Ethyl 2-phenyl-3-(pyridin-2-yl)­acryl­ate

In the title compound, C₁₆H₁₅NO₂, the pyridine and benzene rings are nearly coplanar and form a π-conjugation system with the ethyl­carboxyl­ate susbtituent nearly perpendicular to the styrylpyridine plane. The molecular packing is stabilized by weak C—H...π interactions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.069
• wR factor = 0.157
• Data-to-parameter ratio = 12.3

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S1. Comment

As part of our studies on photoiinduced oxygenation reactions of indolizine derivatives (Tian et al., 2001), we have recently carried out such a reaction on 2-phenyl-3-(4-chlorobenzoyl)indolizine and obtained the title compound, (I), as one of the products. Here we report its crystal structure.

The bond lengths in the title structure are normal (Allen et al., 1987) and show π-conjugation in the styrylpyridine moiety. The exocyclic angles C6—C7—C8 [124.6 (3)°] and C7—C8—C9 [122.2 (3)°] deviate from the normal value of 120°. This may be due to the repulsion between atoms H6 and H9 [2.01 (4) Å]. The dihedral angle between the pyridine and benzene rings of 2.1 (1)° indicates planarity of the styrylpyridine moiety, resulting from the π-conjugation. The ethylcarboxylate susbtituent is also nearly planar, with C14 having a maximum deviation of 0.049 (3) Å from the weighted least-squares plane. The ethylcarboxylate plane is nearly perpendicular to the styrylpyridine plane, making a dihedral angle of 81.5 (1)°. In the crystal packing, symmetry-related molecules are interconnected by C—H···π interactions (Table 2) involving the pyridine and benzene rings to form a network. In Table 2, Cg1 and Cg2 denote the centroids of the pyridine and benzene rings, respectively.

S2. Experimental

The title compound was prepared by the photo-induced oxygenation reaction of 2-phenyl-3-(4-chlorobenzoyl)indolizine in ethanol with methylene blue as a sensitizer, and was isolated by column chromatography on silica gel with petroleum ether–ethyl acetate as eluents. Single crystals suitable for the X-ray diffration were obtained from slow evaporation of a petroleum ether-ethyl acetate solution.

S3. Refinement

All H atoms, apart from the methyl H atoms, were located from a difference Fourier map and refined isotropically; the C—H distances range from 0.89 (4) to 0.99 (4) Å and U_iso values range from 0.063 (8) to 0.098 (12) Ų. The methyl H atoms were fixed geometrically and treated as riding on the parent C atom, with C—H = 0.96 Å and U_iso(H) = 1.5 U_eq(C). Rotating-group refinement was used for the methyl group. As a result of the large fraction of weak data at higher angles, the 2θ maximum was limited to 52°.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Figures

Fig. 1. The structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme.

Ethyl 2-phenyl-3-pyridinylacrylate

Crystal data

C16H15NO2	Dx = 1.216 Mg m^−3
Mr = 253.29	Melting point: 351(1) K K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 4380 reflections
a = 11.0203 (7) Å	θ = 2.3–28.3°
b = 8.0642 (5) Å	µ = 0.08 mm^−1
c = 31.1269 (18) Å	T = 293 K
V = 2766.2 (3) Å^3	Block, colorless
Z = 8	0.40 × 0.24 × 0.20 mm
F(000) = 1072

Data collection

Siemens SMART CCD area-detector diffractometer	1920 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.035
Graphite monochromator	θmax = 26.0°, θmin = 2.3°
Detector resolution: 8.33 pixels mm^-1	h = −13→10
ω scans	k = −9→9
13782 measured reflections	l = −34→38
2709 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.157	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	w = 1/[σ^2(Fo^2) + (0.0455P)^2 + 1.7322P] where P = (Fo^2 + 2Fc^2)/3
2709 reflections	(Δ/σ)max < 0.001
221 parameters	Δρmax = 0.16 e Å^−3
0 restraints	Δρmin = −0.18 e Å^−3

Special details

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 30 s covered 0.3° in ω. The crystal-to-detector distance was 5 cm and the detector swing angle was −35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible.

