Ethyl (E)-2-cyano-3-(4-methyl­phen­yl)acrylate: a second monoclinic polymorph

Chen, Q.-Y.; Ke, W.-D.; Kong, L.

doi:10.1107/S1600536813009550

organic compounds

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Volume 69| Part 5| May 2013| Page o748

https://doi.org/10.1107/S1600536813009550

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Ethyl (E)-2-cyano-3-(4-methylphenyl)acrylate: a second monoclinic polymorph

Qi-Yu Chen,^a,^b Wen-Dong Ke ^a,^b and Lin Kong ^a,^b ^*

^aDeparment of Chemistry, Anhui University, Hefei 230039, People's Republic of China, and ^bKey Laboratory of Functional Inorganic Materials, Chemistry, Hefei 230039, People's Republic of China
^*Correspondence e-mail: kong_lin2009@126.com

(Received 2 December 2012; accepted 8 April 2013; online 17 April 2013)

The title compound, C₁₃H₁₃NO₂, was previously described in space group P2₁/c by He et al. [Acta Cryst. (1993), C49, 2000–2002]. The ethyl group is disordered over two sets of sites in a 0.615 (10):0.385 (10) ratio. The C—O—C—C torsion angles containing the ethyl group are −111.6 (10) and 177.9 (7)°, while in the previously reported polymorph, the torsion angle is −167.3 (2)°. The molecules pack to form a three-dimensional structure in the ABAB style along the c-axis direction in the title compound, but parallel to the a-axis direction in the reported polymorph.

Related literature

For the first polymorph, see: He et al. (1993 ). For background to intramolecular charge-transfer molecules and their use in the construction of one- to three-dimesional organic nanostructures, see: Zhang et al. (2007 ); Zhang et al. (2008 ).

Experimental

Crystal data

C₁₃H₁₃NO₂
M_r = 215.24
Monoclinic, P 2₁ /c
a = 4.7616 (4) Å
b = 17.7989 (15) Å
c = 14.2841 (12) Å
β = 93.8021 (10)°
V = 1207.93 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 K
0.20 × 0.20 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan phi and omega scans T_min = 0.984, T_max = 0.984
8359 measured reflections
2117 independent reflections
1617 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.192
S = 1.11
2117 reflections
168 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813009550/aa2081sup1.cif

Supporting information file. DOI: https://doi.org/10.1107/S1600536813009550/aa2081Isup2.mol

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813009550/aa2081Isup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813009550/aa2081Isup4.cml

checkCIF report

Comment top

The title compound is a typical D–π–A (D = donor, A = acceptor) molecule. This type of compounds can be regarded as intramolecule charge transfer (ICT) molecules (Zhang et al., 2007) and can be used to construct 1-dimesional to 3-dimesional organic nanostructures (Zhang et al., 2008). In the title compound, the benzene cycle can be used as the electron donor unit, cyano group as the electron acceptor unit, the ester group as a flexible chain to increase the solubility of the compound. Thus, the cyano group and benzene cycle are linked by a vinyl bond to form organo-soluble D–π–A molecule.

In title compound (Fig. 1), the C═C group is almost coplanar with the attached phenyl ring, the torsion angle C9—C15—C5—C4 being 2.2 (4) °. The C═C group is also coplanar with ester group. The torsion angle C15—C9—Cl1—O2 is 177.5 (2) °. Excellent coplanarity of conjugated moieties enables the title compound to be a high delocalized electron system.

Related literature top

For the first polymorph, see: He et al. (1993). For background to intramolecular charge-transfer molecules and their use in the construction of one- to three-dimesional organic nanostructures, see: Zhang et al. (2007); Zhang et al. (2008).

Experimental top

p-Toluic aldehyde (0.50 g), ethyl cyanoacetate(0.51 g), and ammonium acetate (0.32 g) were dissolved in 30 ml of ethanol and refluxed for about 4 h to give crude product as a solid. The precipitation was filtered, purified by recrystallization from acetonitrile/water (1:4) and 0.85 g of the titled compound was obtained as a white solid. Yield: 94.9%. ¹H NMR (400 MHz, d⁶-DMSO): 8.35 (s, 1H), 7.98 (d, J = 8.0 Hz, 2H), 7.41 (d, J = 8.0 Hz, 2H), 7.32 (q, J = 7.2 Hz, 2H), 2,40 (s, 3H), 1.31 (t, J = 7.2 Hz, 3H). ¹³C NMR (100 MHz) 13.97, 21.33, 62.24, 101.14, 115.78, 128.68, 129.94, 130.96, 144.39, 154.94, 161.98.

