ethenyl]-2H-1-benzo­pyran-2-one

In the title compound, 4-[2-(4-methyl­thio­phenyl)­ethenyl]-2-oxo-2H-1-benzo­pyran-3-carbo­nitrile, C₁₉H₁₃NO₂S, the benzo­pyran and phenyl rings are individually planar, but the phenyl ring is twisted 56.7 (1)° out of the benzo­pyran ring plane. The configuration about the ethenyl double bond is E.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.030
• wR factor = 0.086
• Data-to-parameter ratio = 8.0

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)  =       1.43 Ang.

General Notes



ABSTM_02  When printed, the submitted absorption T values will be replaced
          by the scaled T values. Since the ratio of scaled T's is
          identical to the ratio of reported T values, the scaling does
          not imply a change to the absorption corrections used in the
          study.
          Ratio of Tmax expected/reported      0.946
          Tmax scaled      0.842 Tmin scaled      0.741

REFLT_03
         From the CIF: _diffrn_reflns_theta_max           67.86
         From the CIF: _reflns_number_total               1676
         Count of symmetry unique reflns         1677
         Completeness (_total/calc)             99.94%
         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          yes
          WARNING: Large fraction of Friedel related reflns may
                   be needed to determine absolute structure


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

The structure determination of the title compound, (I), was taken up as part of our studies on coumarin derivatives which possess a variety of medicinal and biological properties (Parrish et al., 1974; Evans et al., 1981; Fujiwhara et al., 1978; Song & Gordon, 1980; Kawase et al., 2001). It is of physiological interest that there is an apparent close chemical similarity between coumarin and vitamin K (Kralt & Claassen, 1972).

The molecular geometry of (I) is similar to that of 3-cyano-6-methyl-4-[2-(4-methoxyphenyl)ethenyl]-2H-1-benzopyran-2-one (Vijayalakshmi et al., 2001). The bond lengths and angles in the coumarin moiety agree well with the reported values (Jha et al.., 2000; Chinnakali et al., 1998, 1999; Vijayalakshmi et al., 2000, 2001). The dihedral angle between the phenyl and planar benzopyran rings is 56.7 (1)°. The widening of the bond angle C11—C12—C18 to 126.8 (2)° is due to the close approach of the H11 and H17 atoms (2.256 Å). A similar feature is observed in the structures of cinnamanilides (Renganayaki et al., 1999, 2000; Subramanian et al., 1999) and dienethioamide (Nesterov et al., 2000). Also, the slight increase in C4—C11—C12 to 122.2 (2)° is due to steric repulsion between H12 and C21 (H12···C21 2.629 Å). The Csp²—S [1.755 (2) Å] and Csp³—S [1.777 (4) Å] distances show partial double-bond character (Malhotra et al., 1997; Azim et al., 1997; Kumar et al., 1999; Allen et al., 1987). A C—H···N intermolecular short contact is observed [C16···N21ⁱ 3.337 (4) Å and H16···N21ⁱ 2.56 Å; symmetry code: (i) x, y + 1, z].

S2. Experimental

A mixture of 3-cyano-4-methyl-2H-1-benzopyran-2-one (0.01 mol) and 4-methylthiobenzaldehyde (0.01 mol) was dissolved in chloroform (75 ml) and a few drops of piperidine (8–10 drops) was added as catalyst. The mixture was heated on a hotplate with stirring for 15–16 h. After evaporation of the solvent, the solid residue was recrystallized from dimethylformamide to give yellow crystals (m.p. 482 K; yield 64%).

S3. Refinement

All H atoms were fixed using geometrical considerations. The absolute configuration is indeterminate for the title compound.

Computing details

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

Figures

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

4-[2-(4-Methylthiophenyl)ethenyl]-2-oxo-2H-1-benzopyran-3-carbonitrile

Crystal data

C19H13NO2S	Dx = 1.353 Mg m^−3
Mr = 319.36	Cu Kα radiation, λ = 1.54180 Å
Orthorhombic, P212121	Cell parameters from 25 reflections
a = 7.783 (3) Å	θ = 2–25°
b = 7.8653 (10) Å	µ = 1.91 mm^−1
c = 25.610 (3) Å	T = 293 K
V = 1567.7 (7) Å^3	Needle, yellow
Z = 4	0.15 × 0.10 × 0.09 mm
F(000) = 664