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	0.50423 (15)	0.1361 (2)	0.61765 (6)	0.0561 (5)
O2	0.63040 (16)	−0.0746 (3)	0.63257 (6)	0.0630 (6)
N1	0.4593 (2)	0.0321 (3)	0.70753 (8)	0.0622 (7)
C1	0.4703 (3)	0.1033 (4)	0.74568 (11)	0.0700 (9)
C2	0.3859 (4)	0.0924 (5)	0.77801 (11)	0.0732 (10)
C3	0.2832 (4)	0.0002 (5)	0.77039 (12)	0.0760 (10)
C4	0.2689 (3)	−0.0730 (4)	0.73104 (11)	0.0661 (9)
C5	0.3588 (2)	−0.0564 (3)	0.70003 (9)	0.0538 (7)
C6	0.3444 (3)	−0.1382 (4)	0.65819 (10)	0.0559 (7)
C7	0.4174 (2)	−0.1260 (3)	0.62402 (9)	0.0475 (6)
C8	0.3954 (2)	−0.2080 (3)	0.58235 (9)	0.0483 (7)
C9	0.2902 (3)	−0.2992 (4)	0.57410 (11)	0.0629 (8)
C10	0.2704 (3)	−0.3719 (4)	0.53509 (11)	0.0726 (10)
C11	0.3516 (4)	−0.3570 (5)	0.50281 (13)	0.0838 (11)
C12	0.4551 (4)	−0.2677 (5)	0.50977 (13)	0.0895 (12)
C13	0.4773 (3)	−0.1950 (4)	0.54878 (11)	0.0686 (9)
C14	0.5308 (2)	−0.0213 (3)	0.62640 (8)	0.0473 (6)
C15	0.6033 (3)	0.2548 (4)	0.62130 (13)	0.0666 (9)
C16	0.5505 (3)	0.4216 (4)	0.61464 (11)	0.0747 (9)
H16A	0.6142	0.5029	0.6147	0.112*
H16B	0.4942	0.4455	0.6373	0.112*
H16C	0.5090	0.4246	0.5875	0.112*
H1	0.543 (3)	0.173 (4)	0.7490 (11)	0.093 (11)*
H2	0.399 (3)	0.143 (4)	0.8045 (11)	0.080 (10)*
H3	0.223 (3)	−0.012 (4)	0.7919 (10)	0.084 (10)*
H4	0.204 (3)	−0.135 (4)	0.7234 (11)	0.087 (11)*
H6	0.274 (3)	−0.206 (3)	0.6540 (8)	0.063 (8)*
H9	0.236 (3)	−0.303 (4)	0.5959 (9)	0.067 (9)*
H10	0.202 (3)	−0.441 (4)	0.5302 (10)	0.083 (10)*
H11	0.338 (3)	−0.414 (4)	0.4753 (10)	0.076 (10)*
H12	0.508 (3)	−0.262 (5)	0.4882 (12)	0.098 (12)*