Structure description top

For the first polymorph, see: He et al. (1993). For background to intramolecular charge-transfer molecules and their use in the construction of one- to three-dimesional organic nanostructures, see: Zhang et al. (2007); Zhang et al. (2008).

Computing details top

Data collection: APEX2 (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. : The molecular structure of the title molecule with 50% probability ellipsoids.

Ethyl (E)-2-cyano-3-(4-methylphenyl)acrylate top

Crystal data top

C₁₃H₁₃NO₂	F(000) = 456
M_r = 215.24	D_x = 1.184 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3950 reflections
a = 4.7616 (4) Å	θ = 2.3–25.5°
b = 17.7989 (15) Å	µ = 0.08 mm⁻¹
c = 14.2841 (12) Å	T = 298 K
β = 93.8021 (10)°	Needle, white
V = 1207.93 (18) Å³	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2117 independent reflections
Radiation source: fine-focus sealed tube	1617 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
φ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan phi and omega scans	h = −5→5
T_min = 0.984, T_max = 0.984	k = −21→19
8359 measured reflections	l = −16→16

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)] = 0.055	H-atom parameters constrained
wR(F²) = 0.192	w = 1/[σ²(F_o²) + (0.1011P)² + 0.1786P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
2117 reflections	Δρ_max = 0.19 e Å⁻³
168 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.043 (10)

Crystal data top

C₁₃H₁₃NO₂	V = 1207.93 (18) Å³
M_r = 215.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.7616 (4) Å	µ = 0.08 mm⁻¹
b = 17.7989 (15) Å	T = 298 K
c = 14.2841 (12) Å	0.20 × 0.20 × 0.20 mm
β = 93.8021 (10)°