Data collection

Enraf-Nonius CAD-4 diffractometer	1606 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 67.9°, θmin = 3.5°
ω–2θ scans	h = 0→9
Absorption correction: ψ scan (North et al., 1968)	k = 0→9
Tmin = 0.784, Tmax = 0.891	l = 0→30
1676 measured reflections	3 standard reflections every 100 reflections
1676 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.086	w = 1/[σ^2(Fo^2) + (0.0501P)^2 + 0.3363P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
1676 reflections	Δρmax = 0.18 e Å^−3
210 parameters	Δρmin = −0.21 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0037 (4)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	1.0648 (2)	−0.2199 (2)	−0.13279 (6)	0.0528 (4)
O2	1.2001 (3)	−0.3808 (2)	−0.07566 (9)	0.0698 (6)
C2	1.1358 (3)	−0.2453 (3)	−0.08479 (10)	0.0490 (6)
C3	1.1296 (3)	−0.1021 (3)	−0.04888 (9)	0.0414 (5)
C4	1.0554 (3)	0.0500 (3)	−0.06072 (8)	0.0371 (5)
C5	0.9153 (3)	0.2224 (3)	−0.13167 (10)	0.0515 (6)
H5	0.9055	0.3155	−0.1095	0.062*
C6	0.8575 (4)	0.2338 (4)	−0.18233 (11)	0.0652 (8)
H6	0.8104	0.3351	−0.1944	0.078*
C7	0.8691 (4)	0.0966 (4)	−0.21505 (10)	0.0664 (8)
H7	0.8290	0.1055	−0.2491	0.080*
C8	0.9390 (4)	−0.0537 (4)	−0.19829 (10)	0.0585 (7)
H8	0.9467	−0.1464	−0.2207	0.070*
C9	0.9978 (3)	−0.0649 (3)	−0.14741 (9)	0.0458 (5)
C10	0.9890 (3)	0.0708 (3)	−0.11328 (8)	0.0398 (5)
C11	1.0441 (3)	0.1887 (3)	−0.02313 (8)	0.0411 (5)
H11	1.0725	0.2981	−0.0339	0.049*
C12	0.9943 (3)	0.1640 (3)	0.02616 (8)	0.0403 (5)
H12	0.9619	0.0540	0.0351	0.048*
C13	0.9033 (3)	0.2512 (3)	0.11423 (8)	0.0431 (5)
H13	0.8525	0.1450	0.1181	0.052*
C14	0.8963 (3)	0.3662 (3)	0.15478 (9)	0.0457 (5)
H14	0.8408	0.3368	0.1857	0.055*
C15	0.9714 (3)	0.5258 (3)	0.14991 (8)	0.0427 (5)
C16	1.0529 (3)	0.5671 (3)	0.10343 (9)	0.0453 (5)
H16	1.1035	0.6735	0.0996	0.054*
C17	1.0595 (3)	0.4525 (3)	0.06319 (9)	0.0425 (5)
H17	1.1147	0.4827	0.0323	0.051*
C18	0.9853 (3)	0.2915 (3)	0.06744 (8)	0.0385 (5)
S19	0.95810 (10)	0.66348 (9)	0.20370 (2)	0.0607 (2)
C20	1.0518 (7)	0.8544 (4)	0.17999 (13)	0.0950 (13)