H13	0.547 (3)	−0.136 (4)	0.5525 (9)	0.073 (9)*
H15A	0.638 (3)	0.239 (4)	0.6498 (10)	0.073 (9)*
H15B	0.657 (3)	0.228 (4)	0.5996 (10)	0.074 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0373 (9)	0.0499 (11)	0.0811 (13)	−0.0064 (8)	−0.0143 (9)	0.0188 (10)
O2	0.0351 (10)	0.0731 (14)	0.0808 (14)	0.0104 (9)	−0.0076 (9)	0.0066 (11)
N1	0.0497 (14)	0.0674 (16)	0.0695 (16)	−0.0017 (13)	0.0071 (12)	−0.0010 (13)
C1	0.061 (2)	0.072 (2)	0.077 (2)	0.0069 (17)	−0.0048 (18)	−0.0055 (18)
C2	0.083 (3)	0.074 (2)	0.062 (2)	0.024 (2)	−0.0006 (19)	0.0003 (18)
C3	0.079 (3)	0.079 (2)	0.069 (2)	0.0131 (19)	0.0274 (19)	0.0153 (19)
C4	0.055 (2)	0.067 (2)	0.075 (2)	0.0004 (16)	0.0145 (17)	0.0107 (17)
C5	0.0472 (15)	0.0500 (16)	0.0641 (18)	0.0048 (13)	0.0067 (13)	0.0112 (14)
C6	0.0431 (15)	0.0498 (16)	0.075 (2)	−0.0059 (13)	0.0069 (14)	0.0072 (14)
C7	0.0357 (12)	0.0416 (14)	0.0653 (17)	0.0047 (11)	0.0003 (12)	0.0140 (13)
C8	0.0420 (14)	0.0401 (14)	0.0627 (17)	0.0049 (11)	−0.0002 (12)	0.0107 (12)
C9	0.0546 (17)	0.067 (2)	0.067 (2)	−0.0122 (15)	0.0031 (16)	0.0116 (16)
C10	0.072 (2)	0.067 (2)	0.079 (2)	−0.0226 (18)	−0.0146 (19)	0.0109 (18)
C11	0.097 (3)	0.080 (2)	0.075 (2)	−0.019 (2)	0.002 (2)	−0.012 (2)
C12	0.085 (3)	0.105 (3)	0.079 (3)	−0.020 (2)	0.028 (2)	−0.020 (2)
C13	0.0514 (18)	0.074 (2)	0.080 (2)	−0.0161 (17)	0.0111 (16)	−0.0045 (18)
C14	0.0359 (14)	0.0523 (16)	0.0537 (15)	0.0000 (12)	−0.0037 (12)	0.0112 (12)
C15	0.0562 (19)	0.065 (2)	0.078 (2)	−0.0217 (16)	−0.0168 (19)	0.0182 (18)
C16	0.086 (2)	0.0562 (19)	0.082 (2)	−0.0155 (17)	−0.0113 (18)	0.0046 (17)