Data collection top

Bruker APEXII CCD diffractometer	2117 independent reflections
Absorption correction: multi-scan phi and omega scans	1617 reflections with I > 2σ(I)
T_min = 0.984, T_max = 0.984	R_int = 0.020
8359 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.192	H-atom parameters constrained
S = 1.11	Δρ_max = 0.19 e Å⁻³
2117 reflections	Δρ_min = −0.21 e Å⁻³
168 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	Occ. (<1)
C1	0.2687 (8)	−0.0915 (2)	0.4400 (2)	0.1201 (10)
H1A	0.1208	−0.1263	0.4219	0.180*
H1B	0.2004	−0.0549	0.4823	0.180*
H1C	0.4242	−0.1182	0.4705	0.180*
C2	0.3650 (6)	−0.05220 (16)	0.35330 (19)	0.0954 (8)
C3	0.2589 (7)	0.01687 (16)	0.3251 (2)	0.1062 (9)
H3	0.1250	0.0398	0.3601	0.127*
C4	0.3451 (6)	0.05290 (14)	0.24691 (19)	0.0924 (8)
H4	0.2715	0.0999	0.2307	0.111*
C5	0.5404 (5)	0.02009 (12)	0.19193 (16)	0.0740 (6)
C6	0.6416 (6)	−0.05037 (14)	0.21981 (19)	0.0953 (8)
H6	0.7713	−0.0744	0.1842	0.114*
C7	0.5541 (7)	−0.08526 (15)	0.2988 (2)	0.1009 (9)
H7	0.6256	−0.1324	0.3153	0.121*
C9	0.6075 (5)	0.11983 (12)	0.06603 (15)	0.0713 (6)
C10	0.4199 (5)	0.17670 (12)	0.09614 (16)	0.0777 (7)
C11	0.7662 (5)	0.13621 (14)	−0.01789 (17)	0.0829 (7)
C12	0.741 (3)	0.2242 (6)	−0.1547 (6)	0.109 (3)	0.385 (10)
H12A	0.5727	0.2456	−0.1863	0.131*	0.385 (10)
H12B	0.8083	0.1828	−0.1912	0.131*	0.385 (10)
C13	0.965 (3)	0.2823 (9)	−0.1321 (9)	0.136 (4)	0.385 (10)
H13A	0.8843	0.3244	−0.1017	0.204*	0.385 (10)
H13B	1.0425	0.2987	−0.1890	0.204*	0.385 (10)
H13C	1.1117	0.2608	−0.0911	0.204*	0.385 (10)
C15	0.6509 (5)	0.05304 (12)	0.10882 (16)	0.0755 (6)
H15	0.7755	0.0220	0.0796	0.091*
C12'	0.8890 (16)	0.2220 (4)	−0.1310 (5)	0.0961 (19)	0.615 (10)
H12C	1.0818	0.2271	−0.1053	0.115*	0.615 (10)
H12D	0.8819	0.1840	−0.1797	0.115*	0.615 (10)
C13'	0.780 (2)	0.2953 (3)	−0.1689 (5)	0.119 (2)	0.615 (10)
H13D	0.5833	0.2904	−0.1879	0.178*	0.615 (10)
H13E	0.8814	0.3094	−0.2220	0.178*	0.615 (10)
H13F	0.8040	0.3331	−0.1212	0.178*	0.615 (10)
N1	0.2704 (6)	0.22244 (13)	0.11968 (17)	0.1036 (8)
O1	0.9398 (5)	0.09507 (11)	−0.04727 (14)	0.1101 (7)
O2	0.6971 (4)	0.20214 (10)	−0.05566 (13)	0.1045 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.1351 (17)	0.1184 (17)	0.1087 (15)	−0.0055 (14)	0.0237 (13)	0.0261 (13)
C2	0.1080 (15)	0.0895 (14)	0.0898 (13)	−0.0069 (12)	0.0141 (12)	0.0126 (11)
C3	0.123 (2)	0.094 (2)	0.108 (2)	0.0117 (16)	0.0474 (17)	0.0159 (15)
C4	0.1092 (18)	0.0723 (15)	0.0990 (17)	0.0114 (13)	0.0320 (14)	0.0128 (13)
C5	0.0863 (14)	0.0615 (12)	0.0751 (13)	−0.0038 (10)	0.0114 (11)	0.0015 (10)
C6	0.120 (2)	0.0713 (15)	0.0974 (18)	0.0148 (13)	0.0271 (15)	0.0122 (13)
C7	0.131 (2)	0.0749 (16)	0.0985 (18)	0.0101 (14)	0.0183 (16)	0.0203 (14)
C9	0.0841 (13)	0.0612 (12)	0.0695 (12)	−0.0036 (10)	0.0120 (10)	−0.0005 (9)
C10	0.0975 (15)	0.0600 (12)	0.0769 (14)	−0.0010 (11)	0.0151 (11)	0.0059 (10)
C11	0.1033 (17)	0.0688 (14)	0.0783 (14)	0.0001 (12)	0.0191 (12)	0.0043 (11)
C12	0.134 (8)	0.096 (6)	0.099 (6)	0.016 (6)	0.017 (5)	0.014 (4)
C13	0.137 (8)	0.144 (10)	0.132 (8)	−0.025 (8)	0.044 (7)	−0.004 (7)
C15	0.0883 (14)	0.0631 (13)	0.0762 (13)	0.0012 (10)	0.0137 (11)	−0.0020 (10)
C12'	0.104 (4)	0.097 (4)	0.090 (4)	0.011 (4)	0.031 (3)	0.026 (3)
C13'	0.151 (6)	0.101 (4)	0.109 (4)	0.011 (4)	0.042 (4)	0.037 (3)
N1	0.1314 (19)	0.0732 (14)	0.1099 (17)	0.0159 (12)	0.0344 (14)	0.0056 (12)
O1	0.1454 (17)	0.0902 (13)	0.1006 (13)	0.0211 (11)	0.0524 (12)	0.0065 (10)
O2	0.1456 (16)	0.0791 (12)	0.0937 (13)	0.0125 (10)	0.0435 (11)	0.0220 (9)

Geometric parameters (Å, º) top

C1—C2	1.519 (4)	C10—N1	1.147 (3)
C1—H1A	0.9600	C11—O1	1.201 (3)
C1—H1B	0.9600	C11—O2	1.324 (3)
C1—H1C	0.9600	C12—O2	1.496 (8)
C2—C7	1.363 (4)	C12—C13	1.507 (6)
C2—C3	1.379 (4)	C12—H12A	0.9700
C3—C4	1.374 (4)	C12—H12B	0.9700
C3—H3	0.9300	C13—H13A	0.9600
C4—C5	1.385 (3)	C13—H13B	0.9600
C4—H4	0.9300	C13—H13C	0.9600
C5—C6	1.392 (3)	C15—H15	0.9300
C5—C15	1.453 (3)	C12'—C13'	1.492 (5)
C6—C7	1.376 (4)	C12'—O2	1.500 (5)
C6—H6	0.9300	C12'—H12C	0.9700
C7—H7	0.9300	C12'—H12D	0.9700
C9—C15	1.346 (3)	C13'—H13D	0.9600
C9—C10	1.435 (3)	C13'—H13E	0.9600
C9—C11	1.488 (3)	C13'—H13F	0.9600