H20A	1.1670	0.8321	0.1685	0.142*
H20B	1.0537	0.9377	0.2074	0.142*
H20C	0.9852	0.8967	0.1512	0.142*
C21	1.2179 (3)	−0.1305 (3)	−0.00056 (10)	0.0486 (6)
N21	1.2917 (3)	−0.1535 (4)	0.03747 (10)	0.0690 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0611 (10)	0.0435 (8)	0.0539 (9)	0.0054 (8)	0.0076 (8)	−0.0097 (7)
O2	0.0762 (13)	0.0436 (10)	0.0896 (14)	0.0212 (10)	0.0069 (12)	−0.0011 (10)
C2	0.0455 (12)	0.0389 (12)	0.0626 (14)	0.0052 (12)	0.0094 (12)	−0.0007 (11)
C3	0.0385 (10)	0.0374 (11)	0.0482 (11)	0.0002 (10)	0.0059 (10)	0.0038 (9)
C4	0.0329 (10)	0.0348 (10)	0.0437 (11)	0.0002 (10)	0.0057 (9)	0.0006 (9)
C5	0.0515 (13)	0.0486 (13)	0.0543 (13)	0.0106 (12)	0.0014 (11)	0.0042 (11)
C6	0.0647 (16)	0.0729 (18)	0.0581 (15)	0.0163 (16)	−0.0057 (14)	0.0133 (14)
C7	0.0621 (16)	0.090 (2)	0.0469 (13)	0.0039 (17)	−0.0062 (13)	0.0055 (15)
C8	0.0568 (14)	0.0689 (16)	0.0498 (13)	−0.0037 (15)	0.0009 (12)	−0.0102 (12)
C9	0.0394 (12)	0.0490 (12)	0.0491 (12)	0.0015 (11)	0.0073 (10)	−0.0033 (10)
C10	0.0365 (10)	0.0417 (11)	0.0413 (10)	0.0019 (10)	0.0059 (9)	0.0022 (9)
C11	0.0448 (11)	0.0346 (10)	0.0440 (11)	0.0017 (10)	0.0004 (9)	−0.0003 (9)
C12	0.0386 (10)	0.0358 (10)	0.0465 (11)	0.0000 (10)	−0.0010 (9)	−0.0003 (9)
C13	0.0454 (12)	0.0384 (11)	0.0455 (11)	−0.0009 (10)	−0.0009 (10)	0.0060 (10)
C14	0.0499 (13)	0.0481 (12)	0.0391 (11)	0.0021 (11)	0.0029 (10)	0.0047 (10)
C15	0.0461 (12)	0.0422 (11)	0.0397 (10)	0.0082 (11)	−0.0062 (10)	−0.0020 (9)
C16	0.0502 (12)	0.0373 (11)	0.0484 (11)	−0.0022 (11)	−0.0010 (11)	−0.0015 (9)
C17	0.0450 (11)	0.0416 (11)	0.0410 (11)	−0.0014 (11)	0.0029 (10)	−0.0003 (9)
C18	0.0365 (10)	0.0380 (10)	0.0410 (10)	0.0028 (9)	−0.0023 (9)	0.0009 (9)
S19	0.0782 (5)	0.0575 (4)	0.0464 (3)	0.0079 (4)	−0.0010 (3)	−0.0127 (3)
C20	0.162 (4)	0.0479 (15)	0.0749 (19)	−0.008 (3)	−0.003 (2)	−0.0207 (15)
C21	0.0421 (11)	0.0463 (13)	0.0575 (14)	0.0048 (11)	0.0056 (11)	0.0124 (11)
N21	0.0589 (13)	0.0794 (17)	0.0685 (14)	0.0095 (15)	−0.0045 (12)	0.0250 (14)