Geometric parameters (Å, º)

O1—C14	1.331 (3)	C8—C13	1.385 (4)
O1—C15	1.457 (3)	C8—C9	1.397 (4)
O2—C14	1.195 (3)	C9—C10	1.366 (5)
N1—C1	1.325 (4)	C9—H9	0.91 (3)
N1—C5	1.338 (3)	C10—C11	1.351 (5)
C1—C2	1.373 (5)	C10—H10	0.95 (3)
C1—H1	0.99 (4)	C11—C12	1.367 (5)
C2—C3	1.375 (5)	C11—H11	0.98 (3)
C2—H2	0.93 (3)	C12—C13	1.371 (5)
C3—C4	1.369 (5)	C12—H12	0.89 (4)
C3—H3	0.95 (3)	C13—H13	0.91 (3)
C4—C5	1.390 (4)	C15—C16	1.480 (5)
C4—H4	0.91 (3)	C15—H15A	0.97 (3)
C5—C6	1.469 (4)	C15—H15B	0.92 (3)
C6—C7	1.337 (4)	C16—H16A	0.96
C6—H6	0.96 (3)	C16—H16B	0.96
C7—C8	1.476 (4)	C16—H16C	0.96
C7—C14	1.510 (3)
C14—O1—C15	116.5 (2)	C8—C9—H9	115.3 (19)
C1—N1—C5	117.6 (3)	C11—C10—C9	121.1 (3)
N1—C1—C2	124.5 (4)	C11—C10—H10	117 (2)
N1—C1—H1	115 (2)	C9—C10—H10	121 (2)
C2—C1—H1	121 (2)	C10—C11—C12	118.8 (4)
C1—C2—C3	117.8 (4)	C10—C11—H11	120.2 (19)
C1—C2—H2	121 (2)	C12—C11—H11	120.9 (18)
C3—C2—H2	121 (2)	C11—C12—C13	121.0 (4)
C4—C3—C2	118.8 (3)	C11—C12—H12	117 (2)
C4—C3—H3	121 (2)	C13—C12—H12	122 (2)
C2—C3—H3	121 (2)	C12—C13—C8	121.3 (3)
C3—C4—C5	119.9 (3)	C12—C13—H13	119.2 (19)
C3—C4—H4	124 (2)	C8—C13—H13	119 (2)
C5—C4—H4	116 (2)	O2—C14—O1	125.3 (2)
N1—C5—C4	121.4 (3)	O2—C14—C7	124.6 (2)
N1—C5—C6	118.9 (2)	O1—C14—C7	110.0 (2)
C4—C5—C6	119.7 (3)	O1—C15—C16	107.0 (3)
C7—C6—C5	127.4 (3)	O1—C15—H15A	106.2 (18)
C7—C6—H6	114.9 (17)	C16—C15—H15A	113.3 (19)
C5—C6—H6	117.6 (16)	O1—C15—H15B	106 (2)
C6—C7—C8	124.6 (3)	C16—C15—H15B	111 (2)
C6—C7—C14	120.0 (3)	H15A—C15—H15B	113 (3)
C8—C7—C14	115.4 (2)	C15—C16—H16A	109.5
C13—C8—C9	116.2 (3)	C15—C16—H16B	109.5
C13—C8—C7	121.5 (3)	H16A—C16—H16B	109.5
C9—C8—C7	122.2 (3)	C15—C16—H16C	109.5
C10—C9—C8	121.5 (3)	H16A—C16—H16C	109.5
C10—C9—H9	123.2 (19)	H16B—C16—H16C	109.5
C5—N1—C1—C2	0.0 (5)	C13—C8—C9—C10	0.4 (4)
N1—C1—C2—C3	0.5 (5)	C7—C8—C9—C10	178.9 (3)
C1—C2—C3—C4	−1.3 (5)	C8—C9—C10—C11	−0.6 (5)
C2—C3—C4—C5	1.5 (5)	C9—C10—C11—C12	0.2 (6)
C1—N1—C5—C4	0.2 (4)	C10—C11—C12—C13	0.5 (6)
C1—N1—C5—C6	−179.4 (3)	C11—C12—C13—C8	−0.7 (6)
C3—C4—C5—N1	−0.9 (5)	C9—C8—C13—C12	0.2 (5)
C3—C4—C5—C6	178.6 (3)	C7—C8—C13—C12	−178.2 (3)
N1—C5—C6—C7	−5.4 (4)	C15—O1—C14—O2	−8.1 (4)
C4—C5—C6—C7	175.0 (3)	C15—O1—C14—C7	176.3 (3)
C5—C6—C7—C8	−178.0 (2)	C6—C7—C14—O2	99.3 (3)
C5—C6—C7—C14	1.4 (4)	C8—C7—C14—O2	−81.3 (3)
C6—C7—C8—C13	−177.5 (3)	C6—C7—C14—O1	−85.1 (3)
C14—C7—C8—C13	3.0 (4)	C8—C7—C14—O1	94.4 (3)
C6—C7—C8—C9	4.1 (4)	C14—O1—C15—C16	−174.3 (3)
C14—C7—C8—C9	−175.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cg1^i	0.99 (4)	2.95 (3)	3.793 (4)	144 (2)
C4—H4···Cg1^ii	0.91 (3)	2.97 (3)	3.661 (4)	135 (3)
C10—H10···Cg2^ii	0.95 (3)	2.91 (3)	3.682 (4)	140 (2)
C16—H16C···Cg2^iii	0.96	3.13	3.817 (4)	130

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x+1/2, y−1/2, z; (iii) x, y+1, z.