C2—C1—H1A	109.5	N1—C10—C9	179.5 (3)
C2—C1—H1B	109.5	O1—C11—O2	123.8 (2)
H1A—C1—H1B	109.5	O1—C11—C9	124.1 (2)
C2—C1—H1C	109.5	O2—C11—C9	112.1 (2)
H1A—C1—H1C	109.5	O2—C12—C13	96.8 (8)
H1B—C1—H1C	109.5	O2—C12—H12A	112.4
C7—C2—C3	117.4 (2)	C13—C12—H12A	112.4
C7—C2—C1	120.9 (3)	O2—C12—H12B	112.4
C3—C2—C1	121.6 (3)	C13—C12—H12B	112.4
C4—C3—C2	122.0 (3)	H12A—C12—H12B	110.0
C4—C3—H3	119.0	C9—C15—C5	132.4 (2)
C2—C3—H3	119.0	C9—C15—H15	113.8
C3—C4—C5	120.8 (2)	C5—C15—H15	113.8
C3—C4—H4	119.6	C13'—C12'—O2	104.6 (4)
C5—C4—H4	119.6	C13'—C12'—H12C	110.8
C4—C5—C6	116.7 (2)	O2—C12'—H12C	110.8
C4—C5—C15	125.9 (2)	C13'—C12'—H12D	110.8
C6—C5—C15	117.4 (2)	O2—C12'—H12D	110.8
C7—C6—C5	121.5 (2)	H12C—C12'—H12D	108.9
C7—C6—H6	119.2	C12'—C13'—H13D	109.5
C5—C6—H6	119.2	C12'—C13'—H13E	109.5
C2—C7—C6	121.4 (3)	H13D—C13'—H13E	109.5
C2—C7—H7	119.3	C12'—C13'—H13F	109.5
C6—C7—H7	119.3	H13D—C13'—H13F	109.5
C15—C9—C10	124.5 (2)	H13E—C13'—H13F	109.5
C15—C9—C11	117.9 (2)	C11—O2—C12	124.9 (6)
C10—C9—C11	117.57 (19)	C11—O2—C12'	110.8 (3)

C7—C2—C3—C4	−2.1 (5)	C10—C9—C11—O2	−2.9 (3)
C1—C2—C3—C4	179.9 (3)	C10—C9—C15—C5	−1.5 (4)
C2—C3—C4—C5	1.2 (5)	C11—C9—C15—C5	178.0 (2)
C3—C4—C5—C6	0.2 (4)	C4—C5—C15—C9	2.2 (4)
C3—C4—C5—C15	−178.9 (3)	C6—C5—C15—C9	−177.0 (2)
C4—C5—C6—C7	−0.7 (4)	O1—C11—O2—C12	22.4 (7)
C15—C5—C6—C7	178.5 (2)	C9—C11—O2—C12	−158.7 (6)
C3—C2—C7—C6	1.6 (5)	O1—C11—O2—C12'	−7.2 (5)
C1—C2—C7—C6	179.6 (3)	C9—C11—O2—C12'	171.8 (4)
C5—C6—C7—C2	−0.2 (5)	C13—C12—O2—C11	−111.6 (10)
C15—C9—C11—O1	−3.5 (4)	C13—C12—O2—C12'	−42.2 (9)
C10—C9—C11—O1	176.0 (2)	C13'—C12'—O2—C11	177.9 (7)
C15—C9—C11—O2	177.5 (2)	C13'—C12'—O2—C12	53.2 (10)

Experimental details

Crystal data
Chemical formula	C₁₃H₁₃NO₂
M_r	215.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	4.7616 (4), 17.7989 (15), 14.2841 (12)
β (°)	93.8021 (10)
V (Å³)	1207.93 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan phi and omega scans
T_min, T_max	0.984, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	8359, 2117, 1617
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.192, 1.11
No. of reflections	2117
No. of parameters	168
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.21

Computer programs: APEX2 (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

We gratefully acknowledge the NSFC(21101001), and the 211 Project of Anhui University for supporting this study.

References

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