Geometric parameters (Å, º)

O1—C2	1.363 (3)	C11—H11	0.9300
O1—C9	1.378 (3)	C12—C18	1.459 (3)
O2—C2	1.200 (3)	C12—H12	0.9300
C2—C3	1.455 (3)	C13—C14	1.378 (3)
C3—C4	1.362 (3)	C13—C18	1.394 (3)
C3—C21	1.433 (3)	C13—H13	0.9300
C4—C10	1.451 (3)	C14—C15	1.390 (3)
C4—C11	1.458 (3)	C14—H14	0.9300
C5—C6	1.376 (4)	C15—C16	1.388 (3)
C5—C10	1.405 (3)	C15—S19	1.755 (2)
C5—H5	0.9300	C16—C17	1.370 (3)
C6—C7	1.369 (4)	C16—H16	0.9300
C6—H6	0.9300	C17—C18	1.396 (3)
C7—C8	1.370 (4)	C17—H17	0.9300
C7—H7	0.9300	S19—C20	1.777 (4)
C8—C9	1.384 (3)	C20—H20A	0.9600
C8—H8	0.9300	C20—H20B	0.9600
C9—C10	1.381 (3)	C20—H20C	0.9600
C11—C12	1.335 (3)	C21—N21	1.145 (3)
C2—O1—C9	121.92 (18)	C4—C11—H11	118.9
O2—C2—O1	118.4 (2)	C11—C12—C18	126.8 (2)
O2—C2—C3	125.3 (2)	C11—C12—H12	116.6
O1—C2—C3	116.3 (2)	C18—C12—H12	116.6
C4—C3—C21	122.2 (2)	C14—C13—C18	121.1 (2)
C4—C3—C2	123.6 (2)	C14—C13—H13	119.4
C21—C3—C2	114.1 (2)	C18—C13—H13	119.4
C3—C4—C10	117.2 (2)	C13—C14—C15	120.5 (2)
C3—C4—C11	122.39 (19)	C13—C14—H14	119.7
C10—C4—C11	120.44 (19)	C15—C14—H14	119.7
C6—C5—C10	120.3 (3)	C16—C15—C14	118.7 (2)
C6—C5—H5	119.8	C16—C15—S19	123.76 (18)
C10—C5—H5	119.8	C14—C15—S19	117.51 (17)
C7—C6—C5	120.3 (3)	C17—C16—C15	120.6 (2)
C7—C6—H6	119.9	C17—C16—H16	119.7
C5—C6—H6	119.9	C15—C16—H16	119.7
C6—C7—C8	121.0 (2)	C16—C17—C18	121.5 (2)
C6—C7—H7	119.5	C16—C17—H17	119.2
C8—C7—H7	119.5	C18—C17—H17	119.2
C7—C8—C9	118.8 (3)	C13—C18—C17	117.6 (2)
C7—C8—H8	120.6	C13—C18—C12	119.2 (2)
C9—C8—H8	120.6	C17—C18—C12	123.18 (19)
O1—C9—C10	122.0 (2)	C15—S19—C20	103.25 (13)
O1—C9—C8	115.9 (2)	S19—C20—H20A	109.5
C10—C9—C8	122.0 (2)	S19—C20—H20B	109.5
C9—C10—C5	117.6 (2)	H20A—C20—H20B	109.5
C9—C10—C4	118.8 (2)	S19—C20—H20C	109.5
C5—C10—C4	123.5 (2)	H20A—C20—H20C	109.5
C12—C11—C4	122.2 (2)	H20B—C20—H20C	109.5
C12—C11—H11	118.9	N21—C21—C3	178.5 (3)
C9—O1—C2—O2	−176.0 (2)	C6—C5—C10—C4	178.9 (2)
C9—O1—C2—C3	2.8 (3)	C3—C4—C10—C9	2.7 (3)
O2—C2—C3—C4	180.0 (2)	C11—C4—C10—C9	−178.3 (2)
O1—C2—C3—C4	1.2 (3)	C3—C4—C10—C5	−177.5 (2)
O2—C2—C3—C21	3.5 (4)	C11—C4—C10—C5	1.6 (3)
O1—C2—C3—C21	−175.2 (2)	C3—C4—C11—C12	−45.5 (3)
C21—C3—C4—C10	172.3 (2)	C10—C4—C11—C12	135.5 (2)
C2—C3—C4—C10	−3.9 (3)	C4—C11—C12—C18	177.2 (2)
C21—C3—C4—C11	−6.7 (3)	C18—C13—C14—C15	−0.1 (3)
C2—C3—C4—C11	177.1 (2)	C13—C14—C15—C16	0.2 (3)
C10—C5—C6—C7	1.0 (4)	C13—C14—C15—S19	−179.39 (18)
C5—C6—C7—C8	−0.4 (5)	C14—C15—C16—C17	−0.1 (4)
C6—C7—C8—C9	0.1 (4)	S19—C15—C16—C17	179.43 (19)
C2—O1—C9—C10	−4.0 (4)	C15—C16—C17—C18	−0.1 (4)
C2—O1—C9—C8	176.3 (2)	C14—C13—C18—C17	−0.1 (3)
C7—C8—C9—O1	179.3 (2)	C14—C13—C18—C12	178.1 (2)
C7—C8—C9—C10	−0.4 (4)	C16—C17—C18—C13	0.2 (3)
O1—C9—C10—C5	−178.8 (2)	C16—C17—C18—C12	−178.0 (2)
C8—C9—C10—C5	0.9 (4)	C11—C12—C18—C13	169.2 (2)
O1—C9—C10—C4	1.1 (3)	C11—C12—C18—C17	−12.6 (4)
C8—C9—C10—C4	−179.2 (2)	C16—C15—S19—C20	4.9 (3)
C6—C5—C10—C9	−1.2 (4)	C14—C15—S19—C20	−175.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O2^i	0.93	2.66	3.436 (3)	141
C13—H13···O2^i	0.93	2.63	3.459 (3)	149

Symmetry code: (i) x−1/2, −y−1/2, −z.